Sample records for initial hydrate saturation
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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.
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Quantifying Hydrate Formation in Gas-rich Environments Using the Method of Characteristics
NASA Astrophysics Data System (ADS)
You, K.; Flemings, P. B.; DiCarlo, D. A.
2015-12-01
Methane hydrates hold a vast amount of methane globally, and have huge energy potential. Methane hydrates in gas-rich environments are the most promising production targets. We develop a one-dimensional analytical solution based on the method of characteristics to explore hydrate formation in such environments (Figure 1). Our solution shows that hydrate saturation is constant with time and space in a homogeneous system. Hydrate saturation is controlled by the initial thermodynamic condition of the system, and changed by the gas fractional flow. Hydrate saturation increases with the initial distance from the hydrate phase boundary. Different gas fractional flows behind the hydrate solidification front lead to different gas saturations at the hydrate solidification front. The higher the gas saturation at the front, the less the volume available to be filled by hydrate, and hence the lower the hydrate saturation. The gas fractional flow depends on the relative permeability curves, and the forces that drive the flow. Viscous forces (the drive for flow induced from liquid pressure gradient) dominate the flow, and hydrate saturation is independent on the gas supply rates and the flow directions at high gas supply rates. Hydrate saturation can be estimated as one minus the ratio of the initial to equilibrium salinity. Gravity forces (the drive for flow induced from the gravity) dominate the flow, and hydrate saturation depends on the flow rates and the flow directions at low gas supply rates. Hydrate saturation is highest for upward flow, and lowest for downward flow. Hydrate saturation decreases with the flow rate for upward flow, and increases with the flow rate for downward flow. This analytical solution illuminates how hydrate is formed by gas (methane, CO2, ethane, propane) flowing into brine-saturated sediments at both the laboratory and geological scales (Figure 1). It provides an approach to generalize the understanding of hydrate solidification in gas-rich environments, although complicated numerical models have been developed previously. Examples of gas expulsion into hydrate stability zones and the associated hydrate formation in both laboratory and geological scales, and CO2 sequestration into CO2-hydrates near the seafloor and under the permafrost will be presented.
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Methane hydrate formation in partially water-saturated Ottawa sand
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.
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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.
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NASA Astrophysics Data System (ADS)
Meyer, D.
2016-12-01
We generate methane hydrate in a coarse-grained, brine-saturated, vertically-oriented sample through gas injection. From 0 - 80 hours, we estimate a hydrate saturation of 0.56 behind the formation front, using mass balance, indicating that hydrate formation is limited by locally-elevated salinity creating three-phase equilibrium conditions. After 80 hours, the hydrate phase saturation drops to 0.50 and the magnitude of the pressure drop-rebound cycles increases, suggesting temporary reductions in permeability and the development of heterogeneous distributions of free gas in the sample. The sample consists of an industrial, fine sand mixed with a 0.5 wt% fraction of natural, smectitic clay from the Eugene Island region in the Gulf of Mexico (5.08cm diameter, 11.79cm length). The sample is initially saturated with a 7 wt% sodium chloride brine, pressurized to 12.24 MPa, and cooled to 1 degree Celsius, to bring the sample into the hydrate stability zone. Syringe pumps filled with methane gas and brine are connected to the top and bottom of the sample, respectively, to control fluid flow. We withdraw from the base of the sample at a rate of 0.0005 mL/min and inject methane to maintain a constant pressure, initiating hydrate formation. We analyze this experiment, as well as a gas flood experiment executed under the same conditions, using computed-tomography scans and an analytical solution to investigate the formation behavior and thermodynamic state of hydrate in gas-rich, coarse-grained reservoirs.
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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.
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Waite, William F.; Osegovic, J.P.; Winters, William J.; Max, M.D.; Mason, David H.
2008-01-01
An isobaric flow loop added to the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) is being investigated as a means of rapidly forming methane hydrate in watersaturated sand from methane dissolved in water. Water circulates through a relatively warm source chamber, dissolving granular methane hydrate that was pre-made from seed ice, then enters a colder hydrate growth chamber where hydrate can precipitate in a water-saturated sand pack. Hydrate dissolution in the source chamber imparts a known methane concentration to the circulating water, and hydrate particles from the source chamber entrained in the circulating water can become nucleation sites to hasten the onset of hydrate formation in the growth chamber. Initial results suggest hydrate grows rapidly near the growth chamber inlet. Techniques for establishing homogeneous hydrate formation throughout the sand pack are being developed.
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NASA Astrophysics Data System (ADS)
Anderson, B. J.; Gaddipati, M.; Nyayapathi, L.
2008-12-01
This paper presents a parametric study on production rates of natural gas from gas hydrates by the method of depressurization, using CMG STARS. Seven factors/parameters were considered as perturbations from a base-case hydrate reservoir description based on Problem 7 of the International Methane Hydrate Reservoir Simulator Code Comparison Study led by the Department of Energy and the USGS. This reservoir is modeled after the inferred properties of the hydrate deposit at the Prudhoe Bay L-106 site. The included sensitivity variables were hydrate saturation, pressure (depth), temperature, bottom-hole pressure of the production well, free water saturation, intrinsic rock permeability, and porosity. A two-level (L=2) Plackett-Burman experimental design was used to study the relative effects of these factors. The measured variable was the discounted cumulative gas production. The discount rate chosen was 15%, resulting in the gas contribution to the net present value of a reservoir. Eight different designs were developed for conducting sensitivity analysis and the effects of the parameters on the real and discounted production rates will be discussed. The breakeven price in various cases and the dependence of the breakeven price on the production parameters is given in the paper. As expected, initial reservoir temperature has the strongest positive effect on the productivity of a hydrate deposit and the bottom-hole pressure in the production well has the strongest negative dependence. Also resulting in a positive correlation is the intrinsic permeability and the initial free water of the formation. Negative effects were found for initial hydrate saturation (at saturations greater than 50% of the pore space) and the reservoir porosity. These negative effects are related to the available sensible heat of the reservoir, with decreasing productivity due to decreasing available sensible heat. Finally, we conclude that for the base case reservoir, the break-even price (BEP) for natural gas is approximately 7/mcf and for warmer and deeper reservoirs the BEP can approach 5.33/mcf.
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Quantitative degassing of gas hydrate-bearing pressure cores from Green Canyon 955, Gulf of Mexico
NASA Astrophysics Data System (ADS)
Phillips, S. C.; Holland, M. E.; Flemings, P. B.; Schultheiss, P. J.; Waite, W. F.; Petrou, E. G.; Jang, J.; Polito, P. J.; O'Connell, J.; Dong, T.; Meazell, K.
2017-12-01
We present results from 20 quantitative degassing experiments of pressure-core sections collected during Expedition UT-GOM2-1 from Green Canyon 955 in the northern Gulf of Mexico. These experiments highlight an average pore-space methane hydrate saturation, Sh, of 59% (min: 12%; max 87%) in sediments between 413 and 440 mbsf in 2032 m water depth. There is a strong lithofacies control of hydrate saturation within the reservoir, with a high saturation sandy silt facies (Sh of 65 to 87%) interbedded with a low saturation clayey silt facies (Sh of 12 to 30%). Bedding occurs on the scale of tens of centimeters. Outside of the main hydrate reservoir, methane hydrate occurs in low saturations (Sh of 0.8 to 3%). Hydrate saturations exhibit a strong correlation (R2=0.89) with the average P-wave velocity measured through the degassed sections. These preliminary hydrate saturations were calculated assuming a porosity of 40% with core filling the full internal diameter of the core liner. Gas recovered during these experiments is composed of almost entirely methane, with an average of 94 ppm ethane and detectable, but not quantifiable, propane. Degassed pressure cores were depressurized through a manifold by the stepwise release of fluid, and the volumes of produced gas and water were monitored. The core's hydrostatic pressure was measured and recorded continuously at the manifold. Pressure and temperature were also measured by data storage tags within the sample chambers. Two slow, multi-day degassing experiments were performed to estimate the in situ salinity within core sections. Based on temperature and pressure observations at the point of the initial pressure rebound due to hydrate dissociation, we estimate the salinity within these samples to be between 33 and 42 g kg-1.
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Volume change associated with formation and dissociation of hydrate in sediment
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.
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Hydrate morphology: Physical properties of sands with patchy hydrate saturation
Dai, S.; Santamarina, J.C.; Waite, William F.; Kneafsey, T.J.
2012-01-01
The physical properties of gas hydrate-bearing sediments depend on the volume fraction and spatial distribution of the hydrate phase. The host sediment grain size and the state of effective stress determine the hydrate morphology in sediments; this information can be used to significantly constrain estimates of the physical properties of hydrate-bearing sediments, including the coarse-grained sands subjected to high effective stress that are of interest as potential energy resources. Reported data and physical analyses suggest hydrate-bearing sands contain a heterogeneous, patchy hydrate distribution, whereby zones with 100% pore-space hydrate saturation are embedded in hydrate-free sand. Accounting for patchy rather than homogeneous hydrate distribution yields more tightly constrained estimates of physical properties in hydrate-bearing sands and captures observed physical-property dependencies on hydrate saturation. For example, numerical modeling results of sands with patchy saturation agree with experimental observation, showing a transition in stiffness starting near the series bound at low hydrate saturations but moving toward the parallel bound at high hydrate saturations. The hydrate-patch size itself impacts the physical properties of hydrate-bearing sediments; for example, at constant hydrate saturation, we find that conductivity (electrical, hydraulic and thermal) increases as the number of hydrate-saturated patches increases. This increase reflects the larger number of conductive flow paths that exist in specimens with many small hydrate-saturated patches in comparison to specimens in which a few large hydrate saturated patches can block flow over a significant cross-section of the specimen.
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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.
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NASA Astrophysics Data System (ADS)
Oryan, B.; Malinverno, A.; Goldberg, D.; Fortin, W.
2017-12-01
Well GC955-H was drilled in the Green Canyon region under the Gulf of Mexico Gas Hydrates Joint Industry Project in 2009. Logging-while-drilling resistivity logs obtained at the well indicate that the saturation of gas hydrate varies between high and low values in an alternating fashion. This trend is observed from 180 to 360mbsf, depths that correspond to the Late Pleistocene. Similar gas hydrate saturation patterns have been observed in other Gulf of Mexico locations (Walker Ridge sites WR313-G and 313-H) in Late Pleistocene sediments. Our hypothesis is that these variations in saturation can be explained by sea level changes through time during glacial-interglacial cycles. A higher amount of organic matter is deposited and buried in the sediment column during glacial intervals when sea level is low. Microbes in the sediment column degrade organic matter and produce methane gas as a byproduct. Higher availability of organic matter in the sediment column can increase the concentration of methane in the sediment pore water and in turn lead to the formation of gas hydrate. We use a time-dependent numerical model of the formation of gas hydrate to test this hypothesis. The model predicts the volume and distribution of gas hydrates using mass balance equations. Model inputs include in situ porosity determined from bulk density logs; local thermal gradient estimated from the depth of the bottom of the gas hydrate stability zone in proximity to the well; and sedimentation rate determined using the biostratigraphy of an industry well in the vicinity of GC955-H. Initial results show a good match between gas hydrate saturation predicted by the model and resistivity logs obtained in the well. We anticipate that this correlation will establish whether a causal link exists between the saturation of gas hydrate in this reservoir and glacioeustatic sea level changes in the Late Pleistocene.
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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.
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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.
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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.
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Three types of gas hydrate reservoirs in the Gulf of Mexico identified in LWD data
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.
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Effects of core retrieval, handling, and preservation on hydrate-bearing samples
NASA Astrophysics Data System (ADS)
Kneafsey, T. J.; Lu, H.; Winters, W. J.; Hunter, R. B.
2009-12-01
Recovery, preservation, storage, and transport of samples containing natural gas hydrate cause changes in the stress conditions, temperature, pressure, and hydrate saturation of samples. Sample handling at the ground surface and sample preservation, either by freezing in liquid nitrogen (LN) or repressurization using methane, provides additional time and driving forces for sample alteration. The extent to which these disturbances alter the properties of the hydrate bearing sediments (HBS) depend on specific sample handling techniques, as well as on the sample itself. HBS recovered during India’s National Gas Hydrate Program (NGHP) Expedition 01 and the 2007 BP Exploration Alaska - Department of Energy - U.S. Geological Survey (BP-DOE-USGS) Mount Elbert (ME) gas hydrate well on the Alaskan North Slope provide comparisons of sample alterations induced by multiple handling techniques. HBS samples from the NGHP and the ME projects were examined using x-ray computed tomography. Mount Elbert sand samples initially preserved in LN have non-uniform short “crack-like” low-density zones in the center that probably do not extend to the outside perimeter. Samples initially preserved by repressurization show fewer “crack-like” features and higher densities. Two samples were analyzed in detail by Lu and coworkers showing reduced hydrate saturations approaching the outer surface, while substantial hydrate remained in the central region. Non-pressure cored NGHP samples show relatively large altered regions approaching the core surface, while pressure-cored-liquid-nitrogen preserved samples have much less alteration.
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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.
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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.
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NASA Astrophysics Data System (ADS)
Liu, Zhichao; Dai, Sheng; Ning, Fulong; Peng, Li; Wei, Houzhen; Wei, Changfu
2018-01-01
Safe and economic methane gas production, as well as the replacement of methane while sequestering carbon in natural hydrate deposits, requires enhanced geomechanical understanding of the strength and volume responses of hydrate-bearing sediments during shear. This study employs a custom-made apparatus to investigate the mechanical and volumetric behaviors of carbon dioxide hydrate-bearing sediments subjected to direct shear. The results show that both peak and residual strengths increase with increased hydrate saturation and vertical stress. Hydrate contributes mainly the cohesion and dilatancy constraint to the peak strength of hydrate-bearing sediments. The postpeak strength reduction is more evident and brittle in specimens with higher hydrate saturation and under lower stress. Significant strength reduction after shear failure is expected in silty sediments with high hydrate saturation
S h ≥ 0.65. Hydrate contribution to the residual strength is mainly by increasing cohesion at low hydrate saturation and friction at high hydrate saturation. Stress state and hydrate saturation are dominating both the stiffness and the strength of hydrate-bearing sediments; thus, a wave velocity-based peak strength prediction model is proposed and validated, which allows for precise estimation of the shear strength of hydrate-bearing sediments through acoustic logging data. This method is advantageous to geomechanical simulators, particularly when the experimental strength data of natural samples are not available. -
NASA Astrophysics Data System (ADS)
Winters, W. J.; Waite, W. F.; Mason, D. H.; Lorenson, T. L.; Paull, C. K.; Novosel, I.; Boldina, O. M.; Dallimore, S. R.; Collett, T. S.; Page 127 Shipboard Sc. Party
2003-04-01
The U.S. Geological Survey (USGS) has been involved in oceanographic and Arctic field programs and laboratory studies to better understand the relationship between natural gas hydrate and physical properties of surrounding sediment. Recently, the Institut Polaire Francais, Paul-Emile Victor (IPEV) and the USGS jointly conducted a cruise aboard the Marion Dufresne to collect giant piston cores to determine the distribution of gas hydrate in the northern Gulf of Mexico. Hydrates recovered during the cruise did not appear to be lithologically controlled (unlike Canadian Arctic cores) and were either disseminated or were massive layers. Sediment water content typically decreases rapidly to a subbottom depth of about 8 to 9 m, but then decreases at a lower rate. At-sea help was provided by the IMAGES (International Marine Past Global Changes Study) and PAGE (Paleoceanography of the Atlantic and Geochemistry) programs, and funding was provided by the U.S. Dept. of Energy. We have used the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) to analyze sediment containing natural gas hydrate and to examine hydrate formed within (a) initially water-saturated and (b) partly-water saturated sieved Ottawa sand specimens at a pore pressure of 12 MPa and 250 kPa confining stress. Hydrate is formed when methane gas is slowly percolated into a 70-mm diameter by 140-mm long cylindrical specimen and subsequently the temperature is lowered to about 6 degrees C. We have found that acoustic velocity, shear strength, and permeability of samples containing different initial water contents are significantly affected by (a) the amount of hydrate present, (b) its distribution, (c) its position within pores, and (d) concentration at key locations. Acoustic P-wave velocities can increase from 1.7 km/s to 4.0 km/s using different hydrate and synthetic sample formation techniques. Although acoustic properties are significantly affected by hydrate at grain boundaries, the mere presence of hydrate in pores (but not necessarily at grain contacts) causes strength to significantly increase because dilation during undrained shear results in greater negative pore pressures. Recently determined strengths of three Ottawa sand samples are exponentially related to the degree of water saturation, bulk density, and hydrate content.
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Anisotropic Velocities of Gas Hydrate-Bearing Sediments in Fractured Reservoirs
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.
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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.
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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.
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Xiao, Kun; Zou, Changchun; Xiang, Biao; Liu, Jieqiong
2013-01-01
Gas hydrate model and free gas model are established, and two-phase theory (TPT) for numerical simulation of elastic wave velocity is adopted to investigate the unconsolidated deep-water sedimentary strata in Shenhu area, South China Sea. The relationships between compression wave (P wave) velocity and gas hydrate saturation, free gas saturation, and sediment porosity at site SH2 are studied, respectively, and gas hydrate saturation of research area is estimated by gas hydrate model. In depth of 50 to 245 m below seafloor (mbsf), as sediment porosity decreases, P wave velocity increases gradually; as gas hydrate saturation increases, P wave velocity increases gradually; as free gas saturation increases, P wave velocity decreases. This rule is almost consistent with the previous research result. In depth of 195 to 220 mbsf, the actual measurement of P wave velocity increases significantly relative to the P wave velocity of saturated water modeling, and this layer is determined to be rich in gas hydrate. The average value of gas hydrate saturation estimated from the TPT model is 23.2%, and the maximum saturation is 31.5%, which is basically in accordance with simplified three-phase equation (STPE), effective medium theory (EMT), resistivity log (Rt), and chloride anomaly method. PMID:23935407
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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.
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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.
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Estimating pore-space gas hydrate saturations from well log acoustic data
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.
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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
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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.
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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.
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NASA Astrophysics Data System (ADS)
McConnell, D. R.; Boswell, R. M.; Collett, T. S.; Frye, M.; Shedd, W.; Mrozewski, S.; Guerin, G.; Cook, A.; Shelander, D.; Dai, J.; Dufrene, R.; Godfriaux, P. D.; Roy, R.; Jones, E.
2009-12-01
The Gulf of Mexico gas hydrates Joint Industry Project (the JIP), a cooperative research program between the US Department of Energy and an international industrial consortium under the leadership of Chevron, conducted its “Leg II” logging-while-drilling operations in April and May of 2009. GC 955 was one of three sites drilled during Leg II. Three holes were drilled at the GC 955 site. High-saturations of gas hydrate in sands were logged at two of the three holes. The gas hydrate targets at the GC 955 site are just basinward of the Sigsbee Escarpment and outboard of the Green Canyon embayment in a Late Pleistocene Mississippi Fan channel levee sequence (0.5Ma). At the GC 955 site, the sand prone channel levee sediments are uplifted by a salt diapir, faulting the channel levee facies as well as focusing hydrocarbon charge to them. The top of the channel is approximately 1000 ft below seafloor and the sand-prone interval is in excess of 700 ft thick. The site was prospective for gas hydrate primarily due to the observation that seismic indicators of gas charge terminated anomalously within the inferred sand interval along a horizon consistent with the base of gas hydrate stability. Seismic amplitude analysis, as well as rock-physics based inversions of the seismic data, were used to refine the potential high-saturation targets. The gas hydrate targets clustered within a four-way closure caused by salt uplift. Other targets, faulted, with evidence of fluid migration, were identified, on the periphery of the closure. Three holes, locations I, H, and Q, were drilled at site GC955. The data acquired consist of a comprehensive suite of high resolution LWD logs including gamma ray, density, porosity, sonic, and resistivity tools. No physical samples were taken in the field. At the I location, only four feet of pore fill gas hydrate was detected within the sandy reservoir facies. At the H location, gas hydrate in clays and thin sands was found above the target zone and 101 ft of high-saturation gas hydrate was found at the primary target. At the Q location, at least 53 ft of high-saturation gas hydrate was found at the primary target before drilling was aborted. The discovery of thick, highly saturated gas hydrate sands at the GC955 site validates that gas hydrate can be found in reservoir quality sands through the integration of geologic and geophysical data. The LWD acquired data provided unprecedented information on the nature of the sediments and the occurrence of gas hydrate in the Gulf of Mexico.
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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.
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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.
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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.
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Lee, M.W.; Collett, T.S.
2009-01-01
During the Indian National Gas Hydrate Program Expedition 01 (NGHP-Ol), one of the richest marine gas hydrate accumulations was discovered at Site NGHP-01-10 in the Krishna-Godavari Basin. The occurrence of concentrated gas hydrate at this site is primarily controlled by the presence of fractures. Assuming the resistivity of gas hydratebearing sediments is isotropic, th?? conventional Archie analysis using the logging while drilling resistivity log yields gas hydrate saturations greater than 50% (as high as ???80%) of the pore space for the depth interval between ???25 and ???160 m below seafloor. On the other hand, gas hydrate saturations estimated from pressure cores from nearby wells were less than ???26% of the pore space. Although intrasite variability may contribute to the difference, the primary cause of the saturation difference is attributed to the anisotropic nature of the reservoir due to gas hydrate in high-angle fractures. Archie's law can be used to estimate gas hydrate saturations in anisotropic reservoir, with additional information such as elastic velocities to constrain Archie cementation parameters m and the saturation exponent n. Theory indicates that m and n depend on the direction of the measurement relative to fracture orientation, as well as depending on gas hydrate saturation. By using higher values of m and n in the resistivity analysis for fractured reservoirs, the difference between saturation estimates is significantly reduced, although a sizable difference remains. To better understand the nature of fractured reservoirs, wireline P and S wave velocities were also incorporated into the analysis.
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Lee, Myung W.
2012-01-01
Through the use of three-dimensional seismic amplitude mapping, several gas hydrate prospects were identified in the Alaminos Canyon area of the Gulf of Mexico. Two of the prospects were drilled as part of the Gulf of Mexico Gas Hydrate Joint Industry Program Leg II in May 2009, and a suite of logging-while-drilling logs was acquired at each well site. Logging-while-drilling logs at the Alaminos Canyon 21–A site indicate that resistivities of approximately 2 ohm-meter and P-wave velocities of approximately 1.9 kilometers per second were measured in a possible gas-hydrate-bearing target sand interval between 540 and 632 feet below the sea floor. These values are slightly elevated relative to those measured in the hydrate-free sediment surrounding the sands. The initial well log analysis is inconclusive in determining the presence of gas hydrate in the logged sand interval, mainly because large washouts in the target interval degraded well log measurements. To assess gas-hydrate saturations, a method of compensating for the effect of washouts on the resistivity and acoustic velocities is required. To meet this need, a method is presented that models the washed-out portion of the borehole as a vertical layer filled with seawater (drilling fluid). Owing to the anisotropic nature of this geometry, the apparent anisotropic resistivities and velocities caused by the vertical layer are used to correct measured log values. By incorporating the conventional marine seismic data into the well log analysis of the washout-corrected well logs, the gas-hydrate saturation at well site AC21–A was estimated to be in the range of 13 percent. Because gas hydrates in the vertical fractures were observed, anisotropic rock physics models were also applied to estimate gas-hydrate saturations.
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Lee, Myung Woong; Collett, Timothy S.
2013-01-01
Through the use of 2-D and 3-D seismic data, several gas hydrate prospects were identified in the Ulleung Basin, East Sea of Korea and thirteen drill sites were established and logging-while-drilling (LWD) data were acquired from each site in 2010. Sites UBGH2–6 and UBGH2–10 were selected to test a series of high amplitude seismic reflections, possibly from sand reservoirs. LWD logs from the UBGH2–6 well indicate that there are three significant sand reservoirs with varying thickness. Two upper sand reservoirs are water saturated and the lower thinly bedded sand reservoir contains gas hydrate with an average saturation of 13%, as estimated from the P-wave velocity. The well logs at the UBGH2–6 well clearly demonstrated the effect of scale-dependency on gas hydrate saturation estimates. Gas hydrate saturations estimated from the high resolution LWD acquired ring resistivity (vertical resolution of about 5–8 cm) reaches about 90% with an average saturation of 28%, whereas gas hydrate saturations estimated from the low resolution A40L resistivity (vertical resolution of about 120 cm) reaches about 25% with an average saturation of 11%. However, in the UBGH2–10 well, gas hydrate occupies a 5-m thick sand reservoir near 135 mbsf with a maximum saturation of about 60%. In the UBGH2–10 well, the average and a maximum saturation estimated from various well logging tools are comparable, because the bed thickness is larger than the vertical resolution of the various logging tools. High resolution wireline log data further document the role of scale-dependency on gas hydrate calculations.
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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.
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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.
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Compressive strength and hydration processes of concrete with recycled aggregates
DOE Office of Scientific and Technical Information (OSTI.GOV)
Koenders, Eduardus A.B., E-mail: e.a.b.koenders@coc.ufrj.br; Microlab, Delft University of Technology; Pepe, Marco, E-mail: mapepe@unisa.it
2014-02-15
This paper deals with the correlation between the time evolution of the degree of hydration and the compressive strength of Recycled Aggregate Concrete (RAC) for different water to cement ratios and initial moisture conditions of the Recycled Concrete Aggregates (RCAs). Particularly, the influence of such moisture conditions is investigated by monitoring the hydration process and determining the compressive strength development of fully dry or fully saturated recycled aggregates in four RAC mixtures. Hydration processes are monitored via temperature measurements in hardening concrete samples and the time evolution of the degree of hydration is determined through a 1D hydration and heatmore » flow model. The effect of the initial moisture condition of RCAs employed in the considered concrete mixtures clearly emerges from this study. In fact, a novel conceptual method is proposed to predict the compressive strength of RAC-systems, from the initial mixture parameters and the hardening conditions. -- Highlights: •The concrete industry is more and more concerned with sustainability issues. •The use of recycled aggregates is a promising solution to enhance sustainability. •Recycled aggregates affect both hydration processes and compressive strength. •A fundamental approach is proposed to unveil the influence of recycled aggregates. •Some experimental comparisons are presented to validate the proposed approach.« less
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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.
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Lee, J.Y.; Francisca, F.M.; Santamarina, J.C.; Ruppel, C.
2010-01-01
The small-strain mechanical properties (e.g., seismic velocities) of hydrate-bearing sediments measured under laboratory conditions provide reference values for calibration of logging and seismic exploration results acquired in hydrate-bearing formations. Instrumented cells were designed for measuring the compressional (P) and shear (S) velocities of sand, silts, and clay with and without hydrate and subject to vertical effective stresses of 0.01 to 2 MPa. Tetrahydrofuran (THF), which is fully miscible in water, was used as the hydrate former to permit close control over the hydrate saturation Shyd and to produce hydrate from dissolved phase, as methane hydrate forms in most natural marine settings. The results demonstrate that laboratory hydrate formation technique controls the pattern of P and S velocity changes with increasing Shyd and that the small-strain properties of hydrate-bearing sediments are governed by effective stress, δ'v and sediment specific surface. The S velocity increases with hydrate saturation owing to an increase in skeletal shear stiffness, particularly when hydrate saturation exceeds Shyd≈ 0.4. At very high hydrate saturations, the small strain shear stiffness is determined by the presence of hydrates and becomes insensitive to changes in effective stress. The P velocity increases with hydrate saturation due to the increases in both the shear modulus of the skeleton and the bulk modulus of pore-filling phases during fluid-to-hydrate conversion. Small-strain Poisson's ratio varies from 0.5 in soft sediments lacking hydrates to 0.25 in stiff sediments (i.e., subject to high vertical effective stress or having high Shyd). At Shyd ≥ 0.5, hydrate hinders expansion and the loss of sediment stiffness during reduction of vertical effective stress, meaning that hydrate-rich natural sediments obtained through pressure coring should retain their in situ fabric for some time after core retrieval if the cores are maintained within the hydrate stability field.
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Collett, T.S.; Wendlandt, R.F.
2000-01-01
The analyses of downhole log data from Ocean Drilling Program (ODP) boreholes on the Blake Ridge at Sites 994, 995, and 997 indicate that the Schlumberger geochemical logging tool (GLT) may yield useful gas hydrate reservoir data. In neutron spectroscopy downhole logging, each element has a characteristic gamma ray that is emitted from a given neutron-element interaction. Specific elements can be identified by their characteristic gamma-ray signature, with the intensity of emission related to the atomic elemental concentration. By combining elemental yields from neutron spectroscopy logs, reservoir parameters including porosities, lithologies, formation fluid salinities, and hydrocarbon saturations (including gas hydrate) can be calculated. Carbon and oxygen elemental data from the GLT was used to determine gas hydrate saturations at all three sites (Sites 994, 995, and 997) drilled on the Blake Ridge during Leg 164. Detailed analyses of the carbon and oxygen content of various sediments and formation fluids were used to construct specialized carbon/oxygen ratio (COR) fan charts for a series of hypothetical gas hydrate accumulations. For more complex geologic systems, a modified version of the standard three-component COR hydrocarbon saturation equation was developed and used to calculate gas hydrate saturations on the Blake Ridge. The COR-calculated gas hydrate saturations (ranging from about 2% to 14% bulk volume gas hydrate) from the Blake Ridge compare favorably to the gas hydrate saturations derived from electrical resistivity log measurements.
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NASA Astrophysics Data System (ADS)
Mundhra, A.; Sain, K.; Shankar, U.
2012-12-01
The Indian National Gas Hydrate Program Expedition (NGHP) 01 discovered gas hydrate in unconsolidated sediments at several drilling sites along the continental margins of Krishna-Godavari Basin, India. Presence of gas hydrate reduces the attenuation of travelling seismic waves which can be measured by estimation of seismic quality factor (Dasgupta and Clark, 1998). Here, we use log spectral ratio method (Sain et al, 2009) to compute quality factor at three locations, among which two have strong and one has no bottom simulating reflector (BSR), along seismic cross-line near one of the drilling site. Interval quality factor for three submarine sedimentary layers bounded by seafloor, BSR, one reflector above and another reflector below the BSR has been measured. To compute quality factor, unprocessed pre-stack seismic data has been used to avoid any influence of processing sequence. We have estimated that interval quality factor lies within 200-220 in the interval having BSR while it varies within 90-100 in other intervals. Thereby, high interval quality factor ascertains that observed BSR is due to presence of gas hydrates. We have performed rock physics modelling by using isotropic and anisotropic models, to quantitatively estimate gas hydrate saturation at one of the location where an interval has high quality factor. Abruptly high measured resistivity and high P-wave velocity in the interval, leads to towering hydrate saturation (Archie,1942 and Helegrud et al, 1999) in comparison to lower gas hydrate saturations estimated by pressure core and chlorinity measurements. Overestimation of saturation is attributed to presence of near vertical fractures that are identified from logging-while-drilling resistivity images. We have carried out anisotropic modeling (Kennedy and Herrick, 2004 and Lee,2009) by incorporating fracture volume and fracture porosity to estimate hydrate saturation and have observed that modeled gas hydrate saturations agree with the lower gas hydrate saturations obtained from pressure core and chlorinity measurements. Therefore, we find that 1) quality factor is significantly higher in the interval bearing gas hydrates and is a useful tool to discover hydrate deposits, 2) anisotropy due to presence of near vertical hydrate filled fractures translates into elevated saturation because of high measured resistivity and velocity and 3) anisotropic model greatly corrects the saturation estimates in fractured medium. References: Archie, G.E., 1942. Petroleum Transactions of AIME, 146, 54-62. Dasgupta, R., Clark, R.A., 1998. Geophysics 63, 2120-2128. Kennedy, W.D., Herrick, D.C., 2004. Petrophysics 45, 38-58. Lee, M.W., 2009. U.S. Geological Survey Scientific Investigations Report 2009-5141, 13. Sain, K., Singh, A.K., Thakur, N.K., Khanna, R.K., 2009.Marine Geophysical Researches 30, 137-145.
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NASA Astrophysics Data System (ADS)
Dai, S.; Seol, Y.
2015-12-01
In general, hydrate makes the sediments hydraulically less conductive, thermally more conductive, and mechanically stronger; yet the dependency of these physical properties on hydrate saturation varies with hydrate distribution and morphology. Hydrate distribution in sediments may cause the bulk physical properties of their host sediments varying several orders of magnitude even with the same amount of hydrate. In natural sediments, hydrate morphology is inherently governed by the burial depth and the grain size of the host sediments. Compare with patchy hydrate, uniformly distributed hydrate is more destructive to fluid flow, yet leads to higher gas and water permeability during hydrate dissociation due to the easiness of forming percolation paths. Water and hydrate have similar thermal conductivity values; the bulk thermal conductivity of hydrate-bearing sediments depends critically on gas-phase saturation. 60% of gas saturation may result in evident thermal conductivity drop and hinder further gas production. Sediments with patchy hydrate yield lower stiffness than that with cementing hydrate but higher stiffness than that with pore filling and loading bearing hydrate. Besides hydrate distribution, the stress state and loading history also play an important role in the mechanical behavior of hydrate-bearing sediments.
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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.
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Elastic velocity models for gas-hydrate-bearing sediments-a comparison
NASA Astrophysics Data System (ADS)
Chand, Shyam; Minshull, Tim A.; Gei, Davide; Carcione, José M.
2004-11-01
The presence of gas hydrate in oceanic sediments is mostly identified by bottom-simulating reflectors (BSRs), reflection events with reversed polarity following the trend of the seafloor. Attempts to quantify the amount of gas hydrate present in oceanic sediments have been based mainly on the presence or absence of a BSR and its relative amplitude. Recent studies have shown that a BSR is not a necessary criterion for the presence of gas hydrates, but rather its presence depends on the type of sediments and the in situ conditions. The influence of hydrate on the physical properties of sediments overlying the BSR is determined by the elastic properties of their constituents and on sediment microstructure. In this context several approaches have been developed to predict the physical properties of sediments, and thereby quantify the amount of gas/gas hydrate present from observed deviations of these properties from those predicted for sediments without gas hydrate. We tested four models: the empirical weighted equation (WE); the three-phase effective-medium theory (TPEM); the three-phase Biot theory (TPB) and the differential effective-medium theory (DEM). We compared these models for a range of variables (porosity and clay content) using standard values for physical parameters. The comparison shows that all the models predict sediment properties comparable to field values except for the WE model at lower porosities and the TPB model at higher porosities. The models differ in the variation of velocity with porosity and clay content. The variation of velocity with hydrate saturation is also different, although the range is similar. We have used these models to predict velocities for field data sets from sediment sections with and without gas hydrates. The first is from the Mallik 2L-38 well, Mackenzie Delta, Canada, and the second is from Ocean Drilling Program (ODP) Leg 164 on Blake Ridge. Both data sets have Vp and Vs information along with the composition and porosity of the matrix. Models are considered successful if predictions from both Vp and Vs match hydrate saturations inferred from other data. Three of the models predict consistent hydrate saturations of 60-80 per cent from both Vp and Vs from log and vertical seismic profiling data for the Mallik 2L-38 well data set, but the TPEM model predicts 20 per cent higher saturations, as does the DEM model with a clay-water starting medium. For the clay-rich sediments of Blake Ridge, the DEM, TPEM and WE models predict 10-20 per cent hydrate saturation from Vp data, comparable to that inferred from resistivity data. The hydrate saturation predicted by the TPB model from Vp is higher. Using Vs data, the DEM and TPEM models predict very low or zero hydrate saturation while the TPB and WE models predict hydrate saturation very much higher than those predicted from Vp data. Low hydrate saturations are observed to have little effect on Vs. The hydrate phase appears to be connected within the sediment microstructure even at low saturations.
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Study on small-strain behaviours of methane hydrate sandy sediments using discrete element method
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yu Yanxin; Cheng Yipik; Xu Xiaomin
Methane hydrate bearing soil has attracted increasing interest as a potential energy resource where methane gas can be extracted from dissociating hydrate-bearing sediments. Seismic testing techniques have been applied extensively and in various ways, to detect the presence of hydrates, due to the fact that hydrates increase the stiffness of hydrate-bearing sediments. With the recognition of the limitations of laboratory and field tests, wave propagation modelling using Discrete Element Method (DEM) was conducted in this study in order to provide some particle-scale insights on the hydrate-bearing sandy sediment models with pore-filling and cementation hydrate distributions. The relationship between shear wavemore » velocity and hydrate saturation was established by both DEM simulations and analytical solutions. Obvious differences were observed in the dependence of wave velocity on hydrate saturation for these two cases. From the shear wave velocity measurement and particle-scale analysis, it was found that the small-strain mechanical properties of hydrate-bearing sandy sediments are governed by both the hydrate distribution patterns and hydrate saturation.« less
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NASA Astrophysics Data System (ADS)
Chaouachi, Marwen; Falenty, Andrzej; Sell, Kathleen; Enzmann, Frieder; Kersten, Michael; Haberthür, David; Kuhs, Werner F.
2015-06-01
The formation process of gas hydrates in sedimentary matrices is of crucial importance for the physical and transport properties of the resulting aggregates. This process has never been observed in situ at submicron resolution. Here we report on synchrotron-based microtomographic studies by which the nucleation and growth processes of gas hydrate were observed at 276 K in various sedimentary matrices such as natural quartz (with and without admixtures of montmorillonite type clay) or glass beads with different surface properties, at varying water saturation. Both juvenile water and metastably gas-enriched water obtained from gas hydrate decomposition was used. Xenon gas was employed to enhance the density contrast between gas hydrate and the fluid phases involved. The nucleation sites can be easily identified and the various growth patterns are clearly established. In sediments under-saturated with juvenile water, nucleation starts at the water-gas interface resulting in an initially several micrometer thick gas hydrate film; further growth proceeds to form isometric single crystals of 10-20 µm size. The growth of gas hydrate from gas-enriched water follows a different pattern, via the nucleation in the bulk of liquid producing polyhedral single crystals. A striking feature in both cases is the systematic appearance of a fluid phase film of up to several micron thickness between gas hydrates and the surface of the quartz grains. These microstructural findings are relevant for future efforts of quantitative rock physics modeling of gas hydrates in sedimentary matrices and explain the anomalous attenuation of seismic/sonic waves.
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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.
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NASA Astrophysics Data System (ADS)
Dong, Huaimin; Sun, Jianmeng; Lin, Zhenzhou; Fang, Hui; Li, Yafen; Cui, Likai; Yan, Weichao
2018-02-01
Natural gas hydrate is being considered as an alternative energy source for sustainable development and has become a focus of research throughout the world. In this paper, based on CT scanning images of hydrate reservoir rocks, combined with the microscopic distribution of hydrate, a diffusion limited aggregation (DLA) model was used to construct 3D hydrate digital rocks of different distribution types, and the finite-element method was used to simulate their electrical characteristics in order to study the influence of different hydrate distribution types, hydrate saturation and formation of water salinity on electrical properties. The results show that the hydrate digital rocks constructed using the DLA model can be used to characterize the microscopic distribution of different types of hydrates. Under the same conditions, the resistivity of the adhesive hydrate digital rock is higher than the cemented and scattered type digital rocks, and the resistivity of the scattered hydrate digital rock is the smallest among the three types. Besides, the difference in the resistivity of the different types of hydrate digital rocks increases with an increase in hydrate saturation, especially when the saturation is larger than 55%, and the rate of increase of each of the hydrate types is quite different. Similarly, the resistivity of the three hydrate types decreases with an increase in the formation of water salinity. The single distribution hydrate digital rock constructed, combined with the law of microscopic distribution and influence of saturation on the electrical properties, can effectively improve the accuracy of logging identification of hydrate reservoirs and is of great significance for the estimation of hydrate reserves.
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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.
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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).
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Amphibole and Phlogopite Formation on the R Chondrite Parent Body: An Experimental Investigation
NASA Astrophysics Data System (ADS)
Lunning, N. G.; Waters, L. E.; McCoy, T. J.
2017-07-01
High-temperature hydrated minerals can form at the pressures and the temperatures expected for the interiors of planetesimals. Under water-saturated conditions, minimum silicate melting can initiate at temperatures as low as 870°C at 40 MPa.
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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.
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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.
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NASA Astrophysics Data System (ADS)
Jang, Jaewon; Santamarina, J. Carlos
2014-01-01
Capillarity and both gas and water permeabilities change as a function of gas saturation. Typical trends established in the discipline of unsaturated soil behavior are used when simulating gas production from hydrate-bearing sediments. However, the evolution of gas saturation and water drainage in gas invasion (i.e., classical soil behavior) and gas nucleation (i.e., gas production) is inherently different: micromodel experimental results show that gas invasion forms a continuous flow path while gas nucleation forms isolated gas clusters. Complementary simulations conducted using tube networks explore the implications of the two different desaturation processes. In spite of their distinct morphological differences in fluid displacement, numerical results show that the computed capillarity-saturation curves are very similar in gas invasion and nucleation (the gas-water interface confronts similar pore throat size distribution in both cases); the relative water permeability trends are similar (the mean free path for water flow is not affected by the topology of the gas phase); and the relative gas permeability is slightly lower in nucleation (delayed percolation of initially isolated gas-filled pores that do not contribute to gas conductivity). Models developed for unsaturated sediments can be used for reservoir simulation in the context of gas production from hydrate-bearing sediments, with minor adjustments to accommodate a lower gas invasion pressure Po and a higher gas percolation threshold.
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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.
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Examination of Hydrate Formation Methods: Trying to Create Representative Samples
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kneafsey, T.J.; Rees, E.V.L.; Nakagawa, S.
2011-04-01
Forming representative gas hydrate-bearing laboratory samples is important so that the properties of these materials may be measured, while controlling the composition and other variables. Natural samples are rare, and have often experienced pressure and temperature changes that may affect the property to be measured [Waite et al., 2008]. Forming methane hydrate samples in the laboratory has been done a number of ways, each having advantages and disadvantages. The ice-to-hydrate method [Stern et al., 1996], contacts melting ice with methane at the appropriate pressure to form hydrate. The hydrate can then be crushed and mixed with mineral grains under controlledmore » conditions, and then compacted to create laboratory samples of methane hydrate in a mineral medium. The hydrate in these samples will be part of the load-bearing frame of the medium. In the excess gas method [Handa and Stupin, 1992], water is distributed throughout a mineral medium (e.g. packed moist sand, drained sand, moistened silica gel, other porous media) and the mixture is brought to hydrate-stable conditions (chilled and pressurized with gas), allowing hydrate to form. This method typically produces grain-cementing hydrate from pendular water in sand [Waite et al., 2004]. In the dissolved gas method [Tohidi et al., 2002], water with sufficient dissolved guest molecules is brought to hydrate-stable conditions where hydrate forms. In the laboratory, this is can be done by pre-dissolving the gas of interest in water and then introducing it to the sample under the appropriate conditions. With this method, it is easier to form hydrate from more soluble gases such as carbon dioxide. It is thought that this method more closely simulates the way most natural gas hydrate has formed. Laboratory implementation, however, is difficult, and sample formation is prohibitively time consuming [Minagawa et al., 2005; Spangenberg and Kulenkampff, 2005]. In another version of this technique, a specified quantity of gas is placed in a sample, then the sample is flooded with water and cooled [Priest et al., 2009]. We have performed a number of tests in which hydrate was formed and the uniformity of the hydrate formation was examined. These tests have primarily used a variety of modifications of the excess gas method to make the hydrate, although we have also used a version of the excess water technique. Early on, we found difficulties in creating uniform samples with a particular sand/ initial water saturation combination (F-110 Sand, {approx} 35% initial water saturation). In many of our tests we selected this combination intentionally to determine whether we could use a method to make the samples uniform. The following methods were examined: Excess gas, Freeze/thaw/form, Freeze/pressurize/thaw, Excess gas followed by water saturation, Excess water, Sand and kaolinite, Use of a nucleation enhancer (SnoMax), and Use of salt in the water. Below, each method, the underlying hypothesis, and our results are briefly presented, followed by a brief conclusion. Many of the hypotheses investigated are not our own, but were presented to us. Much of the data presented is from x-ray CT scanning our samples. The x-ray CT scanner provides a three-dimensional density map of our samples. From this map and the physics that is occurring in our samples, we are able to gain an understanding of the spatial nature of the processes that occur, and attribute them to the locations where they occur.« less
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Methane hydrate formation in turbidite sediments of northern Cascadia, IODP Expedition 311
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.
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Moridis, G.J.; Silpngarmlert, S.; Reagan, M.T.; Collett, T.; Zhang, K.
2011-01-01
As part of an effort to identify suitable targets for a planned long-term field test, we investigate by means of numerical simulation the gas production potential from unit D, a stratigraphically bounded (Class 3) permafrost-associated hydrate occurrence penetrated in the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well on North Slope, Alaska. This shallow, low-pressure deposit has high porosities (?? = 0.4), high intrinsic permeabilities (k = 10-12 m2) and high hydrate saturations (SH = 0.65). It has a low temperature (T = 2.3-2.6 ??C) because of its proximity to the overlying permafrost. The simulation results indicate that vertical wells operating at a constant bottomhole pressure would produce at very low rates for a very long period. Horizontal wells increase gas production by almost two orders of magnitude, but production remains low. Sensitivity analysis indicates that the initial deposit temperature is by the far the most important factor determining production performance (and the most effective criterion for target selection) because it controls the sensible heat available to fuel dissociation. Thus, a 1 ??C increase in temperature is sufficient to increase the production rate by a factor of almost 8. Production also increases with a decreasing hydrate saturation (because of a larger effective permeability for a given k), and is favored (to a lesser extent) by anisotropy. ?? 2010.
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NASA Astrophysics Data System (ADS)
Khasanov, M. K.; Stolpovsky, M. V.; Gimaltdinov, I. K.
2018-05-01
In this article, in a flat-one-dimensional approximation, a mathematical model is presented for injecting warm carbon dioxide into a methane hydrate formation of finite length. It is established that the model of formation of hydrate of carbon dioxide in the absence of an area saturated with methane and water, under certain parameters, leads to thermodynamic contradiction. The mathematical model of carbon dioxide injection with formation of the region saturated with methane and water is constructed.
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In-situ Micro-structural Studies of Gas Hydrate Formation in Sedimentary Matrices
NASA Astrophysics Data System (ADS)
Kuhs, Werner F.; Chaouachi, Marwen; Falenty, Andrzej; Sell, Kathleen; Schwarz, Jens-Oliver; Wolf, Martin; Enzmann, Frieder; Kersten, Michael; Haberthür, David
2015-04-01
The formation process of gas hydrates in sedimentary matrices is of crucial importance for the physical and transport properties of the resulting aggregates. This process has never been observed in-situ with sub-micron resolution. Here, we report on synchrotron-based micro-tomographic studies by which the nucleation and growth processes of gas hydrate were observed in different sedimentary matrices (natural quartz, glass beds with different surface properties, with and without admixtures of kaolinite and montmorillonite) at varying water saturation. The nucleation sites can be easily identified and the growth pattern is clearly established. In under-saturated sediments the nucleation starts at the water-gas interface and proceeds from there to form predominantly isometric single crystals of 10-20μm size. Using a newly developed synchrotron-based method we have determined the crystallite size distributions (CSD) of the gas hydrate in the sedimentary matrix confirming in a quantitative and statistically relevant manner the impressions from the tomographic reconstructions. It is noteworthy that the CSDs from synthetic hydrates are distinctly smaller than those of natural gas hydrates [1], which suggest that coarsening processes take place in the sedimentary matrix after the initial hydrate formation. Understanding the processes of formation and coarsening may eventually permit the determination of the age of gas hydrates in sedimentary matrices [2], which are largely unknown at present. Furthermore, the full micro-structural picture and its evolution will enable quantitative digital rock physics modeling to reveal poroelastic properties and in this way to support the exploration and exploitation of gas hydrate resources in the future. [1] Klapp S.A., Hemes S., Klein H., Bohrmann G., McDonald I., Kuhs W.F. Grain size measurements of natural gas hydrates. Marine Geology 2010; 274(1-4):85-94. [2] Klapp S.A., Klein H, Kuhs W.F. First determination of gas hydrate crystallite size distribution using high-energy synchrotron radiation. Geophys.Res.Letters, 2007 ; 34 : L13608, DOI:10.1029/2006GL029134
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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.
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Lee, M.W.; Collett, T.S.
2008-01-01
Accurately detecting and quantifying gas hydrate or free gas in sediments from seismic data require downhole well-log data to calibrate the physical properties of the gas hydrate-/free gas-bearing sediments. As part of the Gulf of Mexico Joint Industry Program, a series of wells were either cored or drilled in the Gulf of Mexico to characterize the physical properties of gas hydrate-bearing sediments, to calibrate geophysical estimates, and to evaluate source and transport mechanisms for gas within the gas hydrates. Downhole acoustic logs were used sparingly in this study because of degraded log quality due to adverse wellbore conditions. However, reliable logging while drilling (LWD) electrical resistivity and porosity logs were obtained. To tie the well-log information to the available 3-D seismic data in this area, a velocity log was calculated from the available resistivity log at the Keathley Canyon 151-2 well, because the acoustic log or vertical seismic data acquired at the nearby Keathley Canyon 151-3 well were either of poor quality or had limited depth coverage. Based on the gas hydrate saturations estimated from the LWD resistivity log, the modified Biot-Gassmann theory was used to generate synthetic acoustic log and a synthetic seismogram was generated with a fairly good agreement with a seismic profile crossing the well site. Based on the well-log information, a faintly defined bottom-simulating reflection (BSR) in this area is interpreted as a reflection representing gas hydrate-bearing sediments with about 15% saturation overlying partially gas-saturated sediments with 3% saturation. Gas hydrate saturations over 30-40% are estimated from the resistivity log in two distinct intervals at 220-230 and 264-300 m below the sea floor, but gas hydrate was not physically recovered in cores. It is speculated that the poor recovery of cores and gas hydrate morphology are responsible for the lack of physical gas hydrate recovery.
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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.
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NASA Astrophysics Data System (ADS)
Boswell, R. M.; Collett, T. S.; Frye, M.; McConnell, D.; Shedd, W.; Shelander, D.; Dai, J.; Mrozewski, S.; Guerin, G.; Cook, A.; Dufrene, R.; Godfriaux, P. D.; Roy, R.; Jones, E.
2009-12-01
The Gulf of Mexico gas hydrates Joint Industry Project (the JIP), a cooperative research program between the US Department of Energy and an international industrial consortium under the leadership of Chevron, conducted its “Leg II” logging-while-drilling operations in April and May of 2009. JIP Leg II was intended to expand the existing JIP work from previous emphasis on fine-grained sedimentary systems to the direct evaluation of gas hydrate in sand-dominated reservoirs. The selection of the locations for the JIP Leg II drilling were the result of a geological and geophysical prospecting approach that integrated direct geophysical evidence of gas hydrate-bearing strata with evidence of gas sourcing and migration and occurrence of sand reservoirs within the gas hydrate stability zone. Logging-while-drilling operations included the drilling of seven wells at three sites. The expedition experienced minimal operational problems with the advanced LWD tool string, and successfully managed a number of shallow drilling challenges, including borehole breakouts, and shallow gas and water flows. Two wells drilled in Walker Ridge block 313 (WR-313) confirmed the pre-drill predictions by discovering gas hydrates at high saturations in multiple sand horizons with reservoir thicknesses up to 50 ft. In addition, drilling in WR-313 discovered a thick, strata-bound interval of grain-displacing gas hydrate in shallow fine-grained sediments. Two of three wells drilled in Green Canyon block 955 (GC-955) confirmed the pre-drill prediction of extensive sand occurrence with gas hydrate fill along the crest of a structure with positive indications of gas source and migration. In particular, well GC955-H discovered ~100 ft of gas hydrate in sand at high saturations. Two wells drilled in Alaminos Canyon block 21 (AC-21) confirmed the pre-drill prediction of potential extensive occurrence of gas hydrates in shallow sand reservoirs at low to moderate saturations; however, further data collection and analyses at AC-21 will be needed to better understand the nature of the pore filling material. JIP Leg II fully met its scientific objectives with the collection of abundant high-quality data from gas hydrate bearing sands in the Gulf of Mexico. Ongoing work within the JIP will enable further validation of the geophysical and geological methods used to predict the occurrence of gas hydrate. Expedition results will also support the selection of locations for future JIP drilling, logging and coring operations.
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Gas hydrate formation rates from dissolved-phase methane in porous laboratory specimens
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.
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Lee, J.Y.; Santamarina, J.C.; Ruppel, C.
2010-01-01
The marked decrease in bulk electrical conductivity of sediments in the presence of gas hydrates has been used to interpret borehole electrical resistivity logs and, to a lesser extent, the results of controlled source electromagnetic surveys to constrain the spatial distribution and predicted concentration of gas hydrate in natural settings. Until now, an exhaustive laboratory data set that could be used to assess the impact of gas hydrate on the electromagnetic properties of different soils (sand, silt, and clay) at different effective stress and with different saturations of hydrate has been lacking. The laboratory results reported here are obtained using a standard geotechnical cell and the hydrate-formed tetrahydrofuran (THF), a liquid that is fully miscible in water and able to produce closely controlled saturations of hydrate from dissolved phase. Both permittivity and electrical conductivity are good indicators of the volume fraction of free water in the sediment, which is in turn dependent on hydrate saturation. Permittivity in the microwave frequency range is particularly predictive of free water content since it is barely affected by ionic concentration, pore structure, and surface conduction. Electrical conductivity (or resistivity) is less reliable for constraining water content or hydrate saturation: In addition to fluid-filled porosity, other factors, such as the ionic concentration of the pore fluid and possibly other conduction effects (e.g., surface conduction in high specific surface soils having low conductivity pore fluid), also influence electrical conductivity.
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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.
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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.
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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.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Schaef, Herbert T.; Ilton, Eugene S.; Qafoku, Odeta
2012-01-09
Reactions involving scCO2 and a calcium saturated dioctahedral smectite (Ca-STX-1) were examined by in situ high-pressure x-ray diffraction over a range of temperatures (50° to 100°C) and pressures (90, 125, and 180 bar) relevant to long term geologic storage of CO2. Exposure of Ca-STX-1 containing one water of hydration (1W) to anhydrous scCO2 at 50°C and 90 bar produced an immediate increase of ~0.8 Å in the d001 basal reflection that was sustained for the length of the experiment (~44 hours). Higher ordered basal reflections displayed similar shifts. Following depressurization, positions of basal reflections and FWHM values (d001) returned tomore » initial values, with no measurable modification to the clay structure or water content. Similar results were obtained for tests conducted at 50°C and higher pressures (125 and 180 bar). Exposure of Ca-STX-1 containing two waters of hydration (2W) to scCO2 resulted in a decrease in the d001 reflection from 14.48 Å to 12.52 Å, after pressurization, indicating a partial loss of interlayer water. In addition, the hydration state of the clay became more homogeneous during contact with anhydrous scCO2 and after depressurization. In the presence of scCO2 and water, the clay achieved a 3W hydration state, based on a d001 spacing of 18.8 Å. In contrast to scCO2, comparable testing with N2 gas indicated trivial changes in the d001 series regardless of hydration state (1W or 2W). In the presence of free water and N2, the basal spacing for the Ca-STX-1 expanded slightly, but remained in the 2W hydration state. These experiments indicate that scCO2 can intercalate hydrated clays, where the 1W hydrate state is stable when exposed to anhydrous scCO2 under conditions proposed for geologic storage of CO2. Consequently, clays can act as secondary CO2 traps where potential collapse or expansion of the interlayer spacing depends on the initial hydration state of the clay and scCO2.« less
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NASA Astrophysics Data System (ADS)
Yang, Z.; He, T.
2017-12-01
To more accurately explain geophysical exploration data of natural gas hydrate reservoir and to better assess the formation stability for geological or engineering hazards, it is important to comprehensively understand the geophysical and mechanical properties of hydrate-bearing unconsolidated marine sediments, which are significantly different from sea-water saturated ones. Compared to hard-to-control in-situ measurement, laboratory methods are important and feasible to investigate the parameter effects. With the new designed experimental apparatus, we measured ultrasonic velocity, resistivity and stress-strain relation of methane hydrate-bearing unconsolidated sediments. The experimental mineral mixture is prepared as the composition of sample HY-3 of core SH-7 from Shenhu area, South China Sea. It composed of 0.4 wt. % kaolinite, 23.5 wt. % silt (4 - 63 μm), 32.1 wt. % fine sand (63 - 250 μm), 29.2 wt. % medium sand (250 - 500 μm) and 14.8 wt. % coarse sand (500 - 2000 μm). The pure methane enters into the brine (NaCl salinity of 3.5%) saturated sample all around to synthesis methane hydrate. The methane hydrate saturation was calculated by methane consumption amount, which was in turn calculated by gas state equation using the measured methane pressure drop in high pressure reactor. The ultrasonic velocities and resistivity were measured frequently during methane hydrate saturation increasing to examine the velocity varying pattern, especially for S-wave velocities, which may reflect different hydrate occurrence states in sediment pores: load-bearing or not. The stress - strain curves of methane hydrate - bearing sediments showed typical elastic - plastic characteristics and were used to obtain Young's modulus, Poisson's ratio, failure strength and other mechanical parameters. With these results, we can know better about the hydrate reservoir at Shenhu area.
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Thermodynamics of mercaptopurine dehydration.
Niazi, S
1978-04-01
The hydrate form of mercaptopurine was shown to undergo peritectic decomposition of its water molecule, localized dissolution, and dehydration around 125 degrees. The anhydrate form was prepared by a thermal method, whose effectiveness was confirmed by X-ray diffraction, NMR spectroscopy, and differential scanning calorimetry. The activation energy for mercaptopurine dehydration calculated by various methods ranged from 45.74 to 63.04 kcal/mole. The dehydration enthalpy was calculated to be 8.27 kcal/mole by differential scanning calorimetry. The solution enthalpy for the hydrate was calculated to be 4.85 kcal/mole from its saturation solubility and differential scanning calorimetry. Anhydrate solubility in water was calculated based on initial dissolution rate data since the anhydrate converts to hydrate in aqueous media. The high degree of stability against interconversion of the hydrate and anhydrate forms and the higher solubility of the anhydrate suggest that use of the anhydrate might improve mercaptopurine bioavailability.
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Thermal conductivity of hydrate-bearing sediments
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.
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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
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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.
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NASA Astrophysics Data System (ADS)
Nole, M.; Daigle, H.; Cook, A.; Malinverno, A.; Hillman, J. I. T.
2016-12-01
We explore the gas hydrate-generating capacity of diffusive methane transport induced by solubility gradients due to pore size contrasts in lithologically heterogeneous marine sediments. Through the use of 1D, 2D, and 3D reactive transport simulations, we investigate scale-dependent processes in diffusion-dominated gas hydrate systems. These simulations all track a sand body, or series of sands, surrounded by clays as they are buried through the gas hydrate stability zone. Methane is sourced by microbial methanogenesis in the clays surrounding the sand layers. In 1D, simulations performed in a Lagrangian reference frame demonstrate that gas hydrate in thin sands (3.6 m thick) can occur in high saturations (upward of 70%) at the edges of sand bodies within the upper 400 meters below the seafloor. Diffusion of methane toward the center of the sand layer depends on the concentration gradient within the sand: broader sand pore size distributions with smaller median pore sizes enhance diffusive action toward the sand's center. Incorporating downhole log- and laboratory-derived sand pore size distributions, gas hydrate saturations in the center of the sand can reach 20% of the hydrate saturations at the sand's edges. Furthermore, we show that hydrate-free zones exist immediately above and below the sand and are approximately 5 m thick, depending on the sand-clay solubility contrast. A moving reference frame is also adopted in 2D, and the angle of gravity is rotated relative to the grid system to simulate a dipping sand layer. This is important to minimize diffusive edge effects or numerical diffusion that might be associated with a dipping sand in an Eulerian grid system oriented orthogonal to gravity. Two-dimensional simulations demonstrate the tendency for gas hydrate to accumulate downdip in a sand body because of greater methane transport at depth due to larger sand-clay solubility contrasts. In 3D, basin-scale simulations illuminate how convergent sand layers in a multilayered system can compete for diffusion from clays between them, resulting in relatively low hydrate saturations. All simulations suggest that when hydrate present in clays dissociates with burial, the additional dissolved methane is soaked up by nearby sands preserving high hydrate saturations.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Nole, Michael; Daigle, Hugh; Cook, Ann
We explore the gas hydrate-generating capacity of diffusive methane transport induced by solubility gradients due to pore size contrasts in lithologically heterogeneous marine sediments. Through the use of 1D, 2D, and 3D reactive transport simulations, we investigate scale-dependent processes in diffusion-dominated gas hydrate systems. These simulations all track a sand body, or series of sands, surrounded by clays as they are buried through the gas hydrate stability zone. Methane is sourced by microbial methanogenesis in the clays surrounding the sand layers. In 1D, simulations performed in a Lagrangian reference frame demonstrate that gas hydrate in thin sands (3.6 m thick)more » can occur in high saturations (upward of 70%) at the edges of sand bodies within the upper 400 meters below the seafloor. Diffusion of methane toward the center of the sand layer depends on the concentration gradient within the sand: broader sand pore size distributions with smaller median pore sizes enhance diffusive action toward the sand’s center. Incorporating downhole log- and laboratory-derived sand pore size distributions, gas hydrate saturations in the center of the sand can reach 20% of the hydrate saturations at the sand’s edges. Furthermore, we show that hydrate-free zones exist immediately above and below the sand and are approximately 5 m thick, depending on the sand-clay solubility contrast. A moving reference frame is also adopted in 2D, and the angle of gravity is rotated relative to the grid system to simulate a dipping sand layer. This is important to minimize diffusive edge effects or numerical diffusion that might be associated with a dipping sand in an Eulerian grid system oriented orthogonal to gravity. Two-dimensional simulations demonstrate the tendency for gas hydrate to accumulate downdip in a sand body because of greater methane transport at depth due to larger sand-clay solubility contrasts. In 3D, basin-scale simulations illuminate how convergent sand layers in a multilayered system can compete for diffusion from clays between them, resulting in relatively low hydrate saturations. All simulations suggest that when hydrate present in clays dissociates with burial, the additional dissolved methane is soaked up by nearby sands preserving high hydrate saturations.« less
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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.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Daigle, Hugh; Rice, Mary Anna; Daigle, Hugh
Relative permeabilities to water and gas are important parameters for accurate modeling of the formation of methane hydrate deposits and production of methane from hydrate reservoirs. Experimental measurements of gas and water permeability in the presence of hydrate are difficult to obtain. The few datasets that do exist suggest that relative permeability obeys a power law relationship with water or gas saturation with exponents ranging from around 2 to greater than 10. Critical path analysis and percolation theory provide a framework for interpreting the saturation-dependence of relative permeability based on percolation thresholds and the breadth of pore size distributions, whichmore » may be determined easily from 3-D images or gas adsorption-desorption hysteresis. We show that the exponent of the permeability-saturation relationship for relative permeability to water is related to the breadth of the pore size distribution, with broader pore size distributions corresponding to larger exponents. Relative permeability to water in well-sorted sediments with narrow pore size distributions, such as Berea sandstone or Toyoura sand, follows percolation scaling with an exponent of 2. On the other hand, pore-size distributions determined from argon adsorption measurements we performed on clays from the Nankai Trough suggest that relative permeability to water in fine-grained intervals may be characterized by exponents as large as 10 as determined from critical path analysis. We also show that relative permeability to the gas phase follows percolation scaling with a quadratic dependence on gas saturation, but the threshold gas saturation for percolation changes with hydrate saturation, which is an important consideration in systems in which both hydrate and gas are present, such as during production from a hydrate reservoir. Our work shows how measurements of pore size distributions from 3-D imaging or gas adsorption may be used to determine relative permeabilities.« less
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Archie’s saturation exponent for natural gas hydrate in coarse-grained reservoirs
Cook, Ann E.; Waite, William F.
2018-01-01
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.
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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
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Gulf of Mexico Gas Hydrate Joint Industry Project Leg II: Results from the Walker Ridge 313 Site
NASA Astrophysics Data System (ADS)
Shedd, W.; Frye, M.; Boswell, R. M.; Collett, T. S.; McConnell, D.; Jones, E.; Shelander, D.; Dai, J.; Guerin, G.; Cook, A.; Mrozewski, S.; Godfriaux, P. D.; Dufrene, R.; Hutchinson, D. R.; Roy, R.
2009-12-01
The Gulf of Mexico Gas Hydrate Joint Industry Project Leg II drilling program visited three sites in the Gulf of Mexico during a 21 day drilling program in April and May, 2009. Using both petroleum systems and seismic stratigraphic approaches, the exploration focus for Leg II was to identify sites with the potential for gas hydrate-saturated sand reservoirs. The data acquired consist of a comprehensive suite of high resolution LWD logs including gamma ray, density, porosity, sonic, and resistivity tools. No physical samples were taken in the field. Two holes, locations G and H, were drilled at the Walker Ridge 313 site (WR 313)in the central Gulf of Mexico, just updip of the “salt sheet province”. The primary objective of each well was to determine the presence or absence of gas hydrate from the log data at the predetermined primary targets, picked from industry 3-D seismic data, in dipping Pleistocene turbidite derived sands on the flanks of a salt withdrawal minibasin. The seismic targets were high amplitude positive reflections just updip of phase reversals at the interpreted base of hydrate stability, corresponding to the so-called bottom simulating reflector, or “BSR”. Downdip of the BSR, the sands were clearly troughs, or negative reflections, suggesting free gas charge. An existing industry well, located updip of both JIP locations, contains a slightly sandy zone in the same stratigraphic interval as the JIP targets, that has elevated resistivities correlated to the target sands, suggesting low saturation “shows” of hydrate. Stratigraphically bounded fractured fine grained sediments with probable gas hydrate fill were found in both holes between 800 ft and 1300 ft at G, and between 600 ft and 1000 ft below the seafloor at H. At the primary targets, high saturation gas hydrates in sand were interpreted from logs at both holes. LWD data indicate 50 ft of high saturation gas hydrate in sands starting at 2722 ft below seafloor at the G hole. At H, 37 ft of high saturation gas hydrate was found in the target sand. Numerous minor occurrences of probable pore filling gas hydrate in thin sands were found at both locations. The likely discovery of thick gas hydrate-filled sands at the WR 313 site validates the exploration approach, and strongly indicates that gas hydrate can be found in reservoir quality marine sands. Additionally, the depth below mudline to which these wells were drilled without risers or drivepipe is unprecedented and the information gleaned will aid in marine hydrate exploration efforts worldwide.
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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
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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
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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
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NASA Astrophysics Data System (ADS)
Jiang, J.; Shen, Z.; Jia, Y.
2017-12-01
Methane hydrates are superior energy resources and potential predisposing factors of geohazard. With the success in China's persistent exploitation of methane hydrates in the Shenhu area of South China Sea for 60 days, there is an increasing demand for detailed knowledge of sediment properties and hazard assessment in this area. In this paper, the physical and mechanical properties of both the surface sediments and methane hydrate-bearing sediments (MHBS) in the exploitation area, the Shenhu area of South China Sea, were investigated using laboratory geotechnical experiments, and triaxial tests were carried out on remolded sediment samples using a modified triaxial apparatus. The results show that sediments in this area are mainly silt with high moisture content, high plasticity, low permeability and low shear strength. The moisture content and permeability decrease while the shear strength increases with the increasing depth. The elastic modulus and peak strength of MHBS increase with the increasing effective confining pressure and higher hydrate saturation. The cohesion increases with higher hydrate saturation while the internal friction angle is barely affected by hydrate saturation. The obtained results demonstrate clearly that methane hydrates have significant impacts on the physical and mechanical properties of sediments and there is still a wide gap in knowledge about MHBS.
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Anderson, B.; Hancock, S.; Wilson, S.; Enger, C.; Collett, T.; Boswell, R.; Hunter, R.
2011-01-01
In February 2007, the U.S. Department of Energy, BP Exploration (Alaska), and the U.S. Geological Survey, collected open-hole pressure-response data, as well as gas and water sample collection, in a gas hydrate reservoir (the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well) using Schlumberger's Modular Dynamics Formation Tester (MDT) wireline tool. Four such MDT tests, ranging from six to twelve hours duration, and including a series of flow, sampling, and shut-in periods of various durations, were conducted. Locations for the testing were selected based on NMR and other log data to assure sufficient isolation from reservoir boundaries and zones of excess free water. Test stages in which pressure was reduced sufficiently to mobilize free water in the formation (yet not cause gas hydrate dissociation) produced readily interpretable pressure build-up profiles. Build-ups following larger drawdowns consistently showed gas-hydrate dissociation and gas release (as confirmed by optical fluid analyzer data), as well as progressive dampening of reservoir pressure build-up during sequential tests at a given MDT test station.History matches of one multi-stage, 12-h test (the C2 test) were accomplished using five different reservoir simulators: CMG-STARS, HydrateResSim, MH21-HYDRES, STOMP-HYD, and TOUGH. +. HYDRATE. Simulations utilized detailed information collected across the reservoir either obtained or determined from geophysical well logs, including thickness (11.3. m, 37 ft.), porosity (35%), hydrate saturation (65%), both mobile and immobile water saturations, intrinsic permeability (1000 mD), pore water salinity (5 ppt), and formation temperature (3.3-3.9 ??C). This paper will present the approach and preliminary results of the history-matching efforts, including estimates of initial formation permeability and analyses of the various unique features exhibited by the MDT results. ?? 2010 Elsevier Ltd.
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NASA Astrophysics Data System (ADS)
Wu, Cheng-Yueh; Chiu, Yung-Cheng; Huang, Yi-Jyun; Hsieh, Bieng-Zih
2017-04-01
The future energy police of Taiwan will heavily rely on the clean energy, including renewable energy and low-carbon energy, to meet the target of mitigating CO2 emission. In addition to developing the renewable energies like solar and wind resources, Taiwan will increase the natural gas consumption to obtain enough electrical power with low-carbon emission. The vast resources of gas hydrates recognized in southwestern offshore Taiwan makes a great opportunity for Taiwan to have own energy resources in the future. Therefore, Taiwan put significant efforts on the evaluation of gas hydrate reserves recently. Production behavior of natural gas dissociated from gas hydrate deposits is an important issue to the hydrate reserves evaluation. The depressurization method is a useful engineering recovery method for gas production from a class-3 type hydrate deposit. The dissociation efficiency will be affected by the pressure drawdown disturbance. However, when the pore pressure of hydrate deposits is depressurized for gas production, the rock matrix will surfer more stresses and the formation deformation might be occurred. The purpose of this study was to investigate the effects of geomechanical mechanism on the gas production from a class-3 hydrate deposit using depressurization method. The case of a class-3 type hydrate deposit of Four-Way-Closure Ridge was studied. In this study a reservoir simulator, STARS, was used. STARS is a multiphase flow, heat transfer, geo-chemical and geo-mechanical mechanisms coupling simulator which is capable to simulate the dissociation/reformation of gas hydrate and the deformation of hydrate reservoirs and overburdens. The simulating ability of STARTS simulator was validated by duplicating the hydrate comparison projects of National Energy Technology Lab. The study target, Four-Way-Closure (FWC) Ridge hydrate deposit, was discovered by the bottom simulating reflectors (BSRs). The geological parameters were collected from the geological and geophysical studies and the geo-mechanical data were analogized from Japan's hydrate production case. The first step for the geological modelling was to digitize the structure map of FWC Ridge and built a grid system for the reservoir. The formation parameters, such as formation thickness, porosity and permeability, the phase behavior parameters, rock-fluid parameters, initial conditions (including formation pressure, temperature and hydrate saturation), geo-mechanical parameters were assigned into each grid. In this case we used a horizontal well with specific operating conditions to produce water and dissociated gas from the reservoir. The sensitivity analyses on geological and geo-mechanical parameters were conducted in this study. The case of different pressure drop showed that the recovery factor (RF) was 2.50%, 13.50% and 20.47% when the pressure drop of 60%, 70% and 75% from the initial reservoir pressure was used respectively. Based on the case of pressure drop of 75% (from the initial reservoir pressure), the RF was 35.13%, 25.9%, 20.47% and 16.65% when the initial hydrate saturation of 30%, 40%, 50% and 60% was assumed respectively. The greater formation permeability, the better gas recovery. The capillary pressure had a minor affection on the gas production in this case study. The best well location was at the upper layer because of the gravity effect. For the effects of the geo-mechanics, we observed that the rock mechanisms had impacts on the final cumulative gas production. The larger the Young's Modulus and the smaller the Poisson's Ratio, the smaller the subsidence on the seabed. Our simulation results showed that the seabed subsidence in FWC Ridge was about 1 meter during the production period.
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Influence of temperature on methane hydrate formation.
Zhang, Peng; Wu, Qingbai; Mu, Cuicui
2017-08-11
During gas hydrate formation process, a phase transition of liquid water exists naturally, implying that temperature has an important influence on hydrate formation. In this study, methane hydrate was formed within the same media. The experimental system was kept at 1.45, 6.49, and 12.91 °C respectively, and then different pressurization modes were applied in steps. We proposed a new indicator, namely the slope of the gas flow rates against time (dν g /dt), to represent the intrinsic driving force for hydrate formation. The driving force was calculated as a fixed value at the different stages of formation, including initial nucleation/growth, secondary nucleation/growth, and decay. The amounts of gas consumed at each stage were also calculated. The results show that the driving force during each stage follows an inverse relation with temperature, whereas the amount of consumed gas is proportional to temperature. This opposite trend indicates that the influences of temperature on the specific formation processes and final amounts of gas contained in hydrate should be considered separately. Our results also suggest that the specific ambient temperature under which hydrate is formed should be taken into consideration, when explaining the formation of different configurations and saturations of gas hydrates in natural reservoirs.
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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.
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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.
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NASA Astrophysics Data System (ADS)
LONG, S.; He, T.; Lan, K.; Spence, G.; Yelisetti, S.
2016-12-01
The previous study indicated that Slipstream submarine landslide is one of a gas hydrate-related slope failures on the frontal ridges of the Northern Cascadia accretionary margin, off Vancouver Island, Canada. The OBS data collected during SeaJade project were used to derive the subseafloor Vp & Vs structures. The anomalous high Vp of about 2.0 km/s at shallow depths of 100 (± 10) mbsf closely matches the estimated depth of the glide plane. The modelled Vs above the BSR at a depth of 265-275 mbsf is about 100-150 m/s higher than a theoretical 100% water saturated background value, indicating that the hydrate acts as part of the load-bearing matrix to increase the rigidity of the sediment. Also, the Vp & Vs above BSR both indicate a consistent 40% saturation of gas hydrate. On the basis of high accurate submarine bathymetry obtained by multibeam sounding system, the submarine landform before slump is reconstructed by comparing the slump headwall geometry with surrounding ridges. Using the elastic moduli determined from Vp & Vs, the stress status was calculated by the finite element method for different conditions and confirmed that the undersea sliding process related with gas hydrate starts from the toe of the slope and then progressively retreats to the place of current headwall, in a series of triangular blocks or wedges. The shear stress are then compared with the frame shear strength of geological model, which is critical for controlling slope stability of steep frontal ridges The simulation results found that the ridge was stable under its own weight, but gas hydrate saturation decrease and pore-water pressure increase will greatly reduce shear strength of sediments and may cause a landslide. Since the study area is in the earthquake belt, the large seismic acceleration will greatly affect pore pressure distribution within the ridge. The simulation results indicated that the shallow high-velocity gas hydrate layer coincident with glide plane depth is more likely to fail than the current BSR observations during an earthquake. Combining with regional tectonic background, it is initially deduced that the large earthquake is the most possible trigger of Slipstream landslide.
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Mechanisms Leading to Co-Existence of Gas Hydrate in Ocean Sediments [Part 1 of 2
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bryant, Steven; Juanes, Ruben
In this project we have sought to explain the co-existence of gas and hydrate phases in sediments within the gas hydrate stability zone. We have focused on the gas/brine interface at the scale of individual grains in the sediment. The capillary forces associated with a gas/brine interface play a dominant role in many processes that occur in the pores of sediments and sedimentary rocks. The mechanical forces associated with the same interface can lead to fracture initiation and propagation in hydrate-bearing sediments. Thus the unifying theme of the research reported here is that pore scale phenomena are key to understandingmore » large scale phenomena in hydrate-bearing sediments whenever a free gas phase is present. Our analysis of pore-scale phenomena in this project has delineated three regimes that govern processes in which the gas phase pressure is increasing: fracturing, capillary fingering and viscous fingering. These regimes are characterized by different morphology of the region invaded by the gas. On the other hand when the gas phase pressure is decreasing, the corresponding regimes are capillary fingering and compaction. In this project, we studied all these regimes except compaction. Many processes of interest in hydrate-bearing sediments can be better understood when placed in the context of the appropriate regime. For example, hydrate formation in sub-permafrost sediments falls in the capillary fingering regime, whereas gas invasion into ocean sediments is likely to fall into the fracturing regime. Our research provides insight into the mechanisms by which gas reservoirs are converted to hydrate as the base of the gas hydrate stability zone descends through the reservoir. If the reservoir was no longer being charged, then variation in grain size distribution within the reservoir explain hydrate saturation profiles such as that at Mt. Elbert, where sand-rich intervals containing little hydrate are interspersed between intervals containing large hydrate saturations. Large volumes (of order one pore volume) of gaseous and aqueous phases must be transported into the gas hydrate stability zone. The driver for this transport is the pressure sink induced by a reduction in occupied pore volume that accompanies the formation of hydrate from gas and water. Pore-scale imbibition models and bed-scale multiphase flow models indicate that the rate-limiting step in converting gas to hydrate is the supply of water to the hydrate stability zone. Moreover, the water supply rate is controlled by capillarity-driven flux for conditions typical of the Alaska North Slope. A meter-scale laboratory experiment confirms that significant volumes of fluid phases move into the hydrate stability zone and that capillarity is essential for the water flux. The model shows that without capillarity-driven flux, large saturations of hydrate cannot form. The observations of thick zones of large saturation at Mallik and Mt Elbert thus suggest that the primary control on these systems is the rate of transport of gaseous and aqueous phases, driven by the pressure sink at the base of the gas hydrate stability zone. A key finding of our project is the elucidation of ?capillary fracturing? as a dominant gas transport mechanism in low-permeability media. We initially investigate this phenomenon by means of grain-scale simulations in which we extended a discrete element mechanics code (PFC, by Itasca) to incorporate the dynamics of first single-phase and then multiphase flow. A reductionist model on a square lattice allows us to determine some of the fundamental dependencies of the mode of gas invasion (capillary fingering, viscous fingering, and fracturing) on the parameters of the system. We then show that the morphology of the gas-invaded region exerts a fundamental control on the fabric of methane hydrate formation, and on the overpressures caused by methane hydrate dissociation. We demonstrate the existence of the different invasion regimes by means of controlled laboratory experiments in a radial cell. We collapse the behavior in the form of a phase diagram fully characterized by two dimensionless groups: a modified capillary number and a ?fracturing number? that reflects the balance between the pressure forces that act to open conduits in the granular pack, and frictional forces that resist it. We use all this small-scale knowledge to propose simple mechanistic models of gas migration and hydrate formation at the geologic bed scale. We propose that methane transport in lake and oceanic sediments is controlled by dynamic conduits, which dilate and release gas as the falling hydrostatic pressure reduces the effective stress below the tensile strength of the sediments. We test our model against a four-month record of hydrostatic load and methane flux in Upper Mystic Lake, Mass., USA, and show that it captures the complex episodicity of methane ebullition. Our quantitative conceptualization opens the door to integrated modeling of methane transport to constrain global methane release from lakes and other methane-rich sediment systems, and to assess its climate feedbacks.« less
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Mechanisms Leading to Co-Existence of Gas Hydrate in Ocean Sediments [Part 2 of 2
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bryant, Steven; Juanes, Ruben
In this project we have sought to explain the co-existence of gas and hydrate phases in sediments within the gas hydrate stability zone. We have focused on the gas/brine interface at the scale of individual grains in the sediment. The capillary forces associated with a gas/brine interface play a dominant role in many processes that occur in the pores of sediments and sedimentary rocks. The mechanical forces associated with the same interface can lead to fracture initiation and propagation in hydrate-bearing sediments. Thus the unifying theme of the research reported here is that pore scale phenomena are key to understandingmore » large scale phenomena in hydrate-bearing sediments whenever a free gas phase is present. Our analysis of pore-scale phenomena in this project has delineated three regimes that govern processes in which the gas phase pressure is increasing: fracturing, capillary fingering and viscous fingering. These regimes are characterized by different morphology of the region invaded by the gas. On the other hand when the gas phase pressure is decreasing, the corresponding regimes are capillary fingering and compaction. In this project, we studied all these regimes except compaction. Many processes of interest in hydrate-bearing sediments can be better understood when placed in the context of the appropriate regime. For example, hydrate formation in sub-permafrost sediments falls in the capillary fingering regime, whereas gas invasion into ocean sediments is likely to fall into the fracturing regime. Our research provides insight into the mechanisms by which gas reservoirs are converted to hydrate as the base of the gas hydrate stability zone descends through the reservoir. If the reservoir was no longer being charged, then variation in grain size distribution within the reservoir explain hydrate saturation profiles such as that at Mt. Elbert, where sand-rich intervals containing little hydrate are interspersed between intervals containing large hydrate saturations. Large volumes (of order one pore volume) of gaseous and aqueous phases must be transported into the gas hydrate stability zone. The driver for this transport is the pressure sink induced by a reduction in occupied pore volume that accompanies the formation of hydrate from gas and water. Pore-scale imbibition models and bed-scale multiphase flow models indicate that the rate-limiting step in converting gas to hydrate is the supply of water to the hydrate stability zone. Moreover, the water supply rate is controlled by capillarity-driven flux for conditions typical of the Alaska North Slope. A meter-scale laboratory experiment confirms that significant volumes of fluid phases move into the hydrate stability zone and that capillarity is essential for the water flux. The model shows that without capillarity-driven flux, large saturations of hydrate cannot form. The observations of thick zones of large saturation at Mallik and Mt Elbert thus suggest that the primary control on these systems is the rate of transport of gaseous and aqueous phases, driven by the pressure sink at the base of the gas hydrate stability zone. A key finding of our project is the elucidation of ?capillary fracturing? as a dominant gas transport mechanism in low-permeability media. We initially investigate this phenomenon by means of grain-scale simulations in which we extended a discrete element mechanics code (PFC, by Itasca) to incorporate the dynamics of first singlephase and then multiphase flow. A reductionist model on a square lattice allows us to determine some of the fundamental dependencies of the mode of gas invasion (capillary fingering, viscous fingering, and fracturing) on the parameters of the system. We then show that the morphology of the gas-invaded region exerts a fundamental control on the fabric of methane hydrate formation, and on the overpressures caused by methane hydrate dissociation. We demonstrate the existence of the different invasion regimes by means of controlled laboratory experiments in a radial cell. We collapse the behavior in the form of a phase diagram fully characterized by two dimensionless groups: a modified capillary number and a ?fracturing number? that reflects the balance between the pressure forces that act to open conduits in the granular pack, and frictional forces that resist it. We use all this small-scale knowledge to propose simple mechanistic models of gas migration and hydrate formation at the geologic bed scale. We propose that methane transport in lake and oceanic sediments is controlled by dynamic conduits, which dilate and release gas as the falling hydrostatic pressure reduces the effective stress below the tensile strength of the sediments. We test our model against a four-month record of hydrostatic load and methane flux in Upper Mystic Lake, Mass., USA, and show that it captures the complex episodicity of methane ebullition. Our quantitative conceptualization opens the door to integrated modeling of methane transport to constrain global methane release from lakes and other methane-rich sediment systems, and to assess its climate feedbacks.« less
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NASA Astrophysics Data System (ADS)
Bauer, Klaus; Kulenkampff, Johannes; Henninges, Jan; Spangenberg, Erik
2016-04-01
Nuclear magnetic resonance (NMR) downhole data are analyzed with a new strategy to study gas hydrate-bearing sediments in the Mackenzie Delta (NW Canada). NMR logging is a powerful tool to study geological reservoir formations. The measurements are based on interactions between the magnetic moments of protons in geological formation water and an external magnetic field. Inversion of the measured raw data provides so-called transverse relaxation time (T2) distribution curves or spectra. Different parts of the T2 curve are related with distinct pore radii and corresponding fluid components. A common practice in the analysis of T2 distribution curves is to extract single-valued parameters such as apparent total porosity. Moreover, the derived total NMR apparent porosity and the gamma-gamma density log apparent porosity can be combined to estimate gas hydrate saturation in hydrate-bearing sediments. To avoid potential loss of information, in our new approach we analyze the entire T2 distribution curves as quasi-continuous signals to characterize the rock formation. The approach is applied to NMR data measured in gas hydrate research well Mallik 5L-38. We use self-organizing maps, a neural network clustering technique, to subdivide the data set of NMR T2 distribution curves into classes with a similar and distinctive signal shape. The method includes (1) preparation of data vectors, (2) unsupervised learning, (3) cluster definition, and (4) classification and depth mapping of all NMR signals. Each signal class thus represents a specific pore size distribution which can be interpreted in terms of distinct lithologies and reservoir types. A key step in the interpretation strategy is to reconcile the NMR classes with other log data not considered in the clustering analysis, such as gamma ray, photo-electric factor, hydrate saturation, and other logs. Our results defined six main lithologies within the target zone. Gas hydrate layers were recognized by their low signal amplitudes for all relaxation times. Highly concentrated methane hydrates occur in sand and shaly sand. Most importantly, two subtypes of hydrate-bearing sands and shaly sands were identified. They show distinct NMR signals and differ in hydrate saturation and gamma ray values. An inverse linear relationship between hydrate saturation and clay content was concluded. Finally, we infer that the gas hydrate is not grain coating, but rather, pore filling with matrix support is the preferred growth habit model for the studied formation.
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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.
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Assessing Gas-Hydrate Prospects on the North Slope of Alaska - Theoretical Considerations
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.
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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.
Principal component analysis of spectral decomposition results combined with amplitude and frequency 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 ofmore » Mexico is screened for direct hydrocarbon indicators for gas hydrate saturated sands.« less
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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.
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The Role of H2O in the Carbonation of Forsterite in Supercritical CO2
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kwak, Ja Hun; Hu, Jian Z.; Turcu, Romulus VF
2011-07-01
The water concentration dependence of forsterite carbonation in supercritical CO2 (scCO2) at 80°C and 76 bars was investigated by a combination of NMR, XRD, TEM and XPS. Reaction products were not detected using scCO2 alone without added H2O. When trace amounts of water were included, limited reaction was observed. Below saturation, reaction products were a mixture of partially hydrated/hydroxylated magnesium carbonates and hydroxylated silica species that were mainly in an amorphous state, forming a non-resolved layer on the forsterite surface. At water concentrations above saturation, where forsterite was in contact with both a CO2-saturated aqueous fluid and a water-saturated scCO2more » fluid, solid reaction products were magnesite (MgCO3) and an amorphous polymerized SiO2 dominated by Q4, and to a lesser extent by Q3 silica coordination. Formation of these phases implies H2O initially bound in precursor hydrated/hydroxylated reaction products was liberated, inducing further reaction. Hence, for a given fluid/mineral ratio there is a water threshold above which a significant portion of the water serves in a catalytic role where more extensive carbonation reaction occurs. Defining the role of water, even in low water content environments, is therefore critical to determining the long term impact of CO2 reactivity in the subsurface.« less
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NASA Astrophysics Data System (ADS)
Phillips, S. C.; You, K.; Borgfeldt, T.; Meyer, D.; Dong, T.; Flemings, P. B.
2016-12-01
We performed four dissociation experiments in which experimentally-formed methane hydrate was dissociated via slow, stepwise depressurization, revealing in situ salinity conditions. Overall, these results suggest the occurrence of local pore water freshening around dissociating hydrate in which bulk equilibrium behavior is limited by salt diffusion. Depressurization was performed at a constant confining temperature over 1 to 3 weeks by releasing small volumes of methane gas from the top of a vertically-oriented sample into an inverted graduated cylinder. We identify three distinct regimes of depressurization based on pressure drop behavior: (1) release of free gas down to initial hydrate dissociation at 3.3 MPa in NaBr or 4.64 MPa in NaCl, (2) dissociation of methane hydrate characterized by a slow, logarithmic increase in pressure after each gas release and (3) residual free gas release. Initial hydrate dissociation in NaCl brine at 4.64 MPa corresponds to the phase boundary for hydrate in 9.6 wt% NaCl. In the NaCl experiment, pressure increases of 0.16 MPa while the sample was shut in over 3 days likely correspond to a recovery in salinity of 0.7 wt. %. Salt ions likely diffuse from brine ahead of the hydrate front, based on a length scale for diffusion of NaCl of 6.3 cm for 3 days. In this experiment dissociation at bulk equilibrium is expected to decline from 4.54 to 4.04 MPa; however actual dissociation during 73 gas releases over 15 days, results in a pressure drop from 4.64 to 3.25 MPa. Hydrate samples were formed by injection of methane gas at 1 ºC and 12.24 MPa within a cylinder packed with medium-grained quartz sand and initially saturated in a 7 wt% NaBr or NaCl solution. In two experiments in which the system was thoroughly leak tested, total methane consumed during formation and recovered during depressurization match within 7% indicating this approach to be relatively accurate for determining total methane in experimental or pressure core samples.
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Geotechnical properties of core sample from methane hydrate deposits in Eastern Nankai Trough
NASA Astrophysics Data System (ADS)
Yoneda, J.; Masui, A.; Egawa, K.; Konno, Y.; Ito, T.; Kida, M.; Jin, Y.; Suzuki, K.; Nakatsuka, Y.; Tenma, N.; Nagao, J.
2013-12-01
To date, MH extraction has been simulated in several ways to help ensure the safe and efficient production of gas, with a particular focus on the investigation of landsliding, uneven settlement, and production well integrity. The mechanical properties of deep sea sediments and gas-hydrate-bearing sediments, typically obtained through material tests, are essential for the geomechanical response simulation to hydrate extraction. We conducted triaxial compression tests and the geotechnical properties of the sediments was investigated. Consolidated undrained compression tests were performed for silty sediments. And consolidated drained tests were performed for sandy samples. In addition, permeability was investigated from isotropic consolidation results. These core samples recovered from methane hydrate deposits of Daini Atsumi Knoll in Eastern Nankai Trough during the 2012 JOGMEC/JAPEX Pressure coring operation. The pressure core samples were rapidly depressurized on the ship and it were frozen using liquid nitrogen to prevent MH dissociation. Undrained shear strength of the core samples increase linearly with depth from sea floor. These core samples should be normally consolidated sample in-situ. Drained shear strength increases dramatically with hydrate saturation increases. Peak stress ratio q/p' of the core sample which has 73% of hydrate saturation was approximately 2.0 and it decrease down to 1.3 at the critical state. Dilatancy also changed from compressive tendency to dilative tendency with hydrate saturation increase. This study was financially supported by the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) that carries out Japan's Methane Hydrate R&D Program conducted by the Ministry of Economy, Trade and Industry (METI).
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Lee, Myung W.
2005-01-01
In order to assess the resource potential of gas hydrate deposits in the North Slope of Alaska, 3-D seismic and well data at Milne Point were obtained from BP Exploration (Alaska), Inc. The well-log analysis has three primary purposes: (1) Estimate gas hydrate or gas saturations from the well logs; (2) predict P-wave velocity where there is no measured P-wave velocity in order to generate synthetic seismograms; and (3) edit P-wave velocities where degraded borehole conditions, such as washouts, affected the P-wave measurement significantly. Edited/predicted P-wave velocities were needed to map the gas-hydrate-bearing horizons in the complexly faulted upper part of 3-D seismic volume. The estimated gas-hydrate/gas saturations from the well logs were used to relate to seismic attributes in order to map regional distribution of gas hydrate inside the 3-D seismic grid. The P-wave velocities were predicted using the modified Biot-Gassmann theory, herein referred to as BGTL, with gas-hydrate saturations estimated from the resistivity logs, porosity, and clay volume content. The effect of gas on velocities was modeled using the classical Biot-Gassman theory (BGT) with parameters estimated from BGTL.
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Chen, Po-Chun.; Huang, Wuu-Liang; Stern, Laura A.
2010-01-01
Polycrystalline methane gas hydrate (MGH) was synthesized using an ice-seeding method to investigate the influence of pressurization and ethanol on the hydrate formation rate and gas yield of the resulting samples. When the reactor is pressurized with CH4 gas without external heating, methane hydrate can be formed from ice grains with yields up to 25% under otherwise static conditions. The rapid temperature rise caused by pressurization partially melts the granular ice, which reacts with methane to form hydrate rinds around the ice grains. The heat generated by the exothermic reaction of methane hydrate formation buffers the sample temperature near the melting point of ice for enough time to allow for continuous hydrate growth at high rates. Surprisingly, faster rates and higher yields of methane hydrate were found in runs with lower initial temperatures, slower rates of pressurization, higher porosity of the granular ice samples, or mixtures with sediments. The addition of ethanol also dramatically enhanced the formation of polycrystalline MGH. This study demonstrates that polycrystalline MGH with varied physical properties suitable for different laboratory tests can be manufactured by controlling synthesis procedures or parameters. Subsequent dissociation experiments using a gas collection apparatus and flowmeter confirmed high methane saturation (CH 4·2O, with n = 5.82 ± 0.03) in the MGH. Dissociation rates of the various samples synthesized at diverse conditions may be fitted to different rate laws, including zero and first order.
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NASA Astrophysics Data System (ADS)
Schicks, Judith; Heeschen, Katja; Spangenberg, Erik; Luzi-Helbing, Manja; Beeskow-Strauch, Bettina; Priegnitz, Mike; Giese, Ronny; Abendroth, Sven; Thaler, Jan
2017-04-01
Natural gas hydrates occur at all active and passive continental margins, in permafrost regions, and deep lakes. Since they are supposed to contain enormous amounts of methane, gas hydrates are discussed as an energy resource. For the production of gas from hydrate bearing sediments, three different production methods were tested during the last decade: depressurization, thermal and chemical stimulation as well as combinations of these methods. In the framework of the SUGAR project we developed a Large Scale Reservoir Simulator (LARS) with a total volume of 425L to test these three methods in a pilot plant scale. For this purpose we formed hydrate from methane saturated brine in sediments under conditions close to natural gas hydrate deposits. The obtained hydrate saturations varied between 40-90%. Hydrate saturation and distribution were determined using electrical resistivity tomography (ERT). The volumes of the produced gas and water were determined and the gas phase was analyzed via gas chromatography. Multi-step depressurization, thermal stimulation applying in-situ combustion as well as chemical stimulation via the injection of CO2 and a CO2-N2-mixture were tested. Depressurization and thermal stimulation appear to be less complicated compared to the chemical stimulation. For the understanding of the macroscopically observed processes on a molecular level, we also performed experiments on a smaller scale using microscopic observation, Raman spectroscopy and X-ray diffraction. The results of these experiments are of particular importance for the understanding of the processes occurring during the CO2-CH4 swapping. Under the chosen experimental conditions the observations indicate a (partial) decomposition and reformation of the hydrate structure rather than a diffusion-controlled exchange of the molecules.
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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.
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Hydro-bio-geomechanical properties of hydrate-bearing sediments from Nankai Trough
Santamarina, J.C.; Dai, Shifeng; Terzariol, M.; Jang, Jeonghwan; Waite, William F.; Winters, William J.; Nagao, J.; Yoneda, J.; Konno, Y.; Fujii, T.; Suzuki, K.
2015-01-01
Natural hydrate-bearing sediments from the Nankai Trough, offshore Japan, were studied using the Pressure Core Characterization Tools (PCCTs) to obtain geomechanical, hydrological, electrical, and biological properties under in situ pressure, temperature, and restored effective stress conditions. Measurement results, combined with index-property data and analytical physics-based models, provide unique insight into hydrate-bearing sediments in situ. Tested cores contain some silty-sands, but are predominantly sandy- and clayey-silts. Hydrate saturations Sh range from 0.15 to 0.74, with significant concentrations in the silty-sands. Wave velocity and flexible-wall permeameter measurements on never-depressurized pressure-core sediments suggest hydrates in the coarser-grained zones, the silty-sands where Sh exceeds 0.4, contribute to soil-skeletal stability and are load-bearing. In the sandy- and clayey-silts, where Sh < 0.4, the state of effective stress and stress history are significant factors determining sediment stiffness. Controlled depressurization tests show that hydrate dissociation occurs too quickly to maintain thermodynamic equilibrium, and pressure–temperature conditions track the hydrate stability boundary in pure-water, rather than that in seawater, in spite of both the in situ pore water and the water used to maintain specimen pore pressure prior to dissociation being saline. Hydrate dissociation accompanied with fines migration caused up to 2.4% vertical strain contraction. The first-ever direct shear measurements on never-depressurized pressure-core specimens show hydrate-bearing sediments have higher sediment strength and peak friction angle than post-dissociation sediments, but the residual friction angle remains the same in both cases. Permeability measurements made before and after hydrate dissociation demonstrate that water permeability increases after dissociation, but the gain is limited by the transition from hydrate saturation before dissociation to gas saturation after dissociation. In a proof-of-concept study, sediment microbial communities were successfully extracted and stored under high-pressure, anoxic conditions. Depressurized samples of these extractions were incubated in air, where microbes exhibited temperature-dependent growth rates.
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Site selection for DOE/JIP gas hydrate drilling in the northern Gulf of Mexico
Hutchinson, Deborah; Shelander, Dianna; Dai, J.; McConnell, D.; Shedd, William; Frye, Matthew; Ruppel, Carolyn D.; Boswell, R.; Jones, Emrys; Collett, Timothy S.; Rose, Kelly K.; Dugan, Brandon; Wood, Warren T.
2008-01-01
n the late spring of 2008, the Chevron-led Gulf of Mexico Gas Hydrate Joint Industry Project (JIP) expects to conduct an exploratory drilling and logging campaign to better understand gas hydrate-bearing sands in the deepwater Gulf of Mexico. The JIP Site Selection team selected three areas to test alternative geological models and geophysical interpretations supporting the existence of potential high gas hydrate saturations in reservoir-quality sands. The three sites are near existing drill holes which provide geological and geophysical constraints in Alaminos Canyon (AC) lease block 818, Green Canyon (GC) 955, and Walker Ridge (WR) 313. At the AC818 site, gas hydrate is interpreted to occur within the Oligocene Frio volcaniclastic sand at the crest of a fold that is shallow enough to be in the hydrate stability zone. Drilling at GC955 will sample a faulted, buried Pleistocene channel-levee system in an area characterized by seafloor fluid expulsion features, structural closure associated with uplifted salt, and abundant seismic evidence for upward migration of fluids and gas into the sand-rich parts of the sedimentary section. Drilling at WR313 targets ponded sheet sands and associated channel/levee deposits within a minibasin, making this a non-structural play. The potential for gas hydrate occurrence at WR313 is supported by shingled phase reversals consistent with the transition from gas-charged sand to overlying gas-hydrate saturated sand. Drilling locations have been selected at each site to 1) test geological methods and models used to infer the occurrence of gas hydrate in sand reservoirs in different settings in the northern Gulf of Mexico; 2) calibrate geophysical models used to detect gas hydrate sands, map reservoir thicknesses, and estimate the degree of gas hydrate saturation; and 3) delineate potential locations for subsequent JIP drilling and coring operations that will collect samples for comprehensive physical property, geochemical and other analyses
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NASA Astrophysics Data System (ADS)
Uchida, T.; Waseda, A.; Fujii, T.
2006-12-01
The geological and geophysical evaluations have suggested worldwide methane contents in gas hydrate beneath deep sea floors as well as permafrost-related zones to about twice the total reserves of conventional and unconventional hydrocarbon. In 1998 and 2002 Mallik wells were drilled in the Canadian Arctic that clarified the characteristics of gas hydrate-concentrated sandy 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, whose saturations are evaluated higher than 80 percent in pore volume. In the Nankai Trough forearc basins and accretionary prisms developed and BSRs (bottom simulating reflectors) have been recognized widely, where the multiple wells were drilled in 2000 and 2004, and revealed the presence of pore-space hydrate in 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. High concentration of gas hydrate may need original pore space large enough to occur within a host sandy sediment, and this appears to be a similar mode for conventional petroleum accumulations. The distribution of a porous and coarser-grained sandy sediments should be one of the most important factors controlling occurrences and distributions of gas hydrate, as well as physicochemical conditions. Supplying methane for forming deep marine gas hydrate is commonly attributed to microbial conversion of organic material within the zone of stability or to migration of methane-containing fluids from a deeper source area. Pore water flows are considered to a macroscopic migration through faults/fractures and a microscopic flow in intergranular pore systems of sediment. We should assess the influence of methane supply on observable features of hydrate occurrences.
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Wang, Xiujuan; Qiang, Jin; Collett, Timothy S.; Shi, Hesheng; Yang, Shengxiong; Yan, Chengzhi; Li, Yuanping; Wang, Zhenzhen; Chen, Duanxin
2016-01-01
A new 3D seismic reflection data volume acquired in 2012 has allowed for the detailed mapping and characterization of gas hydrate distribution in the Pearl River Mouth Basin in the South China Sea. Previous studies of core and logging data showed that gas hydrate occurrence at high concentrations is controlled by the presence of relatively coarse-grained sediment and the upward migration of thermogenic gas from the deeper sediment section into the overlying gas hydrate stability zone (BGHSZ); however, the spatial distribution of the gas hydrate remains poorly defined. We used a constrained sparse spike inversion technique to generate acoustic-impedance images of the hydrate-bearing sedimentary section from the newly acquired 3D seismic data volume. High-amplitude reflections just above the bottom-simulating reflectors (BSRs) were interpreted to be associated with the accumulation of gas hydrate with elevated saturations. Enhanced seismic reflections below the BSRs were interpreted to indicate the presence of free gas. The base of the BGHSZ was established using the occurrence of BSRs. In areas absent of well-developed BSRs, the BGHSZ was calculated from a model using the inverted P-wave velocity and subsurface temperature data. Seismic attributes were also extracted along the BGHSZ that indicate variations reservoir properties and inferred hydrocarbon accumulations at each site. Gas hydrate saturations estimated from the inversion of acoustic impedance of conventional 3D seismic data, along with well-log-derived rock-physics models were also used to estimate gas hydrate saturations. Our analysis determined that the gas hydrate petroleum system varies significantly across the Pearl River Mouth Basin and that variability in sedimentary properties as a product of depositional processes and the upward migration of gas from deeper thermogenic sources control the distribution of gas hydrates in this basin.
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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.
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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.
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Geomechanical Behaviors of Laboratory-Formed Non-Cementing Hydrate-Bearing Sediments
NASA Astrophysics Data System (ADS)
Seol, Y.
2015-12-01
Natural hydrate-bearing sediments (HBS) have been known to exist with non-cementing pore habits, i.e., pore-filling, load-bearing, or patchy type. However, few laboratory studies have been conducted to characterize geomechanical behaviors of non-cementing CH4-HBS, which are of great importance in engineering the process of drilling and gas production in natural hydrate reservoir. In this study, we conducted multi-stage drained triaxial tests on laboratory synthesized CH4-HBS samples, which were formed in sand-clay mixtures (5%wt kaolinite) to have non-cementing habits. Three different effective confining stresses, σ3' = 0.69, 1.38, and 2.76 MPa, were applied on the HBS with the hydrate saturation, Sh, in the range of 0 to ~ 40%. The result confirms that the strength and stiffness of HBS increases with effective confining stress and hydrate saturation. It is also demonstrated that when compared to the cementing HBS, the non-cementing HBS has lower strength and cohesion, owing to less inter-particle adhesion effects from non-cementing hydrate.
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Pathak, Arup Kumar; Mukherjee, Tulsi; Maity, Dilip Kumar
2010-01-18
The vibrational (IR and Raman) and photoelectron spectral properties of hydrated iodine-dimer radical-anion clusters, I(2)(*-) x n H(2)O (n=1-10), are presented. Several initial guess structures are considered for each size of cluster to locate the global minimum-energy structure by applying a Monte Carlo simulated annealing procedure including spin-orbit interaction. In the Raman spectrum, hydration reduces the intensity of the I-I stretching band but enhances the intensity of the O-H stretching band of water. Raman spectra of more highly hydrated clusters appear to be simpler than the corresponding IR spectra. Vibrational bands due to simultaneous stretching vibrations of O-H bonds in a cyclic water network are observed for I(2)(*-) x n H(2)O clusters with n > or = 3. The vertical detachment energy (VDE) profile shows stepwise saturation that indicates closing of the geometrical shell in the hydrated clusters on addition of every four water molecules. The calculated VDE of finite-size small hydrated clusters is extrapolated to evaluate the bulk VDE value of I(2)(*-) in aqueous solution as 7.6 eV at the CCSD(T) level of theory. Structure and spectroscopic properties of these hydrated clusters are compared with those of hydrated clusters of Cl(2)(*-) and Br(2)(*-).
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NASA Astrophysics Data System (ADS)
Vieillard, Philippe; Blanc, Philippe; Fialips, Claire I.; Gailhanou, Hélène; Gaboreau, Stéphane
2011-10-01
The aim of the present work was to study the thermodynamic equilibria between water and a homo-ionic montmorillonite SWy-1 saturated by different cations. The choice of this smectite is justified by the large set of experimental data available from the literature for eight different interlayer cations: Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, Sr 2+, and Ba 2+. In particular, studies by Cases et al. (1992, 1997) and Bérend et al. (1995) are providing heat of adsorption data, pairs of desorption-adsorption isotherms, and information about the partition of adsorption-desorption water molecules between external surfaces and internal spaces. By calculating the effective amount of hydration water as the difference between the so-called gravimetric water and the surface covering water, a thermodynamic model was then developed, based on the concept of Ransom and Helgeson (1994) considering an asymmetric subregular binary solid solution between a fully hydrated and a anhydrous smectite. A set of six thermodynamic parameters ( ΔH∘hyd,S∘hyd and four Margules parameters) was extracted by a least square method from measurements of enthalpies of adsorption and paired adsorption-desorption isotherms for each interlayer cation. These six initial parameters were then used to determine a complete set of standard thermodynamic hydration parameters ( ΔH∘hyd,ΔG∘hyd,ΔS∘hyd, heat capacity, molar volume, and number of interlayer H 2O) and quantify, for each cation, the number of moles of hydration water molecules as a function of relative humidity and temperature. The validation of the standard state thermodynamic properties of hydration for each end member was carried out using three approaches: (1) a comparison with experimental isotherms obtained on hetero-ionic and homo-ionic SWy-1 smectite at different temperatures; (2) a comparison with the experimental integral enthalpy and entropy of hydration of the SWy-1 smectite; and (3) a comparison with experimental isotherms acquired on various smectites (Upton, MX80, Arizona) with different layer charges. Eventually, the present work demonstrates that, from a limited number of measurements, it is possible to provide the hydration thermodynamic parameters for hydrated smectites with different compositions and under different conditions of temperature and relative humidity, using the newly developed predictive model.
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Determining the mechanism and parameters of hydrate formation and loss in glucose.
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®
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Gas hydrate exploration of Porangahau Ridge, East Coast, North Island, New Zealand
NASA Astrophysics Data System (ADS)
Pecher, I. A.; Henrys, S. A.; Crutchley, G.; Toulmin, S.; Gorman, A. R.; Wood, W. T.; Kukowski, N.; Greinert, J.; Faure, K.; Coffin, R. B.
2007-12-01
During June and July 2006 the R/V Tangaroa collected high-resolution seismic profiles, EM 300 swath bathymetry, 3.5 sub-bottom, as well as water column echosounder data across Porangahau Ridge east of the North Island. Piston cores were recovered for pore water chemistry, microbiology, and paleoceanographic analyses. We also acquired heatflow data, CTDs, and seawater samples for water-column chemistry. The seismic data show amplitude anomalies beneath the ridge. The anomalies develop along a prominent N-S fault-propagation anticline. We analyzed reflection coefficients and conclude that the anomalies are most likely caused by free gas within the regional gas hydrate stability field as defined by the depth of bottom simulating reflections. We suggest that local warming associated with fluid expulsion through faults keeps the temperature at the anomalies outside of the gas hydrate stability field. Based on the seismic amplitudes, we predict at least ~7% of the pore space to be saturated with gas if gas is evenly distributed. Gas saturation is predicted to be almost 70% for "patchy'' gas distribution. For the pressure-temperature conditions beneath the ridge, gas at a saturation of 7% would form gas hydrate at a saturation of ~10% of pore space. Should the localized heat flow anomaly weaken, e.g., because of sealing of the faults, the ridge could become an area with significant hydrate deposits. We speculate that the Porangahau Ridge constitutes a gas hydrate "sweet spot" in the process of formation. Pore water chemistry shows a shoaling of the base of the sulfate reduction zone across this feature, indicative of elevated methane flux through the hydrate stability field. There is a distinct thermal anomaly across the Porangahau Ridge, albeit with a complex signature. On the other hand, there are no indications of methane expulsion into the water column, neither in the echosounder records nor in the water chemistry profiles from CTDs.
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NASA Astrophysics Data System (ADS)
Meazell, K.; Flemings, P. B.
2017-12-01
Grain size is a controlling factor of hydrate saturation within a Pleistocene channel-levee system investigated by the UT-GOM2-1 expedition within the deepwater northern Gulf of Mexico. Laser diffraction and settling experiments conducted on sediments from 413-440 meters below the seafloor reveal the presence of two interbedded lithologic units, identified as a silty sand and a clayey silt, according Shepard's classification system. The sand-rich lithofacies has low density and high p-wave velocity, suggesting a high degree of hydrate saturation. Conversely, the clay and silt dominated lithofacies is characterized by a higher density and low p-wave velocity, suggesting low hydrate saturation. The sand-rich lithofacies is well-sorted and displays abundant ripple lamination, indicative of deposition within a high-energy environment. The clayey-silt is poorly-sorted and lacks sedimentary structures. The two lithofacies are interbedded throughout the reservoir unit; however, the relative abundance of the sand-rich lithofacies increases with depth, suggesting a potential decrease in flow energy or sediment flux over time, resulting in the most favorable reservoir properties near the base of the unit.
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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.
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Ruppel, C.; Boswell, R.; Jones, E.
2008-01-01
The Gulf of Mexico Gas Hydrates Joint Industry Project (JIP) is a consortium of production and service companies and some government agencies formed to address the challenges that gas hydrates pose for deepwater exploration and production. In partnership with the U.S. Department of Energy and with scientific assistance from the U.S. Geological Survey and academic partners, the JIP has focused on studies to assess hazards associated with drilling the fine-grained, hydrate-bearing sediments that dominate much of the shallow subseafloor in the deepwater (>500 m) Gulf of Mexico. In preparation for an initial drilling, logging, and coring program, the JIP sponsored a multi-year research effort that included: (a) the development of borehole stability models for hydrate-bearing sediments; (b) exhaustive laboratory measurements of the physical properties of hydrate-bearing sediments; (c) refinement of new techniques for processing industry-standard 3-D seismic data to constrain gas hydrate saturations; and (d) construction of instrumentation to measure the physical properties of sediment cores that had never been removed from in situ hydrostatic pressure conditions. Following review of potential drilling sites, the JIP launched a 35-day expedition in Spring 2005 to acquire well logs and sediment cores at sites in Atwater Valley lease blocks 13/14 and Keathley Canyon lease block 151 in the northern Gulf of Mexico minibasin province. The Keathley Canyon site has a bottom simulating reflection at ???392 m below the seafloor, while the Atwater Valley location is characterized by seafloor mounds with an underlying upwarped seismic reflection consistent with upward fluid migration and possible shoaling of the base of the gas hydrate stability (BGHS). No gas hydrate was recovered at the drill sites, but logging data, and to some extent cores, suggest the occurrence of gas hydrate in inferred coarser-grained beds and fractures, particularly between 220 and 330 m below the seafloor at the Keathley Canyon site. This paper provides an overview of the results of the initial phases of the JIP work and introduces the 15 papers that make up this special volume on the scientific results related to the 2005 logging and drilling expedition.
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A New Critical State Model for Geomechanical Behavior of Methane Hydrate-Bearing Sands
NASA Astrophysics Data System (ADS)
Lin, J. S.; Xing, P.; Rutqvist, J.; Seol, Y.; Choi, J. H.
2014-12-01
Methane hydrate bearing sands behave like sands once the hydrate has dissociated, but could exhibit a substantial increase in the shear strength, stiffness and dilatancy as the degree of hydrate saturation increases. A new critical state model was developed that incorporates the spatially mobilized plane (SMP) concept, which has been proven effective in modeling mechanical behavior of sands. While this new model was built on the basic constructs of the critical state model, important enhancements were introduced. The model adopted the t-stress concept, which defined the normal and shear stress on the SMP, in describing the plastic behavior of the soil. In this connection the versatile Matsuoka-Nakai yield criterion was also employed, which defined the general three dimensional yield behavior. The resulting constitutive law was associated in the t-stress space, but became non-associated in the conventional p-q stress space as it should be for sands. The model also introduced a generalized degree of hydrate saturation concept that was modified from the pioneering work of the Cambridge group. The model gives stress change when the sands are subjected to straining, and/or to hydrate saturation changes. The performance of the model has been found satisfactory using data from laboratory triaxial tests on reconstituted samples and core samples taken from Nankai Trough, Japan. The model has been implemented into FLAC3D. A coupling example with the multiphase flow code, TOUGH+, is presented which simulates the mechanical behavior of a sample when the surrounding temperature has been raised, and the hydrate undergoes state change and no longer resides in the stability zone.
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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
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Kõiv, Margit; Liira, Martin; Mander, Ulo; Mõtlep, Riho; Vohla, Christina; Kirsimäe, Kalle
2010-10-01
We studied the phosphorus (P) binding capacity of Ca-rich alkaline filter material - hydrated oil shale ash (i.e. hydrated ash) in two onsite pilot-scale experiments (with subsurface flow filters) in Estonia: one using pre-treated municipal wastewater with total phosphorus (TP) concentration of 0.13-17.0 mg L(-1) over a period of 6 months, another using pre-treated landfill leachate (median TP 3.4 mg L(-1)) for a total of 12 months. The results show efficient P removal (median removal of phosphates 99%) in horizontal flow (HF) filters at both sites regardless of variable concentrations of several inhibitors. The P removal efficiency of the hydrated ash increases with increasing P loading, suggesting direct precipitation of Ca-phosphate phases rather than an adsorption mechanism. Changes in the composition of the hydrated ash suggest a significant increase in P concentration in all filters (e.g. from 489.5 mg kg(-1) in initial ash to 664.9 mg kg(-1) in the HF filter after one year in operation), whereas almost all TP was removed from the inflow leachate (R(2) = 0.99). Efficiency was high throughout the experiments (median outflow from HF hydrated ash filters 0.05-0.50 mg L(-1)), and P accumulation did not show any signs of saturation. Copyright © 2010 Elsevier Ltd. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Grant, Steven A.; Boitnott, Ginger E.; Korhonen, Charles J.
2006-04-15
Tricalcium silicate was hydrated at 274, 278, 283, 298, and 313 K in stirred suspensions of saturated CaO solutions under a nitrogen-gas atmosphere until the end of deceleratory period. The suspension conductivities and energy flows were measured continuously. The individual reaction rates for tricalcium silicate dissolution, calcium silicate hydrate precipitation, and calcium hydroxide precipitation were calculated from these measurements. The results suggest that the proportion of tricalcium silicate dissolved was determined by the rate of tricalcium silicate dissolution and the time to very rapid calcium hydroxide precipitation. The time to very rapid calcium hydroxide precipitation was more sensitive to changesmore » in temperature than was the rate of tricalcium silicate dissolution, so that the proportion of tricalcium silicate hydration dissolved by the deceleratory period increased with decreasing temperature. The average chain length of the calcium silicate hydrate ascertained by magic-angle spinning nuclear magnetic resonance spectroscopy increased with increasing temperature.« less
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Seismic imaging of gas hydrates in the northernmost South China sea
NASA Astrophysics Data System (ADS)
Wang, Tan K.; Yang, Ben Jhong; Deng, Jia-Ming; Lee, Chao-Shing; Liu, Char-Shine
2010-03-01
Horizon velocity analysis and pre-stack depth migration of seismic profiles collected by R/V Maurice Ewing in 1995 across the accretionary prism off SW Taiwan and along the continental slope of the northernmost South China Sea were implemented for identifying gas hydrates. Similarly, a survey of 32 ocean-bottom seismometers (OBS), with a spacing of about 500 m, was conducted for exploring gas hydrates on the accretionary prism off SW Taiwan in April 2006. Travel times of head wave, refraction, reflection and converted shear wave identified from the hydrophone, vertical and horizontal components of these OBS data were applied for imaging P-wave velocity and Poisson’s ratio of hydrate-bearing sediments. In the accretionary prism off SW Taiwan, we found hydrate-bearing sediment, with a thickness of about 100-200 m, a relatively high P-wave velocity of 1.87-2.04 km/s and a relatively low Poisson’s ratio of 0.445-0.455, below anticlinal ridges near imbricate emergent thrusts in the drainage system of the Penghu and Kaoping Canyons. Free-gas layer, with a thickness of about 30-120 m, a relatively low P-wave velocity of 1.4-1.8 km/s and a relatively high Poisson’s ratio (0.47-0.48), was also observed below most of the bottom-simulating reflectors (BSR). Subsequently, based on rock physics of the three-phase effective medium, we evaluated the hydrate saturation of about 12-30% and the free-gas saturation of about 1-4%. The highest saturation (30% and 4%) of gas hydrates is found below anticlines due to N-S trending thrust-bounded folds and NE-SW thrusting and strike-slip ramps in the lower slope of the accretionary prism. We suggest that fluid may have migrated through the relay-fault array due to decollement folding and gas hydrates have been trapped in anticlines formed by the basement rises along the thrust faults. In contrast, in the rifted continental margin of the northernmost South China Sea, P-wave velocities of 1.9-2.2 km/s and 1.3-1.6 km/s, and thicknesses of about 50-200 m and 100-200 m, respectively, for a hydrate layer and a free-gas layer were imaged below the remnant and erosional ridges in the upper continental slope. High P-wave velocity of hydrate-bearing sediment below erosional ridges may also indicate high saturation of hydrates there. Normal faults due to rifting in the South China continental crust may have provided conduits for gas migration below the erosional ridges where P-wave velocity of hydrate-bearing sediment in the passive continental margin of the northernmost South China Sea is greater than that in the active accretionary prism off SW Taiwan.
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Peculiarities of CO2 sequestration in the Permafrost area
NASA Astrophysics Data System (ADS)
Guryeva, Olga; Chuvilin, Evgeny; Moudrakovski, Igor; Lu, Hailong; Ripmeester, John; Istomin, Vladimir
2010-05-01
Natural gas and gas-condensate accumulations in North of Western Siberia contain an admixture of CO2 (about 0.5-1.0 mol.%). Recently, the development and transportation of natural gas in the Yamal peninsula has become of interest to Russian scientists. They suggest liquifaction of natural gas followed by delivery to consumers using icebreaking tankers. The technique of gas liquefaction requires CO2 to be absent from natural gas, and therefore the liquefaction technology includes the amine treatment of gas. This then leads to a problem with utilization of recovered CO2. It is important to note, that gas reservoirs in the northern part of Russia are situated within the Permafrost zone. The thickness of frozen sediment reaches 500 meters. That is why one of the promising places for CO2 storage can be gas-permeable collectors in under-permafrost horizons. The favorable factors for preserving CO2 in these places are as follows: low permeability of overlying frozen sediments, low temperatures, the existence of a CO2 hydrate stability zone, and the possibility of sequestration at shallow depths (less then 800-1000 meters). When CO2 (in liquid or gas phase) is pumped into the under-permafrost collectors it is possible that some CO2 migrates towards the hydrate stability zone and hydrate-saturated horizons can be formed. This can result on the one hand in the increase of effective capacity of the collector, and on the other hand, in the increase of isolating properties of cap rock. Therefore, CO2 injection sometimes can be performed without a good cap rock. In connection with the abovementioned, to elaborate an effective technology for CO2 injection it is necessary to perform a comprehensive experimental investigation with computer simulation of different utilization schemes, including the process of CO2 hydrate formation in porous media. There are two possible schemes of hydrate formation in pore medium of sediments: from liquid CO2 or the gas. The pore water in the sediment may be either in frozen or liquid states. To study these processes, an experimental investigation of hydrate formation kinetics from liquid and gaseous CO2 has been performed using the method of NMR imaging*. Experiments were made with samples of quartz sand (particles' diameter 0,21-0,297mm) with different water saturation in the range of temperatures between -3 and +8oC and pressures between 3 and 6 MPa. The experiments performed revealed the main regularities of hydrate accumulation from liquid CO2 in sediment. The influence of temperature on the rate of pore hydrate growth was analyzed. For example, the rate of hydrate growth at +7.2oC was 6 times smaller then at -3 оС. Fast hydrate formation from liquid CO2 was observed in sand samples with water saturation below 20-30%. With an increase in water saturation to 50%, the rate of hydrate formation decreased significantly, and when water saturation was 60% or more, nucleation was not observed during the time of the experiment (1-3 days). Experimental results revealed that pressure variation in the range between 4 and 6 MPa does not have any influence on the kinetics of hydrate formation from liquid CO2. Comparison of kinetics of hydrate formation from liquid and gas CO2 showed that hydrate accumulation is faster from gas CO2 then from liquid CO2. Thus, 50% of pore water that reacted with liquid CO2 transformed into hydrate in 0.8 hours after nucleation, and when reacted with CO2-gas, it transformed in 0.3 hours. The completed experiments allowed us to consider the peculiarities of hydrate formation and filtration of liquid and gaseous CO2 towards the hydrate stability zone, which is important to take into account during the elaboration of industrial techniques of CO2 injection in under-permafrost collectors. * Experiments have been made in the laboratory of NRC of Canada.
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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.
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Reservoir Models for Gas Hydrate Numerical Simulation
NASA Astrophysics Data System (ADS)
Boswell, R.
2016-12-01
Scientific and industrial drilling programs have now providing detailed information on gas hydrate systems that will increasingly be the subject of field experiments. The need to carefully plan these programs requires reliable prediction of reservoir response to hydrate dissociation. Currently, a major emphasis in gas hydrate modeling is the integration of thermodynamic/hydrologic phenomena with geomechanical response for both reservoir and bounding strata. However, also critical to the ultimate success of these efforts is the appropriate development of input geologic models, including several emerging issues, including (1) reservoir heterogeneity, (2) understanding of the initial petrophysical characteristics of the system (reservoirs and seals), the dynamic evolution of those characteristics during active dissociation, and the interdependency of petrophysical parameters and (3) the nature of reservoir boundaries. Heterogeneity is ubiquitous aspect of every natural reservoir, and appropriate characterization is vital. However, heterogeneity is not random. Vertical variation can be evaluated with core and well log data; however, core data often are challenged by incomplete recovery. Well logs also provide interpretation challenges, particularly where reservoirs are thinly-bedded due to limitation in vertical resolution. This imprecision will extend to any petrophysical measurements that are derived from evaluation of log data. Extrapolation of log data laterally is also complex, and should be supported by geologic mapping. Key petrophysical parameters include porosity, permeability and it many aspects, and water saturation. Field data collected to date suggest that the degree of hydrate saturation is strongly controlled by/dependant upon reservoir quality and that the ratio of free to bound water in the remaining pore space is likely also controlled by reservoir quality. Further, those parameters will also evolve during dissociation, and not necessary in a simple/linear way. Significant progress has also occurred in recent years with regard to the geologic characterization of reservoir boundaries. Vertical boundaries with overlying clay-rich "seals" are now widely-appreciated to have non-zero permeability, and lateral boundaries are sources of potential lateral fluid flow.
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Methane gas hydrate effect on sediment acoustic and strength properties
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.
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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).
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Convective Hydration and Dehydration in the Tropical Upper Troposphere
NASA Astrophysics Data System (ADS)
Schoeberl, M. R.; Pfister, L.; Ueyama, R.; Jensen, E. J.; Avery, M. A.; Dessler, A. E.
2017-12-01
As air moves up through the tropical tropopause layer (TTL), water vapor condenses and ice falls out irreversibly dehydrating the air. Convection penetrates the TTL changing the concentration of water vapor. Using a Lagrangian model, we find that convection hydrates the local TTL if the air is sub-saturated, and dehydrates the air if the layer is super-saturated. We analyze the frequency and location of both types of convective events using our forward domain filling trajectory model with satellite observed convection. We find that hydration events exceed dehydration events at all levels above 360K although because few convective events penetrate to the upper TTL, the net water vapor impact weakens with altitude. Maps of hydration and dehydration events show that both types of events occur where convection is strongest The average, convection above 360K adds about 0.5 ppmv of water to the stratosphere.
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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.
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Well log characterization of natural gas-hydrates
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.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Rose, Kelly K.; Johnson, Joel E.; Torres, Marta E.
In addition to well established properties that control the presence or absence of the hydrate stability zone, such as pressure, temperature, and salinity, additional parameters appear to influence the concentration of gas hydrate in host sediments. The stratigraphic record at Site 17A in the Andaman Sea, eastern Indian Ocean, illustrates the need to better understand the role pore-scale phenomena play in the distribution and presence of marine gas hydrates in a variety of subsurface settings. In this paper we integrate field-generated datasets with newly acquired sedimentology, physical property, imaging and geochemical data with mineral saturation and ion activity products ofmore » key mineral phases such as amorphous silica and calcite, to document the presence and nature of secondary precipitates that contributed to anomalous porosity preservation at Site 17A in the Andaman Sea. This study demonstrates the importance of grain-scale subsurface heterogeneities in controlling the occurrence and distribution of concentrated gas hydrate accumulations in marine sediments, and document the importance that increased permeability and enhanced porosity play in supporting gas concentrations sufficient to support gas hydrate formation. The grain scale relationships between porosity, permeability, and gas hydrate saturation documented at Site 17A likely offer insights into what may control the occurrence and distribution of gas hydrate in other sedimentary settings.« less
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Biot-type scattering effects in gas hydrate-bearing sediments
NASA Astrophysics Data System (ADS)
Rubino, J. GermáN.; Ravazzoli, Claudia L.; Santos, Juan E.
2008-06-01
This paper studies the energy conversions that take place at discontinuities within gas hydrate-bearing sediments and their influence on the attenuation of waves traveling through these media. The analysis is based on a theory recently developed by some of the authors, to describe wave propagation in multiphasic porous media composed of two solids saturated by a single-phase fluid. Real data from the Mallik 5L-38 Gas Hydrate Research well are used to calibrate the physical model, allowing to obtain information about the characteristics of the cementation between the mineral grains and gas hydrates for this well. Numerical experiments show that, besides energy conversions to reflected and transmitted classical waves, significant fractions of the energy of propagating waves may be converted into slow-waves energy at plane heterogeneities within hydrated sediments. Moreover, numerical simulations of wave propagation show that very high levels of attenuation can take place in the presence of heterogeneous media composed of zones with low and high gas hydrate saturations with sizes smaller or on the order of the wavelengths of the fast waves at sonic frequencies. These attenuation levels are in very good agreement with those measured at the Mallik 5L-38 Gas Hydrate Research Well, suggesting that these scattering-type effects may be a key-parameter to understand the high sonic attenuation observed at gas hydrate-bearing sediments.
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Submarine landslides triggered by destabilization of high-saturation hydrate anomalies
NASA Astrophysics Data System (ADS)
Handwerger, Alexander L.; Rempel, Alan W.; Skarbek, Rob M.
2017-07-01
Submarine landslides occur along continental margins at depths that often intersect the gas hydrate stability zone, prompting suggestions that slope stability may be affected by perturbations that arise from changes in hydrate stability. Here we develop a numerical model to identify the conditions under which the destabilization of hydrates results in slope failure. Specifically, we focus on high-saturation hydrate anomalies at fine-grained to coarse-grained stratigraphic boundaries that can transmit bridging stresses that decrease the effective stress at sediment contacts and disrupt normal sediment consolidation. We evaluate slope stability before and after hydrate destabilization. Hydrate anomalies act to significantly increase the overall slope stability due to large increases in effective cohesion. However, when hydrate anomalies destabilize there is a loss of cohesion and increase in effective stress that causes the sediment grains to rapidly consolidate and generate pore pressures that can either trigger immediate slope failure or weaken the surrounding sediment until the pore pressure diffuses away. In cases where failure does not occur, the sediment can remain weakened for months. In cases where failure does occur, we quantify landslide dynamics using a rate and state frictional model and find that landslides can display either slow or dynamic (i.e., catastrophic) motion depending on the rate-dependent properties, size of the stress perturbation, and the size of the slip patch relative to a critical nucleation length scale. Our results illustrate the fundamental mechanisms through which the destabilization of gas hydrates can pose a significant geohazard.
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Hassanpouryouzband, Aliakbar; Yang, Jinhai; Tohidi, Bahman; Chuvilin, Evgeny; Istomin, Vladimir; Bukhanov, Boris; Cheremisin, Alexey
2018-04-03
Injection of flue gas or CO 2 -N 2 mixtures into gas hydrate reservoirs has been considered as a promising option for geological storage of CO 2 . However, the thermodynamic process in which the CO 2 present in flue gas or a CO 2 -N 2 mixture is captured as hydrate has not been well understood. In this work, a series of experiments were conducted to investigate the dependence of CO 2 capture efficiency on reservoir conditions. The CO 2 capture efficiency was investigated at different injection pressures from 2.6 to 23.8 MPa and hydrate reservoir temperatures from 273.2 to 283.2 K in the presence of two different saturations of methane hydrate. The results showed that more than 60% of the CO 2 in the flue gas was captured and stored as CO 2 hydrate or CO 2 -mixed hydrates, while methane-rich gas was produced. The efficiency of CO 2 capture depends on the reservoir conditions including temperature, pressure, and hydrate saturation. For a certain reservoir temperature, there is an optimum reservoir pressure at which the maximum amount of CO 2 can be captured from the injected flue gas or CO 2 -N 2 mixtures. This finding suggests that it is essential to control the injection pressure to enhance CO 2 capture efficiency by flue gas or CO 2 -N 2 mixtures injection.
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NASA Astrophysics Data System (ADS)
Strauch, B.; Heeschen, K. U.; Priegnitz, M.; Abendroth, S.; Spangenberg, E.; Thaler, J.; Schicks, J. M.
2015-12-01
The GFZ's LArge Reservoir Simulator LARS allows for the simulation of the 2008 Mallik gas hydrate production test and the comparison of fluid flow patterns and their driving forces. Do we see the gas flow pattern described for Mallik [Uddin, M. et al., J. Can. Petrol Tech, 50, 70-89, 2011] in a pilot scale test? If so, what are the driving forces? LARS has a network of temperature sensors and an electric resistivity tomography (ERT) enabling a good spatial resolution of gas hydrate occurrences, water and gas distribution, and changes in temperature in the sample. A gas flow meter and a water trap record fluid flow patterns and a backpressure valve has controlled the depressurization equivalent to the three pressure stages (7.0 - 5.0 - 4.2 MPa) applied in the Mallik field test. The environmental temperature (284 K) and confining pressure (13 MPa) have been constant. The depressurization induced immediate endothermic gas hydrate dissociation until re-establishment of the stability conditions by a consequent temperature decrease. Slight gas hydrate dissociation continued at the top and upper lateral border due to the constant heat input from the environment. Here transport pathways were short and permeability higher due to lower gas hydrate saturation. At pressures of 7.0 and 5.0 MPa the LARS tests showed high water flow rates and short irregular spikes of gas production. The gas flow patterns at 4.2 MPa and 3.0MPa resembled those of the Mallik test. In LARS the initial gas surges overlap with times of hydrate instability while water content and lengths of pathways had increased. Water production was at a minimum. A rapidly formed continuous gas phase caused the initial gas surges and only after gas hydrate dissociation decreased to a minimum the single gas bubbles get trapped before slowly coalescing again. In LARS, where pathways were short and no additional water was added, a transport of microbubbles is unlikely to cause a gas surge as suggested for Mallik.
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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.
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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.
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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.
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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.
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NASA Astrophysics Data System (ADS)
Enkin, Randolph J.; Baker, Judith; Nourgaliev, Danis; Iassonov, Pavel; Hamilton, Tark S.
2007-06-01
The J meter coercivity spectrometer is a machine capable of rapid and simple measurement of magnetic hysteresis, isothermal remanence acquisition and magnetic viscosity of rocks and sediments. The J meter was used to study a suite of samples collected from strata in the gas hydrate-bearing JAPEX/JNOC/GSC Mallik 5L-38 well (69.5°N, 134.6°W) in the Mackenzie Delta of the northwestern Canadian Arctic. The Day plot of magnetic hysteresis ratios for these samples is exotic in that the points do not plot along a hyperbola as is usually observed. Rather, they plot as a scatter which is shown to contour into vertical slices using coercivity field (HC) or saturation magnetization (JS), and horizontal slices using the relative quantity of superparamagnetism (JSPM/JS). Optical microscopy reveals that the magnetic minerals are detrital magnetite and authigenic greigite. Greigite is dominant in sands which in situ had >70% gas hydrate saturation and in silts in which gas hydrate growth was blocked by insufficient porosity. We infer that the silts were the accumulation sites for solutes which had been excluded from the pore waters in neighboring coarser-grained sediments during the course of gas hydrate formation. Consequently, we conclude that magnetic properties are related to gas hydrate-related processes, and as such, may have potential as a method of remote sensing for gas hydrate deposits.
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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.
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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.
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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.
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Torres, M.E.; Collett, T.S.; Rose, K.K.; Sample, J.C.; Agena, W.F.; Rosenbaum, E.J.
2011-01-01
The BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well was drilled and cored from 606.5 to 760.1. m on the North Slope of Alaska, to evaluate the occurrence, distribution and formation of gas hydrate in sediments below the base of the ice-bearing permafrost. Both the dissolved chloride and the isotopic composition of the water co-vary in the gas hydrate-bearing zones, consistent with gas hydrate dissociation during core recovery, and they provide independent indicators to constrain the zone of gas hydrate occurrence. Analyses of chloride and water isotope data indicate that an observed increase in salinity towards the top of the cored section reflects the presence of residual fluids from ion exclusion during ice formation at the base of the permafrost layer. These salinity changes are the main factor controlling major and minor ion distributions in the Mount Elbert Well. The resulting background chloride can be simulated with a one-dimensional diffusion model, and the results suggest that the ion exclusion at the top of the cored section reflects deepening of the permafrost layer following the last glaciation (???100 kyr), consistent with published thermal models. Gas hydrate saturation values estimated from dissolved chloride agree with estimates based on logging data when the gas hydrate occupies more than 20% of the pore space; the correlation is less robust at lower saturation values. The highest gas hydrate concentrations at the Mount Elbert Well are clearly associated with coarse-grained sedimentary sections, as expected from theoretical calculations and field observations in marine and other arctic sediment cores. ?? 2009 Elsevier Ltd.
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NASA Astrophysics Data System (ADS)
Yoneda, J.; Masui, A.; Konno, Y.; Jin, Y.; Kida, M.; Suzuki, K.; Nakatsuka, Y.; Tenma, N.; Nagao, J.
2014-12-01
Natural gas hydrate-bearing pressure core sediments have been sheared in compression using a newly developed Transparent Acrylic Cell Triaxial Testing (TACTT) system to investigate the geophysical and geomechanical behavior of sediments recovered from the deep seabed in the Eastern Nankai Trough, the first Japanese offshore production test region. The sediments were recovered by hybrid pressure core system (hybrid PCS) and pressure cores were cut by pressure core analysis tools (PCATs) on board. These pressure cores were transferred to the AIST Hokkaido centre and trimmed by pressure core non-destructive analysis tools (PNATs) for TACTT system which maintained the pressure and temperature conditions within the hydrate stability boundary, through the entire process of core handling from drilling to the end of laboratory testing. An image processing technique was used to capture the motion of sediment in a transparent acrylic cell, and digital photographs were obtained at every 0.1% of vertical strain during the test. Analysis of the optical images showed that sediments with 63% hydrate saturation exhibited brittle failure, although nonhydrate-bearing sediments exhibited ductile failure. In addition, the increase in shear strength with hydrate saturation increase of natural gas hydrate is in agreement with previous data from synthetic gas hydrate. This research was financially supported by the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) that carries out Japan's Methane Hydrate R&D Program by the Ministry of Economy, Trade and Industry (METI).
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NASA Astrophysics Data System (ADS)
Poveshchenko, Yu A.; Podryga, V. O.; Rahimly, P. I.; Sharova, Yu S.
2018-01-01
The thermodynamically equilibrium model for splitting by the physical processes of a two-component three-phase filtration fluid dynamics with gas hydrate inclusions is considered in the paper, for which a family of two-layer completely conservative difference schemes of the support operators method with time weights profiled in space is constructed. On the irregular grids of the theory of the support-operators method applied to the specifics of the processes of transfer of saturations and internal energies of water and gas in a medium with gas hydrate inclusions, methods of directwind approximation of these processes are considered. These approximations preserve the continual properties of divergence-gradient operations in their difference form and are related to the velocity field providing saturations transfer and internal energies of fluids. Fluid dynamics with gas hydrate inclusions are also calculated on the basis of the proposed approach, in particular, in areas of severe pressure depression in the collector space.
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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.
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Inks, T.L.; Agena, W.F.
2008-01-01
In February 2007, the Mt. Elbert Prospect stratigraphic test well, Milne Point, North Slope Alaska encountered thick methane gas hydrate intervals, as predicted by 3D seismic interpretation and modeling. Methane gas hydrate-saturated sediment was found in two intervals, totaling more than 100 ft., identified and mapped based on seismic character and wavelet modeling.
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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
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NASA Astrophysics Data System (ADS)
Kim, H.; Kwon, T.; Cho, G.
2012-12-01
Synthesizing gas hydrate in a fine-grained natural seabed sediment sample, mainly composed of silty-to-clayey soils, has been hardly attempted due to the low permeability. It has been known that hydrate loci in pore spaces and heterogeneity of hydrate growth in core-scale play a critical role in determining physical properties of hydrate-bearing sediments. In the presented study, we attempted to identify the effect of hydrate growth morphology on seismic velocities in natural fine-grained sediments sampled from the Ulleung Basin in East Sea. We synthesized CO2 hydrate in clayey silt sediments in an instrumented oedometric cell and measured seismic velocities during hydrate formation and loading processes. Herein, we present the experiment results on P-wave and S-wave velocities of gas hydrate-bearing fine-grained sediments. It is found that the geophysical properties of gas hydrate-bearing sediments are governed by hydrate saturation and effective stress as well as morphological feature of hydrate formation in sediments.
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Zhang, Wenhua; Wang, Zixin; Song, Xingrong; Fan, Yanting; Tian, Hang; Li, Bilian
2016-03-01
Chloral hydrate, a commonly used sedative in children during noninvasive diagnostic procedures, is associated with side effects like prolonged sedation, paradoxical excitement, delirium, and unpleasant taste. Dexmedetomidine, a highly selective α-2 agonist, has better pharmacokinetic properties than chloral hydrate. We conducted this prospective, double-blind, randomized controlled trial to evaluate efficacy of intranasal dexmedetomidine with that of a second oral dose of chloral hydrate for rescue sedation during magnetic resonance imaging (MRI) studies in infants. One hundred and fifty infants (age group: 1-6 months), who were not adequately sedated after initial oral dose of 50 mg · kg(-1) chloral hydrate, were randomly divided into three groups with the following protocol for each group. Group C: second oral dose chloral hydrate 25 mg · kg(-1); Group L and Group H: intranasal dexmedetomidine in a dosage of 1 and 2 mcg · kg(-1), respectively. Status of sedation, induction time, time to wake up, vital signs, oxygen saturation, and recovery characteristics were recorded. Successful rescue sedation in Groups C, L, and H were achieved in 40 (80%), 47 (94%), and 49 (98%) of infants, respectively, on an intention to treat analysis, and the proportion of infants successfully sedated in Group H was more than that of Group L (P ˂ 0.01). There were no significant differences in sedation induction time; however, the time to wake up was significantly shorter in Group L as compared to that in Group C or H (P < 0.01). No significant adverse hemodynamic or hypoxemic effects were observed in the study. Intranasal dexmedetomidine induced satisfactory rescue sedation in 1- to 6-month-old infants during MRI study, and appears to cause sedation in a dose-dependent manner. © 2015 John Wiley & Sons Ltd.
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NASA Astrophysics Data System (ADS)
Peltzer, E. T.; Walz, P. M.; Brewer, P. G.
2016-02-01
Oil droplets rising from the sea floor, whether from seeps or well leakage, contain very large quantities of dissolved gas that profoundly affects their density and critical oil-water interfacial characteristics. The primary dissolved gas is methane which may be up to 30% of the molar volume. This can create a hydrate skin as the methane gas is shed from the oil as it rises through the water column, thus decreasing in pressure and increasing in temperature, and steadily changing the rising droplet buoyancy. We have explored this phenomenon by executing controlled ROV based experiments with a "bubble cup" technique in which a small volume of gas saturated decane (saturated with pure methane, a mix of methane and nitrogen , or a mix of methane and CO2) is interrogated by laser Raman spectroscopy. The use of decane as an oil "substitute" is required since natural oil samples are highly fluorescent due to the presence of polycyclic aromatic hydrocarbons. We have devised Matlab techniques for extracting the spectroscopic dissolved methane signal from the thicket of decane peaks that surround it. We have directly observed the rate at which gases are lost from the "oil" per unit area at depths in the water column that are both within and outside the hydrate forming phase boundary. We have compared the behavior of both a non-hydrate forming dissolved gas (nitrogen) with CO2 where the hydrate phase boundary is at significantly shallower depth. The results indicate complex interfacial behavior and physical chemistry. We did not observe direct gas bubble formation on the decane outer surface but did observe gas bubble formation within the oil droplets as they rose through the water column. Because there are significant energy barriers for homogeneous bubble formation within the decane phase, we took this as evidence of significant gas super-saturation within the oil droplet. The gas loss rates increased significantly in all cases when the hydrate phase boundary was crossed.
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NASA Astrophysics Data System (ADS)
Yin, Z.; Moridis, G. J.; Chong, Z. R.; Linga, P.
2017-12-01
Methane hydrates (MH) are known to trap enormous amounts of CH4 in oceanic and permafrost-associated deposits, and are being considered as a potential future energy source. Several powerful numerical simulators were developed to describe the behavior of natural hydrate-bearing sediments (HBS). The complexity and strong nonlinearities in HBS do not allow analytical solutions for code validation. The only reliable method to develop confidence in these models is through comparisons to laboratory and/or field experiments. The objective of this study is to reproduce numerically the results from earlier experiments of MH formation and depressurization (and the corresponding fluid production) in 1.0L reactor involving unconsolidated sand, thus validating and calibrating the TOUGH+Hydrate v1.5 simulator. We faithfully describe the reactor geometry and the experimental process that involves both hydrate formation and dissociation. We demonstrate that the laboratory experiments can only be captured by a kinetic hydration model. There is an excellent agreement between observations and predictions (a) of the cumulative gas depletion (during formation) and production (during dissociation) and (b) of pressure over time. The temperature agreement is less satisfactory, and the deviations are attributed to the fixed locations of the limited number of sensors that cannot fully capture the hydrate heterogeneity. We also predict the spatial distributions over time of the various phase (gas, aqueous and hydrate) saturations. Thus, hydrates form preferentially along the outer boundary of the sand core, and the hydrate front moves inward leaving a significant portion of the sand at the center hydrate-free. During depressurization, dissociation advances again inward from the reactor boundary to the center of the reactor. As expected, methane gas accumulates initially at the locations of most intense dissociation, and then gradually migrates to the upper section of the reactor because of buoyancy and of the pressure gradient caused by the pressure outlet. Sensitivity analysis indicates that the composite thermal conductivity of the HBS and the kinetic parameters of the hydration reaction are the dominant factors. The absolute permeability of the sand does not play a significant role in this small reactor.
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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.
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QUANTIFICATION OF IN-SITU GAS HYDRATES WITH WELL LOGS.
Collett, Timothy S.; Godbole, Sanjay P.; Economides, Christine
1984-01-01
This study evaluates in detail the expected theoretical log responses and the actual log responses within one stratigraphically controlled hydrate horizon in six wells spaced throughout the Kuparuk Oil Field. Detailed examination of the neutron porosity and sonic velocity responses within the horizon is included. In addition, the theoretical effect of the presence of hydrates on the neutron porosity and sonic velocity devices has been examined in order to correct for such an effect on the calculation of formation properties such as porosity and hydrate saturation. Also presented in the paper is a technique which allows the conclusive identification of a potential hydrate occurrence.
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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.
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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.
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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.
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Efficiency of a borehole seal by means of pre-compacted bentonite blocks
NASA Astrophysics Data System (ADS)
Van Geet, M.; Volckaert, G.; Bastiaens, W.; Maes, N.; Weetjens, E.; Sillen, X.; Vallejan, B.; Gens, A.
The backfilling and sealing of shafts and galleries is an essential part of the design of underground repositories for high-level radioactive waste. Part of the EC funded project RESEAL studied the feasibility of sealing off a borehole in plastic Boom Clay by means of pre-compacted bentonite blocks. Two bentonites, namely the FoCa and Serrata clay, have been used. Based on laboratory tests, the bentonite blocks had an initial dry density of about 1.8 g/cm 3 to obtain a swelling pressure of about 4.4 MPa, corresponding to the in situ lithostatic stress, at full saturation. The set-up was equipped with several sensors to follow-up the behaviour of the seal and the surrounding host rock during hydration. Full saturation was reached after five months and was mainly reached by natural hydration. Swelling pressure was lower than originally foreseen due to the slow reconsolidation of the host rock. Later on, the efficiency of the seal with respect to water, gas and radionuclide migration was tested. The in situ measured permeability of the seals was about 5 × 10 -13 m/s. A gas breakthrough experiment did not show any preferential gas migration through the seal. No evidences of a preferential pathway could be detected from 125I tracer test results.
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NASA Astrophysics Data System (ADS)
Peng, C.; Zou, C.; Tang, Y.; Liu, A.; Hu, X.
2017-12-01
In the Qilian Mountain, gas hydrates not only occur in pore spaces of sandstones, but also fill in fractures of mudstones. This leads to the difficulty in identification and evaluation of gas hydrate reservoir from resistivity and velocity logs. Understanding electrical conductive mechanism is the basis for log interpretation. However, the research is insufficient in this area. We have collected well logs from 30 wells in this area. Well logs and rock samples from DK-9, DK-11 and DK-12 wells were used in this study. The experiments including SEM, thin section, NMR, XRD, synthesis of gas hydrate in consolidated rock cores under low temperature and measurement of their resistivity and others were performed for understanding the effects of pore structure, rock composition, temperature and gas hydrate on conductivity. The results show that the porosity of reservoir of pore filling type is less than 10% and its clay mineral content is high. As good conductive passages, fractures can reduce resistivity of water-saturated rock. If fractures in the mudstone are filled by calcite, resistivity increases significantly. The resistivity of water-saturated rock at 2°C is twice of that at 18°C. The gas hydrate formation process in the sandstone was studied by resistivity recorded in real time. In the early stage of gas hydrate formation, the increase of residual water salinity may lead to the decrease of resistivity. In the late stage of gas hydrate formation, the continuity decrease of water leads to continuity increase of resistivity. In summary, fractures, rock composition, temperature and gas hydrate are important factors influencing resistivity of formation. This study is helpful for more accurate evaluation of gas hydrate from resistivity log. Acknowledgment: We acknowledge the financial support of the National Special Program for Gas Hydrate Exploration and Test-production (GZH201400302).
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Anderson, B.J.; Kurihara, M.; White, M.D.; Moridis, G.J.; Wilson, S.J.; Pooladi-Darvish, M.; Gaddipati, M.; Masuda, Y.; Collett, T.S.; Hunter, R.B.; Narita, H.; Rose, K.; Boswell, R.
2011-01-01
Following the results from the open-hole formation pressure response test in the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well (Mount Elbert well) using Schlumberger's Modular Dynamics Formation Tester (MDT) wireline tool, the International Methane Hydrate Reservoir Simulator Code Comparison project performed long-term reservoir simulations on three different model reservoirs. These descriptions were based on 1) the Mount Elbert gas hydrate accumulation as delineated by an extensive history-matching exercise, 2) an estimation of the hydrate accumulation near the Prudhoe Bay L-pad, and 3) a reservoir that would be down-dip of the Prudhoe Bay L-pad and therefore warmer and deeper. All of these simulations were based, in part, on the results of the MDT results from the Mount Elbert Well. The comparison group's consensus value for the initial permeability of the hydrate-filled reservoir (k = 0.12 mD) and the permeability model based on the MDT history match were used as the basis for subsequent simulations on the three regional scenarios. The simulation results of the five different simulation codes, CMG STARS, HydrateResSim, MH-21 HYDRES, STOMP-HYD, and TOUGH+HYDRATE exhibit good qualitative agreement and the variability of potential methane production rates from gas hydrate reservoirs is illustrated. As expected, the predicted methane production rate increased with increasing in situ reservoir temperature; however, a significant delay in the onset of rapid hydrate dissociation is observed for a cold, homogeneous reservoir and it is found to be repeatable. The inclusion of reservoir heterogeneity in the description of this cold reservoir is shown to eliminate this delayed production. Overall, simulations utilized detailed information collected across the Mount Elbert reservoir either obtained or determined from geophysical well logs, including thickness (37 ft), porosity (35%), hydrate saturation (65%), intrinsic permeability (1000 mD), pore water salinity (5 ppt), and formation temperature (3.3-3.9 ??C). This paper presents the approach and results of extrapolating regional forward production modeling from history-matching efforts on the results from a single well test. ?? 2010 Elsevier Ltd.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Anderson, Brian J.; Kurihara, Masanori; White, Mark D.
2011-02-01
Following the results from the open-hole formation pressure response test in the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well (Mount Elbert well) using Schlumberger's Modular Dynamics Formation Tester (MDT) wireline tool, the International Methane Hydrate Reservoir Simulator Code Comparison project performed long-term reservoir simulations on three different model reservoirs. These descriptions were based on 1) the Mount Elbert gas hydrate accumulation as delineated by an extensive history-matching exercise, 2) an estimation of the hydrate accumulation near the Prudhoe Bay L-pad, and 3) a reservoir that would be down-dip of the Prudhoe Bay L-pad and therefore warmer and deeper. Allmore » of these simulations were based, in part, on the results of the MDT results from the Mount Elbert Well. The comparison group's consensus value for the initial permeability of the hydrate-filled reservoir (k = 0.12 mD) and the permeability model based on the MDT history match were used as the basis for subsequent simulations on the three regional scenarios. The simulation results of the five different simulation codes, CMG STARS, HydrateResSim, MH-21 HYDRES, STOMP-HYD, and TOUGH+HYDRATE exhibit good qualitative agreement and the variability of potential methane production rates from gas hydrate reservoirs is illustrated. As expected, the predicted methane production rate increased with increasing in situ reservoir temperature; however, a significant delay in the onset of rapid hydrate dissociation is observed for a cold, homogeneous reservoir and it is found to be repeatable. The inclusion of reservoir heterogeneity in the description of this cold reservoir is shown to eliminate this delayed production. Overall, simulations utilized detailed information collected across the Mount Elbert reservoir either obtained or determined from geophysical well logs, including thickness (37 ft), porosity (35%), hydrate saturation (65%), intrinsic permeability (1000 mD), pore water salinity (5 ppt), and formation temperature (3.3–3.9 °C). Finally, this paper presents the approach and results of extrapolating regional forward production modeling from history-matching efforts on the results from a single well test.« less
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NASA Astrophysics Data System (ADS)
Schwalenberg, Katrin; Hölz, Sebastian; Gehrmann, Romina; Rippe, Dennis; Dannowski, Anke; Zander, Timo; Duan, Shuangmin; Jegen, Marion; Bialas, Jörg
2017-04-01
Marine controlled source electromagnetic (CSEM) data have been collected over gas hydrate targets in the Danube Delta off the coasts of Bulgaria and Romania in early 2014 during voyage MSM35 on R/V Maria S. MERIAN. The cruise was part of the German SUGAR Project, a joint venture project with the goal to study submarine gas hydrates as a source of methane. Within European waters the Black Sea is one of the most prospective hydrocarbon areas. Thick sedimentary basins, the existence of an extended gas hydrate stability zone and the observation of multiple bottom simulating reflectors (BSR) in the western part indicate a huge gas hydrate potential in sandy sediments. Low pore-water salinities between 1 and 4 ppt have been observed in borehole data at depths below 30 mbsf, and are attributed to sea level low stands in the past. 2D and 3D CSEM data sets have been collected over one of the channel levee systems of the Danube Delta fan. High-resolution 2D and 3D seismic, and OBS data are available in the same target area providing structural information and porosity profiles from seismic velocity data. Analysis of subsets of the 3D CSEM data reveal pore-water salinities around 4 ppt for the shallow sediment section, thus are not as low as suggested by the borehole data. The inversion of both 2D and 3D CSEM data sets reveal highly anomalous resistivities within the gas hydrate stability field. We believe that high gas hydrate saturations are the likely cause, as low pore-water salinities are not sufficient to explain the high resistivities, seismic data indicate no clear gas migration pathways through the stability field, nor do hydro-acoustic data show areas of gas seepage which are confined to the landward edge of the stability field. Estimates of the gas hydrate saturation are commonly derived from Archie's Law, and strongly depend on the proper choice of input parameters. We apply porosities from seismic velocity profiles, pore-water resistivities derived from salinity and temperature profiles, and Archie coefficients a, m, and n derived from laboratory studies with various sands and porosities. Gas hydrate saturation estimates vary between 20 and 60 % due to the wide range of input parameter, but are generally higher than estimates from seismic velocity data, an outcome also observed in other gas hydrate areas.
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NASA Astrophysics Data System (ADS)
Qian, Jin; Wang, Xiu-Juan; Wu, Shi-Guo; Wang, Zhen-zhen; Yang, Sheng-Xiong
2014-06-01
Gas hydrates have been identified from two-dimensional (2D) seismic data and logging data above bottom simulating reflector (BSR) during China's first gas hydrate drilling expedition in 2007. The multichannel reflection seismic data were processed to be preserved amplitudes for quantitatively analyzing amplitude variation with offset (AVO) at BSRs. Low P-wave velocity anomaly below BSR, coinciding with high amplitude reflections in 2D seismic data, indicates the presence of free gas. The absolute values of reflection coefficient versus incidence angles for BSR range from 0 to 0.12 at different CMPs near Site SH2. According to logging data and gas hydrate saturations estimated from resistivity of Site SH2, P-wave velocities calculated from effective media theory (EMT) fit the measured sonic velocities well and we choose EMT to calculate elastic velocities for AVO. The rock-physics modeling and AVO analysis were combined to quantitatively assess free gas saturations and distribution by the reflection coefficients variation of the BSRs in Shenhu area, South China Sea. AVO estimation indicates that free gas saturations immediately beneath BSRs may be about 0.2 % (uniform distribution) and up to about 10 % (patchy distribution) at Site SH2.
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NASA Astrophysics Data System (ADS)
Musakaev, N. G.; Khasanov, M. K.; Borodin, S. L.
2018-03-01
In the work on the basis of methods and equations of mechanics of multiphase systems the mathematical model of the process of carbon dioxide burial in the reservoir saturated with methane hydrate is proposed. Estimates are obtained that allow for this problem to neglect diffusion mixing of carbon dioxide and methane. The features of the process of methane displacement from CH4 hydrate by filling them with carbon dioxide are studied.
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NASA Astrophysics Data System (ADS)
Schwalenberg, Katrin; Rippe, Dennis; Koch, Stephanie; Scholl, Carsten
2017-05-01
Marine controlled source electromagnetic (CSEM) data have been collected to investigate methane seep sites and associated gas hydrate deposits at Opouawe Bank on the southern tip of the Hikurangi Margin, New Zealand. The bank is located in about 1000 m water depth within the gas hydrate stability field. The seep sites are characterized by active venting and typical methane seep fauna accompanied with patchy carbonate outcrops at the seafloor. Below the seeps, gas migration pathways reach from below the bottom-simulating reflector (at around 380 m sediment depth) toward the seafloor, indicating free gas transport into the shallow hydrate stability field. The CSEM data have been acquired with a seafloor-towed, electric multi-dipole system measuring the inline component of the electric field. CSEM data from three profiles have been analyzed by using 1-D and 2-D inversion techniques. High-resolution 2-D and 3-D multichannel seismic data have been collected in the same area. The electrical resistivity models show several zones of highly anomalous resistivities (>50 Ωm) which correlate with high amplitude reflections located on top of narrow vertical gas conduits, indicating the coexistence of free gas and gas hydrates within the hydrate stability zone. Away from the seeps the CSEM models show normal background resistivities between 1 and 2 Ωm. Archie's law has been applied to estimate gas/gas hydrate saturations below the seeps. At intermediate depths between 50 and 200 m below seafloor, saturations are between 40 and 80% and gas hydrate may be the dominating pore filling constituent. At shallow depths from 10 m to the seafloor, free gas dominates as seismic data and gas plumes suggest.
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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.
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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.
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Elastic properties of gas hydrate-bearing sediments
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.
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NASA Astrophysics Data System (ADS)
Bauer, K.; Haberland, Ch.; Pratt, R. G.; Ryberg, T.; Weber, M. H.; Mallik Working Group
2003-04-01
We present crosswell seismic data from the Mallik 2002 Production Research Well Program, an international research project on Gas Hydrates in the Northwest Territories of Canada. The program participants include 8 partners; The Geological Survey of Canada (GSC), The Japan National Oil Corporation (JNOC), GeoForschungsZentrum Potsdam (GFZ), United States Geological Survey (USGS), United States Department of the Energy (USDOE), India Ministry of Petroleum and Natural Gas (MOPNG)/Gas Authority of India (GAIL) and the Chevron-BP-Burlington joint venture group. The crosswell seismic measurements were carried out by making use of two 1160 m deep observation wells (Mallik 3L-38 and 4L-38) both 45 m from and co-planar with the 1188 m deep production research well (5L-38). A high power piezo-ceramic source was used to generate sweeped signals with frequencies between 100 and 2000 Hz recorded with arrays of 8 hydrophones per depth level. A depth range between 800 and 1150 m was covered, with shot and receiver spacings of 0.75 m. High quality data could be collected during the survey which allow for application of a wide range of crosswell seismic methods. The initial data analysis included suppression of tube wave energy and picking of first arrivals. A damped least-squares algorithm was used to derive P-wave velocities from the travel time data. Next, t* values were derived from the decay of the amplitude spectra, which served as input parameters for a damped least-squares attenuation tomography. The initial results of the P-wave velocity and attenuation tomography reveal significant features reflecting the stratigraphic environment and allow for detection and eventually quantification of gas hydrate bearing sediments. A prominent correlation between P velocity and attenuation was found for the gas hydrate layers. This contradicts to the apparently more meaningful inverse correlation as it was determined for the gas hydrates at the Blake Ridge but supports the results from the Mallik 2L-38 sonic log data. The P velocities and attenuation values, if combined with other information can be important for the quantitative evaluation of the gas hydrate saturation, and may further constrain petrophysical models of the hydrate bearing sediment formation.
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Connection equation and shaly-sand correction for electrical resistivity
Lee, Myung W.
2011-01-01
Estimating the amount of conductive and nonconductive constituents in the pore space of sediments by using electrical resistivity logs generally loses accuracy where clays are present in the reservoir. Many different methods and clay models have been proposed to account for the conductivity of clay (termed the shaly-sand correction). In this study, the connectivity equation (CE), which is a new approach to model non-Archie rocks, is used to correct for the clay effect and is compared with results using the Waxman and Smits method. The CE presented here requires no parameters other than an adjustable constant, which can be derived from the resistivity of water-saturated sediments. The new approach was applied to estimate water saturation of laboratory data and to estimate gas hydrate saturations at the Mount Elbert well on the Alaska North Slope. Although not as accurate as the Waxman and Smits method to estimate water saturations for the laboratory measurements, gas hydrate saturations estimated at the Mount Elbert well using the proposed CE are comparable to estimates from the Waxman and Smits method. Considering its simplicity, it has high potential to be used to account for the clay effect on electrical resistivity measurement in other systems.
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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.
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Bahk, J.-J.; Kim, G.-Y.; Chun, J.-H.; Kim, J.-H.; Lee, J.Y.; Ryu, B.-J.; Lee, J.-H.; Son, B.-K.; Collett, Timothy S.
2013-01-01
Examinations of core and well-log data from the Second Ulleung Basin Gas Hydrate Drilling Expedition (UBGH2) drill sites suggest that Sites UBGH2-2_2 and UBGH2-6 have relatively good gas hydrate reservoir quality in terms of individual and total cumulative thicknesses of gas-hydrate-bearing sand (HYBS) beds. In both of the sites, core sediments are generally dominated by hemipelagic muds which are intercalated with turbidite sands. The turbidite sands are usually thin-to-medium bedded and mainly consist of well sorted coarse silt to fine sand. Anomalies in infrared core temperatures and porewater chlorinity data and pressure core measurements indicate that “gas hydrate occurrence zones” (GHOZ) are present about 68–155 mbsf at Site UBGH2-2_2 and 110–155 mbsf at Site UBGH2-6. In both the GHOZ, gas hydrates are preferentially associated with many of the turbidite sands as “pore-filling” type hydrates. The HYBS identified in the cores from Site UBGH2-6 are medium-to-thick bedded particularly in the lower part of the GHOZ and well coincident with significant high excursions in all of the resistivity, density, and velocity logs. Gas-hydrate saturations in the HYBS range from 12% to 79% with an average of 52% based on pore-water chlorinity. In contrast, the HYBS from Site UBGH2-2_2 are usually thin-bedded and show poor correlations with both of the resistivity and velocity logs owing to volume averaging effects of the logging tools on the thin HYBS beds. Gas-hydrate saturations in the HYBS range from 15% to 65% with an average of 37% based on pore-water chlorinity. In both of the sites, large fluctuations in biogenic opal contents have significant effects on the sediment physical properties, resulting in limited usage of gamma ray and density logs in discriminating sand reservoirs.
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Gulf of Mexico Gas Hydrate Joint Industry Project Leg II: Results from the Alaminos Canyon 21 Site
NASA Astrophysics Data System (ADS)
Godfriaux, P. D.; Shedd, W.; Frye, M.; Collett, T. S.; Lee, M. W.; Boswell, R. M.; Cook, A.; Mrozewski, S.; Guerin, G.; McConnell, D.; Dufrene, R.; Jones, E.
2009-12-01
The Gulf of Mexico Gas Hydrate Joint Industry Project Leg II drilling program visited three sites in the Gulf of Mexico during a 21 day drilling program in April and May, 2009. Using both petroleum systems and seismic stratigraphic approaches, the exploration focus for Leg II was to identify sites with the potential for gas hydrate-saturated sand reservoirs. Two holes were drilled at the AC 21 site in the Diana Basin located in the western Gulf of Mexico. The data acquired consist of a comprehensive suite of high resolution LWD logs including gamma ray, density, porosity, sonic, and resistivity tools. No physical samples were taken in the field. The primary objective of each well was to determine the presence or absence of gas hydrate from the log data at the predetermined primary targets in a Pleistocene basin floor turbidite complex approximately 500 ft below seafloor. At the AC 21-A location, two high net to gross target sands were encountered that measured 15 ft and 60 ft, respectively. The AC 21-A well was drilled through the interpreted base of gas hydrate stability to a depth approximately 1500 ft below sea floor. The AC 21-B well encountered a single high net to gross target sand measuring over 120 ft thick. At both AC 21 well locations, all target sand intervals had elevated formation resistivity measurements relative to clearly wet, stratigraphically equivalent sands encountered in the region, interpreted to indicate low to moderate levels of gas hydrate saturation. The likely discovery of thick gas hydrate-filled sands at the AC 21 site validates the exploration approach, and strongly indicates that gas hydrate can be found in reservoir quality sands. The LWD acquired data provided unprecedented information on the nature of the sediments and the occurrence of gas hydrate in the Gulf of Mexico.
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Lee, Myung Woong; Collett, Timothy S.
2013-01-01
Through the use of 2-D and 3-D seismic data, a total of thirteen sites were selected and drilled in the East Sea of Korea in 2010. A suite of logging-while-drilling (LWD) logs was acquired at each site. LWD logs from the UBGH2-3A well indicate significant gas hydrate in clay-bearing sediments including several zones with massive gas hydrate with a bulk density less than 1.0 g/m3 for depths between 5 and 103 m below the sea floor. The UBGH2-3A well was drilled on a seismically identified chimney structure with a mound feature at the sea floor. Average gas hydrate saturations estimated from the isotropic analysis of ring resistivity and P-wave velocity logs are 80 ± 13% and 47 ± 16%, respectively, whereas they are 46 ± 17% and 45 ± 16%, respectively from the anisotropic analysis. Modeling indicates that the upper part of chimney (between 5 and 45 m below sea floor [mbsf]) is characterized by gas hydrate filling near horizontal fractures (7° dip) and the lower part of chimney (between 45 and 103 mbsf) is characterized by gas hydrate filling high angle fractures on the basis of ring resistivity and P-wave velocity. The anisotropic analysis using P40H resistivity (phase shift resistivity at 32 mHz with 40 inch spacing) and the P-wave velocity yields a gas hydrate saturation of 46 ± 15% and 46 ± 15% respectively, similar to those estimated using ring resistivity and P-wave velocity, but with quite different fracture dip angles. Differences in vertical resolution, depth of investigation, and a finite fracture dimension relative to the tool separation appear to contribute to this discrepancy. Forward modeling of anisotropic resistivity and velocity are essential to identify gas hydrate in fractures and to estimate accurate gas hydrate amounts.
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Effect of Moisture Exchange on Interface Formation in the Repair System Studied by X-ray Absorption
Lukovic, Mladena; Ye, Guang
2015-01-01
In concrete repair systems, material properties of the repair material and the interface are greatly influenced by the moisture exchange between the repair material and the substrate. If the substrate is dry, it can absorb water from the repair material and reduce its effective water-to-cement ratio (w/c). This further affects the hydration rate of cement based material. In addition to the change in hydration rate, void content at the interface between the two materials is also affected. In this research, the influence of moisture exchange on the void content in the repair system as a function of initial saturation level of the substrate is investigated. Repair systems with varying level of substrate saturation are made. Moisture exchange in these repair systems as a function of time is monitored by the X-ray absorption technique. After a specified curing age (3 d), the internal microstructure of the repair systems was captured by micro-computed X-ray tomography (CT-scanning). From reconstructed images, different phases in the repair system (repair material, substrate, voids) can be distinguished. In order to quantify the void content, voids were thresholded and their percentage was calculated. It was found that significantly more voids form when the substrate is dry prior to application of the repair material. Air, initially filling voids and pores of the dry substrate, is being released due to the moisture exchange. As a result, air voids remain entrapped in the repair material close to the interface. These voids are found to form as a continuation of pre-existing surface voids in the substrate. Knowledge about moisture exchange and its effects provides engineers with the basis for recommendations about substrate preconditioning in practice. PMID:28787801
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Kumar, P.; Collett, Timothy S.; Vishwanath, K.; Shukla, K.M.; Nagalingam, J.; Lall, M.V.; Yamada, Y; Schultheiss, P.; Holland, M.
2016-01-01
The India National Gas Hydrate Program Expedition 02 (NGHP-02) was conducted from 3-March-2015 to 28-July-2015 off the eastern coast of India using the deepwater drilling vessel Chikyu. The primary goal of this expedition was to explore for highly saturated gas hydrate occurrences in sand reservoirs that would become targets for future production tests. The first two months of the expedition were dedicated to logging-whiledrilling (LWD) operations, with a total of 25 holes drilled and logged. The next three months were dedicated to coring operations at 10 of the most promising sites. With a total of five months of continuous field operations, the expedition was the most comprehensive dedicated gas hydrate investigation ever undertaken.
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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.
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Lee, M.W.; Collett, T.S.
2012-01-01
High-quality logging-while-drilling (LWD) downhole logs were acquired in seven wells drilled during the Gulf of MexicoGasHydrateJointIndustryProjectLegII in the spring of 2009. Well logs obtained in one of the wells, the GreenCanyon Block 955Hwell (GC955-H), indicate that a 27.4-m thick zone at the depth of 428 m below sea floor (mbsf; 1404 feet below sea floor (fbsf)) contains gashydrate within sand with average gashydrate saturations estimated at 60% from the compressional-wave (P-wave) velocity and 65% (locally more than 80%) from resistivity logs if the gashydrate is assumed to be uniformly distributed in this mostly sand-rich section. Similar analysis, however, of log data from a shallow clay-rich interval between 183 and 366 mbsf (600 and 1200 fbsf) yielded average gashydrate saturations of about 20% from the resistivity log (locally 50-60%) and negligible amounts of gashydrate from the P-wave velocity logs. Differences in saturations estimated between resistivity and P-wave velocities within the upper clay-rich interval are caused by the nature of the gashydrate occurrences. In the case of the shallow clay-rich interval, gashydrate fills vertical (or high angle) fractures in rather than fillingpore space in sands. In this study, isotropic and anisotropic resistivity and velocity models are used to analyze the occurrence of gashydrate within both the clay-rich and sand dominated gas-hydrate-bearing reservoirs in the GC955-Hwell.
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Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.
2011-01-01
Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769
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Microstructural characteristics of natural gas hydrates hosted in various sand sediments.
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.
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Thermodynamic properties of methane hydrate in quartz powder.
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.
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Elastic-wave velocity in marine sediments with gas hydrates: Effective medium modeling
Helgerud, M.B.; Dvorkin, J.; Nur, A.; Sakai, A.; Collett, T.
1999-01-01
We offer a first-principle-based effective medium model for elastic-wave velocity in unconsolidated, high porosity, ocean bottom sediments containing gas hydrate. The dry sediment frame elastic constants depend on porosity, elastic moduli of the solid phase, and effective pressure. Elastic moduli of saturated sediment are calculated from those of the dry frame using Gassmann's equation. To model the effect of gas hydrate on sediment elastic moduli we use two separate assumptions: (a) hydrate modifies the pore fluid elastic properties without affecting the frame; (b) hydrate becomes a component of the solid phase, modifying the elasticity of the frame. The goal of the modeling is to predict the amount of hydrate in sediments from sonic or seismic velocity data. We apply the model to sonic and VSP data from ODP Hole 995 and obtain hydrate concentration estimates from assumption (b) consistent with estimates obtained from resistivity, chlorinity and evolved gas data. Copyright 1999 by the American Geophysical Union.
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Site-specific hydration and dehydration of San Carlos olivine
NASA Astrophysics Data System (ADS)
Ferriss, E.; Plank, T. A.; Walker, D.
2016-12-01
Hydrogen incorporation and diffusion in olivine is critical to understanding fundamental Earth processes such as mantle rheology, plate tectonics, melt generation and magma ascent. Interpreting measured H profiles in olivine requires a more comprehensive understanding of H point defect reactions than currently exists because H diffusivity (D) ranges over 6 orders of magnitude, from slow diffusing H incorporated as (4H+)Si [1] to rapid `proton-polaron' bulk H diffusion [2]. Here we present the first experiments on H diffusing into and then out of Fe-bearing olivine using the whole-block method [3], which allows a finely-resolved time series of H profiles in 3 crystallographic directions using the same sample for all dehydration steps. A piece of nearly-dry, oriented San Carlos olivine was hydrated in a piston cylinder apparatus using H2O and solid buffers of Ni/NiO and San Carlos olivine and enstatite at 800 °C and 10 kbar for 17.5 hours, just long enough to saturate the `proton-polaron' mechanism. The sample was then dehydrated in a CO/CO2 gas-mixing furnace at 800°C and 10-14 bar fO2 for total heating times of 1, 3, 7, 13, 19, 43, and 68 hrs, at which point most, but not all, of the H had left the crystal. FTIR profiles at 1, 3, and 7 hours show bulk H profiles consistent with `proton-polaron' diffusion. Later the pace of dehydration slowed, and in several cases the bulk H profile shape differed from what would be expected during simple diffusive loss. The small peak at 3600 cm-1, (4H+)Si, remained essentially unchanged throughout all experiments. The peak at 3573 cm-1, (Ti4+)Mg(2H+)Mg, was initially present but tiny, grew to become the largest peak after hydration, and then during dehydration returned to its initial height. The apparent diffusivity of this peak during hydration and the initial stages of dehydration is 4 orders of magnitude faster than the same peak in synthetic forsterite [2]. Peaks at 3542, 3525, 3489, and 3480 cm-1 were not present initially, grew during hydration, and were removed completely during dehydration. No lower-wavenumber H peaks were observed. These results represent a major step toward reconciling the peak-specific understanding of H diffusion [1] with the 2-mechanism H bulk diffusion model [2]. [1] Padrón-Navarta et al. 2014 [2] Kohlstedt & Mackwell 1998 [3] Ferriss et al. 2015
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NASA Astrophysics Data System (ADS)
Loring, J. S.; Chen, J.; Thompson, C.; Schaef, T.; Miller, Q. R.; Martin, P. F.; Ilton, E. S.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.
2012-12-01
The effectiveness of geologic sequestration as an enterprise for CO2 storage depends partly on the reactivity of supercritical CO2 (scCO2) with caprock minerals. Injection of scCO2 will displace formation water, and the pore space adjacent to overlying caprocks could eventually be dominated by dry to water-saturated scCO2. Caprock formations have high concentrations of clay minerals, including expandable montmorillonites. Water-bearing scCO2 is highly reactive and capable of hydrating or dehydrating clays, possibly leading to porosity and permeability changes that directly impact caprock performance. Dehydration will cause montmorillonite clay minerals in caprocks to contract, thereby decreasing solid volume and possibly increasing caprock permeability and porosity. On the other hand, water intercalation will cause these clays to expand, thereby increasing solid volume and possibly leading to self-sealing of caprock fractures. Pacific Northwest National Laboratory's Carbon Sequestration Initiative is developing capabilities for studying wet scCO2-mineral reactions in situ. Here, we introduce novel in situ infrared (IR) spectroscopic instrumentation that enables quantitative titrations of reactant minerals with water in scCO2. Results are presented for the infrared spectroscopic titrations of Na-, Ca-, and Mg-saturated Wyoming betonites with water over concentrations ranging from zero to scCO2 saturated. These experiments were carried out at 50°C and 90 bar. Transmission IR spectroscopy was used to measure concentrations of water dissolved in the scCO2 or intercalated into the clays. The titration curves evaluated from the transmission-IR data are compared between the three types of clays to assess the effects of the cation on water partitioning. Single-reflection attenuated total reflection (ATR) IR spectroscopy was used to collect the spectrum of the clays as they hydrate at every total water concentration during the titration. Clay hydration is evidenced by increases in absorbance of the OH stretching and HOH bending modes of the intercalated waters. The ATR-IR data also indicate that CO2 is intercalated in the clay. The asymmetric stretching band of the CO2 molecules that are intercalated in the clay is narrower than that stretching band of bulk scCO2, which indicates that the spectral contribution from rotational fine structure is minimal and the intercalated CO2 is rotationally constrained. A chemometrics analysis of the complete set of ATR-IR spectra spanning the range of total water concentrations covered in the titration finds that there are at least two types of intercalated waters, two types of intercalated CO2 molecules, and the concentrations of these intercalated waters and CO2 molecules are correlated. These quantitative data, when coupled with in situ XRD results that predict interlayer spacing and clay volume, demonstrate that water and CO2 intercalation processes in expandable montmorillonite clays could lead to porosity and permeability changes that directly impact caprock performance.
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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.
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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.
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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.
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Karaoui, Mohammed; Varadaraj, Varshini; Munoz, Beatriz; Collins, Megan E; Al Djasim, Leyla; Al Naji, Esam; Hamweyah, Karam; Shamrani, Mohammed Al; Craven, Earl Randy; Friedman, David S
2018-05-10
To determine safety and efficacy of oral chloral hydrate sedation (CHS) for outpatient pediatric ophthalmic procedures. Prospective, interventional case series METHODS-SETTING: - King Khaled Eye Specialist Hospital. Children ages 1 month to 5 years undergoing CHS for ocular imaging/evaluation PROCEDURES: Details on chloral hydrate dose administered, sedation achieved, vitals, and adverse events were recorded OUTCOME MEASURES: Primary Outcome: Percent of patients with a sedation level ≥4 at 45 minutes post chloral hydrate administration. Time from sedation to discharge; adverse events, including changes in vital signs following chloral hydrate administration. 324 children were recruited with a mean age of 2.2 (SD: 1.3) years and mean weight of 10.9 (SD: 3.3) kg. Adequate sedation was obtained with a mean chloral hydrate first dose of 77.4 (SD: 14.7) mg/kg in 306 (94.4%) patients, with an additional 6 patients (1.9%) achieving adequate sedation with a second dose (overall adequate sedation: 96.3%). Mean reductions in heart rate, respiratory rate and oxygen (O 2 ) saturation from pre-sedation to 25 min post-sedation were 11.7 (SD: 14.3) beats-per-minute, 1.2 (SD: 2.4) breaths-per-minute, and 0.81 (SD: 1.2) %, respectively (p<0.001 for all). In multivariable regression, odds of remaining sedated 45 minutes after chloral hydrate administration was 2.53 times higher for American Society of Anesthesiologists (ASA) class II or III patients than for ASA I (95% CI: 1.11-5.78, p=0.03), 1.03 times higher per mg increase in initial dose of chloral hydrate (95% CI: 1.01-1.06, p=0.006), and 2.70 times higher per unit increase in number of planned procedures (95% CI: 1.63-4.47, p<0.001). Three patients developed minor adverse events: 2 cases of O 2 desaturation and 1 paradoxical reaction, none requiring significant intervention. Patients were discharged a median of 90 minutes after chloral hydrate administration. Chloral hydrate administered by a dedicated sedation service as in this prospective assessment can be used safely and effectively for outpatient pediatric ophthalmic procedures. Copyright © 2018 Elsevier Inc. All rights reserved.
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Competitive Sorption of CO2 and H2O in 2:1 Layer Phyllosilicates
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schaef, Herbert T.; Loring, John S.; Glezakou, Vassiliki Alexandra
The salting out effect, where increasing the ionic strength of aqueous solutions decreases the solubility of dissolved gases is a well-known phenomenon. Less explored is the opposite process where an initially anhydrous system containing a volatile, relatively non-polar component and inorganic ions is systematically hydrated. Expandable clays such as montmorillonite are ideal systems for exploring this scenario as they have readily accessible exchange sites containing cations that can be systematically dehydrated or hydrated, from near anhydrous to almost bulk-like water conditions. This phenomenon has new significance with the simultaneous implementation of geological sequestration and secondary utilization of CO2 to bothmore » mitigate climate warming and enhance extraction of methane from hydrated clay-rich formations. Here, the partitioning of CO2 and H2O between Na-, Ca-, and Mg-exchanged montmorillonite and variably hydrated supercritical CO2 (scCO2) was investigated using in situ X-ray diffraction, infrared (IR)spectroscopic titrations, and quartz crystal microbalance (QCM) measurements. Density functional theory calculations provided mechanistic insights. Structural volumetric changes were correlated to quantified changes in sorbed H2O and CO2 concentrations as a function of %H2O saturated in scCO2. Intercalation of CO2 is favored at low H2O/CO2 ratios in the interlayer region, where CO2 can solvate the interlayer cation. As the clay becomes more hydrated and the H2O/CO2 ratio increases, H2O displaces CO2 from the solvation shell of the cation and CO2 tends to segregate. This transition decreases both the entropic and enthalpic driving force for CO2 intercalation, consistent with experimentally observed loss of intercalated CO2.« less
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Influence of smectite hydration and swelling on atrazine sorption behavior.
Chappell, Mark A; Laird, David A; Thompson, Michael L; Li, Hui; Teppen, Brian J; Aggarwal, Vaneet; Johnston, Cliff T; Boyd, Stephen A
2005-05-01
Smectites, clay minerals commonly found in soils and sediments, vary widely in their ability to adsorb organic chemicals. Recent research has demonstrated the importance of surface charge density and properties of exchangeable cations in controlling the affinity of smectites for organic molecules. In this study, we induced hysteresis in the crystalline swelling of smectites to test the hypothesis that the extent of crystalline swelling (or interlayer hydration status) has a large influence on the ability of smectites to adsorb atrazine from aqueous systems. Air-dried K-saturated Panther Creek (PC) smectite swelled less (d(001) = 1.38 nm) than never-dried K-PC (d(001) = 1.7 nm) when rehydrated in 20 mM KCl. Correspondingly, the air-dried-rehydrated K-PC had an order of magnitude greater affinity for atrazine relative to the never-dried K-PC. Both air-dried-rehydrated and never-dried Ca-PC expanded to approximately 2.0 nm in 10 mM CaCl2 and both samples had similar affinities for atrazine that were slightly lower than that of never-dried K-PC. The importance of interlayer hydration status in controlling sorption affinity was confirmed by molecular modeling, which revealed much greater interaction between interlayer water molecules and atrazine in a three-layer hydrate relative to a one-layer hydrate. The entropy change on moving atrazine from a fully hydrated state in the bulk solution to a partially hydrated state in the smectite interlayers is believed to be a major factor influencing sorption affinity. In an application test, choice of background solution (20 mM KCl versus 10 mM CaCl2) and air-drying treatments significantly affected atrazine sorption affinities for three-smectitic soils; however, the trends were not consistent with those observed for the reference smectite. Further, extending the initial rehydration time from 24 to 240 h (prior to adding atrazine) significantly decreased the soil's sorption affinity for atrazine. We conclude that interlayer hydration status has a large influence on the affinity of smectites for atrazine and that air-drying treatments have the potential to modify the sorption affinity of smectitic soils for organic molecules such as atrazine.
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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.
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Magnetic resonance imaging (MRI) and relaxation time mapping of concrete
NASA Astrophysics Data System (ADS)
Beyea, Steven Donald
2001-07-01
The use of Magnetic Resonance Imaging (MRI) of water in concrete is presented. This thesis will approach the problem of MR imaging of concrete by attempting to design new methods, suited to concrete materials, rather than attempting to force the material to suit the method. A number of techniques were developed, which allow the spatial observation of water in concrete in up to three dimensions, and permits the determination of space resolved moisture content, as well as local NMR relaxation times. These methods are all based on the Single-Point Imaging (SPI) method. The development of these new methods will be described, and the techniques validated using phantom studies. The study of one-dimensional moisture transport in drying concrete was performed using SPI. This work examined the effect of initial mixture proportions and hydration time on the drying behaviour of concrete, over a period of three months. Studies of drying concrete were also performed using spatial mapping of the spin-lattice (T1) and effective spin-spin (T2*) relaxation times, thereby permitting the observation of changes in the water occupied pore surface-to-volume ratio (S/V) as a function of drying. Results of this work demonstrated changes in the S/V due to drying, hydration and drying induced microcracking. Three-dimensional MRI of concrete was performed using SPRITE (Single-Point Ramped Imaging with T1 Enhancement) and turboSPI (turbo Single Point Imaging). While SPRITE allows for weighting of MR images using T 1 and T2*, turboSPI allows T2 weighting of the resulting images. Using relaxation weighting it was shown to be possible to discriminate between water contained within a hydrated cement matrix, and water in highly porous aggregates, used to produce low-density concrete. Three dimensional experiments performed using SPRITE and turboSPI examined the role of self-dessication, drying, initial aggregate saturation and initial mixture conditions on the transport of moisture between porous aggregates and the hydrated matrix. The results demonstrate that water is both added and removed from the aggregates, depending upon the physical conditions. The images also appear to show an influx of cement products into cracks in the solid aggregate. (Abstract shortened by UMI.)
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Natural gas hydrates and the mystery of the Bermuda Triangle
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gruy, H.J.
1998-03-01
Natural gas hydrates occur on the ocean floor in such great volumes that they contain twice as much carbon as all known coal, oil and conventional natural gas deposits. Releases of this gas caused by sediment slides and other natural causes have resulted in huge slugs of gas saturated water with density too low to float a ship, and enough localized atmospheric contamination to choke air aspirated aircraft engines. The unexplained disappearances of ships and aircraft along with their crews and passengers in the Bermuda Triangle may be tied to the natural venting of gas hydrates. The paper describes whatmore » gas hydrates are, their formation and release, and their possible link to the mystery of the Bermuda Triangle.« less
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Wang, Pingkang; Zhang, Xuhui; Zhu, Youhai; Li, Bing; Huang, Xia; Pang, Shouji; Zhang, Shuai; Lu, Cheng; Xiao, Rui
2014-12-01
The gas hydrate petroleum system in the permafrost of the Qilian Mountains, which exists as an epigenetic hydrocarbon reservoir above a deep-seated hydrocarbon reservoir, has been dynamic since the end of the Late Pleistocene because of climate change. The permafrost limits the occurrence of gas hydrate reservoirs by changing the pressure-temperature (P-T) conditions, and it affects the migration of the underlying hydrocarbon gas because of its strong sealing ability. In this study, we reconstructed the permafrost structure of the Qilian Mountains using a combination of methods and measured methane permeability in ice-bearing sediment permafrost. A relationship between the ice saturation of permafrost and methane permeability was established, which permitted the quantitative evaluation of the sealing ability of permafrost with regard to methane migration. The test results showed that when ice saturation is >80%, methane gas can be completely sealed within the permafrost. Based on the permafrost properties and genesis of shallow gas, we suggest that a shallow "gas pool" occurred in the gas hydrate petroleum system in the Qilian Mountains. Its formation was related to a metastable gas hydrate reservoir controlled by the P-T conditions, sealing ability of the permafrost, fault system, and climatic warming. From an energy perspective, the increasing volume of the gas pool means that it will likely become a shallow gas resource available for exploitation; however, for the environment, the gas pool is an underground "time bomb" that is a potential source of greenhouse gas.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Myshakin, Evgeniy M.; Gaddipati, Manohar; Rose, Kelly
2012-06-01
In 2009, the Gulf of Mexico (GOM) Gas Hydrates Joint-Industry-Project (JIP) Leg II drilling program confirmed that gas hydrate occurs at high saturations within reservoir-quality sands in the GOM. A comprehensive logging-while-drilling dataset was collected from seven wells at three sites, including two wells at the Walker Ridge 313 site. By constraining the saturations and thicknesses of hydrate-bearing sands using logging-while-drilling data, two-dimensional (2D), cylindrical, r-z and three-dimensional (3D) reservoir models were simulated. The gas hydrate occurrences inferred from seismic analysis are used to delineate the areal extent of the 3D reservoir models. Numerical simulations of gas production from themore » Walker Ridge reservoirs were conducted using the depressurization method at a constant bottomhole pressure. Results of these simulations indicate that these hydrate deposits are readily produced, owing to high intrinsic reservoir-quality and their proximity to the base of hydrate stability. The elevated in situ reservoir temperatures contribute to high (5–40 MMscf/day) predicted production rates. The production rates obtained from the 2D and 3D models are in close agreement. To evaluate the effect of spatial dimensions, the 2D reservoir domains were simulated at two outer radii. The results showed increased potential for formation of secondary hydrate and appearance of lag time for production rates as reservoir size increases. Similar phenomena were observed in the 3D reservoir models. The results also suggest that interbedded gas hydrate accumulations might be preferable targets for gas production in comparison with massive deposits. Hydrate in such accumulations can be readily dissociated due to heat supply from surrounding hydrate-free zones. Special cases were considered to evaluate the effect of overburden and underburden permeability on production. The obtained data show that production can be significantly degraded in comparison with a case using impermeable boundaries. The main reason for the reduced productivity is water influx from the surrounding strata; a secondary cause is gas escape into the overburden. The results dictate that in order to reliably estimate production potential, permeability of the surroundings has to be included in a model.« less
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Nandanwar, Manish S.; Anderson, Brian J.; Ajayi, Taiwo; Collett, Timothy S.; Zyrianova, Margarita V.
2016-01-01
An evaluation of the gas production potential of Sunlight Peak gas hydrate accumulation in the eastern portion of the National Petroleum Reserve Alaska (NPRA) of Alaska North Slope (ANS) is conducted using numerical simulations, as part of the U.S. Geological Survey (USGS) gas hydrate Life Cycle Assessment program. A field scale reservoir model for Sunlight Peak is developed using Advanced Processes & Thermal Reservoir Simulator (STARS) that approximates the production design and response of this gas hydrate field. The reservoir characterization is based on available structural maps and the seismic-derived hydrate saturation map of the study region. A 3D reservoir model, with heterogeneous distribution of the reservoir properties (such as porosity, permeability and vertical hydrate saturation), is developed by correlating the data from the Mount Elbert well logs. Production simulations showed that the Sunlight Peak prospect has the potential of producing 1.53 × 109 ST m3 of gas in 30 years by depressurization with a peak production rate of around 19.4 × 104 ST m3/day through a single horizontal well. To determine the effect of uncertainty in reservoir properties on the gas production, an uncertainty analysis is carried out. It is observed that for the range of data considered, the overall cumulative production from the Sunlight Peak will always be within the range of ±4.6% error from the overall mean value of 1.43 × 109 ST m3. A sensitivity analysis study showed that the proximity of the reservoir from the base of permafrost and the base of hydrate stability zone (BHSZ) has significant effect on gas production rates. The gas production rates decrease with the increase in the depth of the permafrost and the depth of BHSZ. From the overall analysis of the results it is concluded that Sunlight Peak gas hydrate accumulation behaves differently than other Class III reservoirs (Class III reservoirs are composed of a single layer of hydrate with no underlying zone of mobile fluids) due to its smaller thickness and high angle of dip.
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NASA Astrophysics Data System (ADS)
Carcione, José M.; Gei, Davide
2004-05-01
We estimate the concentration of gas hydrate at the Mallik 2L-38 research site using P- and S-wave velocities obtained from well logging and vertical seismic profiles (VSP). The theoretical velocities are obtained from a generalization of Gassmann's modulus to three phases (rock frame, gas hydrate and fluid). The dry-rock moduli are estimated from the log profiles, in sections where the rock is assumed to be fully saturated with water. We obtain hydrate concentrations up to 75%, average values of 37% and 21% from the VSP P- and S-wave velocities, respectively, and 60% and 57% from the sonic-log P- and S-wave velocities, respectively. The above averages are similar to estimations obtained from hydrate dissociation modeling and Archie methods. The estimations based on the P-wave velocities are more reliable than those based on the S-wave velocities.
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Biosurfactant as a Promoter of Methane Hydrate Formation: Thermodynamic and Kinetic Studies
Arora, Amit; Cameotra, Swaranjit Singh; Kumar, Rajnish; Balomajumder, Chandrajit; Singh, Anil Kumar; Santhakumari, B.; Kumar, Pushpendra; Laik, Sukumar
2016-01-01
Natural gas hydrates (NGHs) are solid non-stoichiometric compounds often regarded as a next generation energy source. Successful commercialization of NGH is curtailed by lack of efficient and safe technology for generation, dissociation, storage and transportation. The present work studied the influence of environment compatible biosurfactant on gas hydrate formation. Biosurfactant was produced by Pseudomonas aeruginosa strain A11 and was characterized as rhamnolipids. Purified rhamnolipids reduced the surface tension of water from 72 mN/m to 36 mN/m with Critical Micelle Concentration (CMC) of 70 mg/l. Use of 1000 ppm rhamnolipids solution in C type silica gel bed system increased methane hydrate formation rate by 42.97% and reduced the induction time of hydrate formation by 22.63% as compared to water saturated C type silica gel. Presence of rhamnolipids also shifted methane hydrate formation temperature to higher values relative to the system without biosurfactant. Results from thermodynamic and kinetic studies suggest that rhamnolipids can be applied as environment friendly methane hydrate promoter. PMID:26869357
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Haines, Seth S.; Hart, Patrick E.; Shedd, William W.; Frye, Matthew
2014-01-01
The U.S. Geological Survey led a seismic acquisition cruise at Green Canyon 955 (GC955) and Walker Ridge 313 (WR313) in the Gulf of Mexico from April 18 to May 3, 2013, acquiring multicomponent and high-resolution 2D seismic data. GC955 and WR313 are established, world-class study sites where high gas hydrate saturations exist within reservoir-grade sands in this long-established petroleum province. Logging-while-drilling (LWD) data acquired in 2009 by the Gulf of Mexico Gas Hydrates Joint Industry Project provide detailed characterization at the borehole locations, and industry seismic data provide regional- and local-scale structural and stratigraphic characterization. Significant remaining questions regarding lithology and hydrate saturation between and away from the boreholes spurred new geophysical data acquisition at these sites. The goals of our 2013 surveys were to (1) achieve improved imaging and characterization at these sites and (2) refine geophysical methods for gas hydrate characterization in other locations. In the area of GC955 we deployed 21 ocean-bottom seismometers (OBS) and acquired approximately 400 km of high-resolution 2D streamer seismic data in a grid with line spacing as small as 50 m and along radial lines that provide source offsets up to 10 km and diverse azimuths for the OBS. In the area of WR313 we deployed 25 OBS and acquired approximately 450 km of streamer seismic data in a grid pattern with line spacing as small as 250 m and along radial lines that provide source offsets up to 10 km for the OBS. These new data afford at least five times better resolution of the structural and stratigraphic features of interest at the sites and enable considerably improved characterization of lithology and the gas and gas hydrate systems. Our recent survey represents a unique application of dedicated geophysical data to the characterization of confirmed reservoir-grade gas hydrate accumulations.
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NASA Astrophysics Data System (ADS)
Tanahashi, M.; Morita, S.; Matsumoto, R.
2017-12-01
Two dedicated LWD (Logging While Drilling) cruises, GR14 and HR15, were conducted in summers of 2014 and 2015, respectively, by Meiji University and Geological Survey of Japan, AIST to explore the gas chimney structures, which are characterized by the columnar acoustic blanking below the topographic mound and/or pockmarks in eastern margin of Japan Sea. Shallow (33 to 172m-bsf, average 136m-bsf) 33 LWD drillings were carried out generally in and around gas chimney structures which are in Oki Trough, Off-Joetsu, and Mogami Trough areas, eastern margin of Japan Sea, during two cruises. Schlumberger LWD tools, GeoVISION (resistivity), TeleScope, ProVISION (NMR) and SonicVISION (sonic) were applied during GR14. NeoScope (neutron) was added and SonicScope was replaced for SonicVISION during HR15. The presence of thick highly-anomalous intervals within the LWD data at site J24L suggests the development of massive gas hydrate within Off-Joetsu, by very high resistivity ( 10,000 Ωm), high Vp ( 3,700 m/s) and Vs (370-1,839 m/s), high neutron porosity ( 1.2), low natural gamma ray intensity ( 0 API), low neutron gamma density ( 0.8 g/cm3), low NMR porosity ( 0.0), low permeability (10-2-10-4 mD), low formation neutron sigma (26-28). The extreme physical properties intervals suggest the development of the almost pure hydrate. Because of the clear contrast between pure hydrate and seawater saturated fine sediments, the hydrate amount can be estimated quantitatively based on the assumptions as the two component system of pure hydrate and the monotonous seawater saturated fine sediments. This study was conducted as a part of the methane hydrate research project funded by METI (the Ministry of Economy, Trade and Industry, Japan).
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Effects of ensembles on methane hydrate nucleation kinetics.
Zhang, Zhengcai; Liu, Chan-Juan; Walsh, Matthew R; Guo, Guang-Jun
2016-06-21
By performing molecular dynamics simulations to form a hydrate with a methane nano-bubble in liquid water at 250 K and 50 MPa, we report how different ensembles, such as the NPT, NVT, and NVE ensembles, affect the nucleation kinetics of the methane hydrate. The nucleation trajectories are monitored using the face-saturated incomplete cage analysis (FSICA) and the mutually coordinated guest (MCG) order parameter (OP). The nucleation rate and the critical nucleus are obtained using the mean first-passage time (MFPT) method based on the FS cages and the MCG-1 OPs, respectively. The fitting results of MFPT show that hydrate nucleation and growth are coupled together, consistent with the cage adsorption hypothesis which emphasizes that the cage adsorption of methane is a mechanism for both hydrate nucleation and growth. For the three different ensembles, the hydrate nucleation rate is quantitatively ordered as follows: NPT > NVT > NVE, while the sequence of hydrate crystallinity is exactly reversed. However, the largest size of the critical nucleus appears in the NVT ensemble, rather than in the NVE ensemble. These results are helpful for choosing a suitable ensemble when to study hydrate formation via computer simulations, and emphasize the importance of the order degree of the critical nucleus.
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Gal, Jean-Yves; Fovet, Yannick; Gache, Nathalie
2002-02-01
In the first part, we have designed a new model of evolution for the calco-carbonic system which includes the hydrated forms of CaCO3: CaCO3 amorphous, CaCO3 x 6H2O (ikaite) and CaCO3 x H2O (monohydrate) (J. Eur. Hydr. 30 (1999) 47). According to this model, it is the precipitation of one or other of these hydrated forms which could be responsible for the breakdown of the metastable state. After this first step, the precipitates evolve to dehydrated solid forms. Through the elaboration of computer programs in which the CaCO3(0) (aq) ion pair formation was considered, this model was compared to experimental data obtained by the critical pH method applied to synthetic solutions. In the present article, the same method was applied for four French mineral waters, at 25 degrees C under study. Three samples formed a precipitation during the sodium hydroxide addition. For these three cases, this precipitation began for the CaCO3 H2O saturation. The added volume of sodium hydroxide was more than what was required for neutralizing free CO2 initially in solution. These results indicate that during a spontaneous scaling phenomenon, the pH rises at the same time by loss of the initial free CO2 and of the one produced by the hydrogen carbonate ions decomposition. Then we calculated, at various temperatures for the three studied scaling waters: CO2 partial pressures and loss of total carbon corresponding to the solubility products of CaCO3 hydrated forms. The results show that the partial pressure monitoring of the carbon dioxide is important in managing the behavior of scaling waters.
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NASA Astrophysics Data System (ADS)
Ning, F.; Wu, N.; Jiang, G.; Zhang, L.
2009-12-01
Under the condition of over-pressure drilling, the solid-phase and liquid-phase in drilling fluids immediately penetrate into the oceanic gas hydrates-bearing sediment, which causes the water content surrounding the borehole to increase largely. At the same time, the hydrates surrounding borehole maybe quickly decompose into water and gas because of the rapid change of temperature and pressure. The drilling practices prove that this two factors may change the rock characteristics of wellbore, such as rock strength, pore pressure, resistivity, etc., and then affect the logging response and evaluation, wellbore stability and well safty. The invasion of filtrate can lower the angle of friction and weaken the cohesion of hydrates-bearing sediment,which is same to the effect of invading into conventional oil and gas formation on borehole mechnical properties. The difference is that temperature isn’t considered in the invasion process of conventional formations while in hydrates-bearing sediments, it is a factor that can not be ignored. Temperature changes can result in hydrates dissociating, which has a great effect on mechanical properties of borehole. With the application of numerical simulation method, we studied the changes of pore pressure and variation of water content in the gas hydrates-bearing sediment caused by drilling fluid invasion under pressure differential and gas hydrate dissociation under temperature differential and analyzed their influence on borehole stability.The result of simulation indicated that the temperature near borehole increased quickly and changed hardly any after 6 min later. About 1m away from the borehole, the temperature of formation wasn’t affected by the temperature change of borehole. At the place near borehole, as gas hydrate dissociated dramatically and drilling fluid invaded quickly, the pore pressure increased promptly. The degree of increase depends on the permeability and speed of temperature rise of formation around bohole. If the formation has a low permeability and is heated quickly, the dissociated gas and water couldn’t flow away in time, which is likely to bring a hazard of excess pore pressure. Especially in the area near the wall of borehole, the increase degree of pore pressure is high than other area because the dissociation of gas hydrates is relatively violent and hydraulic gradient is bigger. We also studied the distribution of water saturation around borehole after 10min, 30min and 60min respectively. It revealed that along with the invasion of drilling fluid and dissociation of gas hydrate, the degree of water saturation increased gradually. The effect of gas hydrate dissociation and drilling fluids invasion on borehole stability is to weaken mechanical properties of wellbore and change the pore pressure, then changes the effective stress of gas hydrates-bearing sediment. So temperature, pressure in the borehole and filter loss of drilling fluids should be controlled strictly to prevent gas hydrates from decomposing largely and in order to keep the borehole stability in the gas hydrates-bearing formations.
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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.
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Gas hydrate concentration estimated from P- and S-wave velocities
NASA Astrophysics Data System (ADS)
Carcione, J. M.; Gei, D.
2003-04-01
We estimate the concentration of gas hydrate at the Mallik 2L-38 research site, Mackenzie Delta, Canada, using P- and S-wave velocities obtained from well logging and vertical seismic profiles (VSP). The theoretical velocities are obtained from a poro-viscoelastic model based on a Biot-type approach. It considers the existence of two solids (grains and gas hydrate) and a fluid mixture and is based on the assumption that hydrate fills the pore space and shows interconnection. The moduli of the matrix formed by gas hydrate are obtained from the percolation model described by Leclaire et al., (1994). An empirical mixing law introduced by Brie et al., (1995) provides the effective bulk modulus of the fluid phase, giving Wood's modulus at low frequency and Voigt's modulus at high frequencies. The dry-rock moduli are estimated from the VSP profile where the rock is assumed to be fully saturated with water, and the quality factors are obtained from the velocity dispersion observed between the sonic and VSP velocities. Attenuation is described by using a constant-Q model for the dry rock moduli. The amount of dissipation is estimated from the difference between the seismic velocities and the sonic-log velocities. We estimate the amount of gas hydrate by fitting the sonic-log and seismic velocities to the theoretical velocities, using the concentration of gas hydrate as fitting parameter. We obtain hydrate concentrations up to 75 %, average values of 43 and 47 % from the VSP P- and S-wave velocities, respectively, and 47 and 42 % from the sonic-log P- and S-wave velocities, respectively. These averages are computed from 897 to 1110 m, excluding the zones where there is no gas hydrate. We found that modeling attenuation is important to obtain reliable results. largeReferences} begin{description} Brie, A., Pampuri, F., Marsala A.F., Meazza O., 1995, Shear Sonic Interpretation in Gas-Bearing Sands, SPE Annual Technical Conference and Exhibition, Dallas, 1995. Carcione, J.M. and Gei, D., Gas hydrate concentration estimated from P- and S-wave velocities at the Mallik 2L-38 research well, Mackenzie Delta, Canada, submitted to Geophysics. Gei, D. and Carcione, J.M., Acoustic properties of sediments saturated with gas hydrate, free gas and water, Geophysical Prospecting, in press. Leclarie, Ph., Cohen-Tenoudji, F., and Aguirre-Puente, J., 1994, Extension of Biot's theory of wave propagation to frozen porous media, J. Acoust. Soc. Am., 96, 6, 3753-3768.
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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.
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Subsurface gas hydrates in the northern Gulf of Mexico
Boswell, Ray; Collett, Timothy S.; Frye, Matthew; Shedd, William; McConnell, Daniel R.; Shelander, Dianna
2012-01-01
The northernGulf of Mexico (GoM) has long been a focus area for the study of gashydrates. Throughout the 1980s and 1990s, work focused on massive gashydrates deposits that were found to form at and near the seafloor in association with hydrocarbon seeps. However, as global scientific and industrial interest in assessment of the drilling hazards and resource implications of gashydrate accelerated, focus shifted to understanding the nature and abundance of "buried" gashydrates. Through 2005, despite the drilling of more than 1200 oil and gas industry wells through the gashydrate stability zone, published evidence of significant sub-seafloor gashydrate in the GoM was lacking. A 2005 drilling program by the GoM GasHydrate Joint Industry Project (the JIP) provided an initial confirmation of the occurrence of gashydrates below the GoM seafloor. In 2006, release of data from a 2003 industry well in Alaminos Canyon 818 provided initial documentation of gashydrate occurrence at high concentrations in sand reservoirs in the GoM. From 2006 to 2008, the JIP facilitated the integration of geophysical and geological data to identify sites prospective for gashydrate-bearing sands, culminating in the recommendation of numerous drilling targets within four sites spanning a range of typical deepwater settings. Concurrent with, but independent of, the JIP prospecting effort, the Bureau of Ocean Energy Management (BOEM) conducted a preliminary assessment of the GoM gashydratepetroleum system, resulting in an estimate of 607 trillion cubic meters (21,444 trillion cubic feet) gas-in-place of which roughly one-third occurs at expected high concentrations in sand reservoirs. In 2009, the JIP drilled seven wells at three sites, discovering gashydrate at high saturation in sand reservoirs in four wells and suspected gashydrate at low to moderate saturations in two other wells. These results provide an initial confirmation of the complex nature and occurrence of gashydrate-bearing sands in the GoM, the efficacy of the integrated geological/geophysical prospecting approach used to identify the JIP drilling sites, and the relevance of the 2008 BOEM assessment.
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Well log characterization of natural gas hydrates
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.
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NASA Astrophysics Data System (ADS)
Xiao, Kun; Zou, Changchun; Yu, Changqing; Pi, Jinyun
2015-10-01
Audio-magnetotelluric (AMT) method is a kind of frequency-domain sounding technique, which can be applied to gas hydrate prospecting and assessments in the permafrost region due to its high frequency band. Based on the geological conditions of gas hydrate reservoir in the Qilian Mountain permafrost, by establishing high-resistance abnormal model for gas hydrate and carrying out numerical simulation using finite element method (FEM) and nonlinear conjugate gradient (NLCG) method, this paper analyzed the application range of AMT method and the best acquisition parameters setting scheme. When porosity of gas hydrate reservoir is less than 5%, gas hydrate saturation is greater than 70%, occurrence scale is less than 50 m, or bury depth is greater than 500 m, AMT technique cannot identify and delineate the favorable gas hydrate reservoir. Survey line should be more than twice the length of probable occurrence scale, while tripling the length will make the best result. The number of stations should be no less than 6, and 11 stations are optimal. At the high frequency section (10˜1000 Hz), there should be no less than 3 frequency points, 4 being the best number.
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The Role of Natural Hydrate on the Strength of Sands: Load-bearing or Cementing?
NASA Astrophysics Data System (ADS)
Priest, J. A.; Hayley, J. L.
2017-12-01
The strength of hydrate bearing sands is a key parameter for simulating the long-term performance of hydrate reservoirs during gas production and assessing reservoir and wellbore stability. Historically this parameter has been determined from testing synthesized hydrate sand samples, which has led to significant differences in measured strength that appears to reflect different formation methods adopted. At present, formation methods can be grouped into either those that form hydrate at grain contacts leading to a high strength `cemented' sand, or those where the hydrate forms a `load-bearing' structure in which the hydrate grains reside in the pore space resulting in more subtle changes in strength. Recovered natural hydrate-bearing cores typically exhibit this `load-bearing' behavior, although these cores have generally undergone significant changes in temperature and pressure during recovery, which may have altered the structure of the hydrate and sediment. Recent drilling expeditions using pressure coring, such as NGHP2 offshore India, have enabled intact hydrate bearing sediments to be recovered that have maintained hydrostatic stresses minimizing any changes in the hydrate structure within the core. Triaxial testing on these samples highlight enhanced strength even at zero effective stresses. This suggests that the hydrate forms a connected framework within the pore space apparently `cementing' the sand grains in place: we differentiate here between true cementation where hydrate is sintered onto the sand grains and typical observed behavior for cemented sands (cohesion, peak strength, post-peak strain softening). This inter-connected hydrate, and its ability to increase strength of the sands, appears to occur even at hydrate saturations as low as 30%, where typical `load-bearing' hydrates just start to increase strength. The results from pressure cores suggest that hydrate formation techniques that lead to `load-bearing' behavior may not capture the true interaction between the hydrate and sand and thus further research is needed to form synthesized hydrate bearing samples that more realistically mimic the observed strength behavior of natural hydrate bearing cores.
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NASA Astrophysics Data System (ADS)
Suzuki, K.; Takayama, T.; Fujii, T.
2016-12-01
We will present possible heterogeneity of pore-water salinity within methane hydrate reservoir of Daini-Atsumi knoll, on the basis of Logging-while-drilling (LWD) data and several kind of wire-line logging dataset. The LWD and the wire-line logging had been carried out during 2012 to 2013, before/after the first offshore gas-production-test from marine-methane-hydrate reservoir at Daini-Atsumi Knoll along the northeast Nankai trough. Several data from the logging, especially data from the reservoir saturation tool; RST, gave us some possible interpretation for heterogeneity distribution of chlorinity within the methane-hydrate reservoir. The computed pore-water chlorinity could be interpreted as condense of chlorinity at gas-hydrate formation. This year, we drilled several number of wells at Daini-Atsumi Knoll, again for next gas production test, and we have also found out possibility of chlorinity heterogeneity from LWD data of Neutron-capture cross section; i.e. Sigma. The distribution of chlorinity within gas-hydrate reservoir may help our understanding of gas hydrate-crystallization and/or dissociation in turbidite reservoir at Daini-Atsumi Knoll. This research is conducted as a part of the Research Consortium for Methane Hydrate Resource in Japan (MH21 Research consortium).
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New observations and insights into the morphology and growth kinetics of hydrate films.
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.
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New Observations and Insights into the Morphology and Growth Kinetics of Hydrate Films
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
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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.
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Collett, Timothy S.; Lee, Myung 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 MexicoGasHydrateJointIndustryProjectLegII (GOM JIP LegII) 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 gashydrates under various geologic conditions and to understand the geologic controls on the occurrence of gashydrate 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 gashydrate. There has been significant advancements in the use of downhole well-logging tools to acquire detailed information on the occurrence of gashydrate in nature: From using electrical resistivity and acoustic logs to identify gashydrate occurrences in wells to where wireline and advanced logging-while-drilling tools are routinely used to examine the petrophysical nature of gashydrate reservoirs and the distribution and concentration of gashydrates 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 gashydrate saturations in sediment grain supported (isotropic) systems such as sand reservoirs, but more advanced log analysis models are required to characterize gashydrate in fractured (anisotropic) reservoir systems. In support of the GOM JIP LegII 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.
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Cohesive Strength of Gas-hydrate-bearing Marine Sediments
NASA Astrophysics Data System (ADS)
Cook, A. E.; Goldberg, D.
2005-12-01
We examine the relationship between gas hydrate saturation and the cohesive strength of marine sediments in a variety of continental margin settings. The cohesive strength (cohesion) is a fundamental physical property controlling sediment resistance to compressive failure. The cohesion (Co), is typically defined by the uncompressive rock strength and the friction angle, but it can also be related to the dynamic Young's modulus (ED), where: Co = 1.5*10-3 ED. The dynamic Young's modulus is computed using in situ Vp, Vs, and bulk density borehole logs. The Co profiles are compared to estimates of the in situ hydrate saturation, Sh, calculated using electrical resistivity logs and the modified Archie formula: Sh = 1 - (aRw/RΦm)1/n. We will present results of these comparisons from data collected during Ocean Drilling Program Legs at Cascadia margin (204 & 168) and Blake Ridge (164), the JIP gas hydrate drilling project in the Gulf of Mexico, and Malik permafrost wells. In general, at all the sites investigated, Co steadily increases downhole as sediments compact due to overburden. In marine sediments, cohesion ranges from 500-2000kPa above the BSR, with a baseline gradient usually between 5 and 10 kPa/m. Preliminary results show at Cascadia margin that sediments with Sh > 15%, Co increases dramatically, at least 200kPa greater than the general trend of the downhole gradient. This suggests that Co is affected directly by Sh, and may be related to the rate of change in Sh (e.g. gradual or sharp) as a function of depth. Further study on the relationship between Co and Sh may provide information on the growth habit of gas hydrates in sediment pore spaces.
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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.
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García-González, Julia; Rodríguez-Robles, Desirée; Juan-Valdés, Andrés; Morán-del Pozo, Julia Mª; Guerra-Romero, M. Ignacio
2014-01-01
The replacement of natural aggregates by recycled aggregates in the concrete manufacturing has been spreading worldwide as a recycling method to counteract the large amount of construction and demolition waste. Although legislation in this field is still not well developed, many investigations demonstrate the possibilities of success of this trend given that concrete with satisfactory mechanical and durability properties could be achieved. However, recycled aggregates present a low quality compared to natural aggregates, the water absorption being their main drawback. When used untreated in concrete mix, the recycled aggregate absorb part of the water initially calculated for the cement hydration, which will adversely affect some characteristics of the recycled concrete. This article seeks to demonstrate that the technique of pre-saturation is able to solve the aforementioned problem. In order to do so, the water absorption of the aggregates was tested to determine the necessary period of soaking to bring the recycled aggregates into a state of suitable humidity for their incorporation into the mixture. Moreover, several concrete mixes were made with different replacement percentages of natural aggregate and various periods of pre-saturation. The consistency and compressive strength of the concrete mixes were tested to verify the feasibility of the proposed technique. PMID:28788188
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Anderson, B.I.; Collett, T.S.; Lewis, R.E.; Dubourg, I.
2008-01-01
Gas hydrates, which are naturally occurring ice-like combinations of gas and water, have the potential to provide vast amounts of natural gas from the world's oceans and polar regions. However, producing gas economically from hydrates entails major technical challenges. Proposed recovery methods such as dissociating or melting gas hydrates by heating or depressurization are currently being tested. One such test was conducted in northern Canada by the partners in the Mallik 2002 Gas Hydrate Production Research Well Program. This paper describes how resistivity logs were used to determine the size of the annular region of gas hydrate dissociation that occurred around the wellbore during the thermal test in the Mallik 5L-38 well. An open-hole logging suite, run prior to the thermal test, included array induction, array laterolog, nuclear magnetic resonance and 1.1-GHz electromagnetic propagation logs. The reservoir saturation tool was run both before and after the thermal test to monitor formation changes. A cased-hole formation resistivity log was run after the test.Baseline resistivity values in each formation layer (Rt) were established from the deep laterolog data. The resistivity in the region of gas hydrate dissociation near the wellbore (Rxo) was determined from electromagnetic propagation and reservoir saturation tool measurements. The radius of hydrate dissociation as a function of depth was then determined by means of iterative forward modeling of cased-hole formation resistivity tool response. The solution was obtained by varying the modeled dissociation radius until the modeled log overlaid the field log. Pretest gas hydrate production computer simulations had predicted that dissociation would take place at a uniform radius over the 13-ft test interval. However, the post-test resistivity modeling showed that this was not the case. The resistivity-derived dissociation radius was greatest near the outlet of the pipe that circulated hot water in the wellbore, where the highest temperatures were recorded. The radius was smallest near the center of the test interval, where a conglomerate section with low values of porosity and permeability inhibited dissociation. The free gas volume calculated from the resistivity-derived dissociation radii yielded a value within 20 per cent of surface gauge measurements. These results show that the inversion of resistivity measurements holds promise for use in future gas hydrate monitoring. ?? 2008 Society of Petrophysicists and Well Log Analysts. All rights reserved.
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Adsorption of Dissolved Gases (CH4, CO2, H2, Noble Gases) by Water-Saturated Smectite Clay Minerals
NASA Astrophysics Data System (ADS)
Bourg, I. C.; Gadikota, G.; Dazas, B.
2016-12-01
Adsorption of dissolved gases by water-saturated clay minerals plays important roles in a range of fields. For example, gas adsorption in on clay minerals may significantly impact the formation of CH4 hydrates in fine-grained sediments, the behavior of CH4 in shale, CO2 leakage across caprocks of geologic CO2 sequestration sites, H2 leakage across engineered clay barriers of high-level radioactive waste repositories, and noble gas geochemistry reconstructions of hydrocarbon migration in the subsurface. Despite its importance, the adsorption of gases on clay minerals remains poorly understood. For example, some studies have suggested that clay surfaces promote the formation of CH4 hydrates, whereas others indicate that clay surfaces inhibit the formation of CH4 hydrates. Here, we present molecular dynamics (MD) simulations of the adsorption of a range of gases (CH4, CO2, H2, noble gases) on clay mineral surfaces. Our results indicate that the affinity of dissolved gases for clay mineral surfaces has a non-monotone dependence on the hydrated radius of the gas molecules. This non-monotone dependence arises from a combination of two effects: the polar nature of certain gas molecules (in particular, CO2) and the templating of interfacial water structure by the clay basal surface, which results in the presence of interfacial water "cages" of optimal size for intermediate-size gas molecules (such as Ne or Ar).
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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.
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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.
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NASA Astrophysics Data System (ADS)
Wang, X.; Wu, S.; Yang, S.
2012-12-01
Wireline logging data acquired during China's first gas hydrate drilling expedition (GMGS-1) in April-June of 2007 and seismic data indicate the occurrences of gas hydrate above the base of gas hydrate stability (BGHS). Bottom simulating reflectors (BSRs) are widespread in the drilling zone, predominantly occurring beneath the ridges of migrating submarine canyons. Higher P-wave velocities and higher resistivity above BGHS at sites SH3, SH2 and SH7 indicate the presence of gas hydrate in the thickness range from 10 to 25 meters below seafloor. However, the measured compressional (P-wave) velocities at site SH3 show there are three abnormal P-wave velocities zones above the BGHS, which are lower than those of water-saturated sediments, indicating the presence of free gas in the pore space. The P-wave velocities drop as low as 1.0 m/s at the depth of 125 m. While the recovered core at 100 bars degassed show that methane was under unsaturated. Below the BSR, seismic data show enhanced reflections and the P-impedances have lower values, which inferred these reflections to be caused by free gas. To determine whether the low well-log P-wave velocity is caused by in-situ gas, synthetic seismograms were generated using the measured well-log P-wave velocity and calculated assuming water-saturated in the pore space. Comparing the surface seismic data with synthetic seismograms suggests that low P-wave velocities are likely caused by migrating gas due to borehole drilling. Three dimensional (3D) multi-channel seismic (MCS) data, inverted P-wave velocity, and RMS amplitude are used to study the detailed distribution and occurrences of the BSR and associated with the migration of gas in this basin. Three types of BSR and amplitude anomalies zones are identified from 3D seismic data. Gas hydrate in this basin are linked to and associated with gas accumulation below gas hydrate stability zone, which has a closerelationship with focused fluid flow features such as gas chimneys, faults, diapir, pipe.
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Effective-Medium Models for Marine Gas Hydrates, Mallik Revisited
NASA Astrophysics Data System (ADS)
Terry, D. A.; Knapp, C. C.; Knapp, J. H.
2011-12-01
Hertz-Mindlin type effective-medium dry-rock elastic models have been commonly used for more than three decades in rock physics analysis, and recently have been applied to assessment of marine gas hydrate resources. Comparisons of several effective-medium models with derivative well-log data from the Mackenzie River Valley, Northwest Territories, Canada (i.e. Mallik 2L-38 and 5L-38) were made several years ago as part of a marine gas hydrate joint industry project in the Gulf of Mexico. The matrix/grain supporting model (one of the five models compared) was clearly a better representation of the Mallik data than the other four models (2 cemented sand models; a pore-filling model; and an inclusion model). Even though the matrix/grain supporting model was clearly better, reservations were noted that the compressional velocity of the model was higher than the compressional velocity measured via the sonic logs, and that the shear velocities showed an even greater discrepancy. Over more than thirty years, variations of Hertz-Mindlin type effective medium models have evolved for unconsolidated sediments and here, we briefly review their development. In the past few years, the perfectly smooth grain version of the Hertz-Mindlin type effective-medium model has been favored over the infinitely rough grain version compared in the Gulf of Mexico study. We revisit the data from the Mallik wells to review assertions that effective-medium models with perfectly smooth grains are a better predictor than models with infinitely rough grains. We briefly review three Hertz-Mindlin type effective-medium models, and standardize nomenclature and notation. To calibrate the extended effective-medium model in gas hydrates, we use a well accepted framework for unconsolidated sediments through Hashin-Shtrikman bounds. We implement the previously discussed effective-medium models for saturated sediments with gas hydrates and compute theoretical curves of seismic velocities versus gas hydrate saturation to compare with well log data available from the Canadian gas hydrates research site. By directly comparing the infinitely rough and perfectly smooth grain versions of the Hertz-Mindlin type effective-medium model, we provide additional insight to the discrepancies noted in the Gulf of Mexico study.
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NASA Astrophysics Data System (ADS)
Flemings, P. B.; Phillips, S. C.
2017-12-01
In May 2017, a science team led by the University of Texas-Austin conducted drilling and coring operations from the Helix Q4000 targeting gas hydrates in sand-rich reservoirs in the Green Canyon 955 block in the northern Gulf of Mexico. The UT-GOM2-1 expedition goals were to 1) test two configurations of pressure coring devices to assess relative performance with respect to recovery and quality of samples and 2) gather sufficient samples to allow laboratories throughout the US to investigate a range of outstanding science questions related to the origin and nature of gas hydrate-bearing sands. In the first well (UT-GOM2-1-H002), 1 of the 8 cores were recovered under pressure with 34% recovery. In the second well (UT-GOM2-1-H005), 12 of 13 cores were recovered under pressure with 77% recovery. The pressure cores were imaged and logged under pressure. Samples were degassed both shipboard and dockside to interpret hydrate concentration and gas composition. Samples for microbiological and porewater analysis were taken from the depressurized samples. 21 3 ft pressure cores were returned to the University of Texas for storage, distribution, and further analysis. Preliminary analyses document that the hydrate-bearing interval is composed of two interbedded (cm to m thickness) facies. Lithofacies II is composed of sandy silt and has trough cross bedding whereas Lithofacies III is composed of clayey silt and no bedforms are observed. Lithofacies II has low density (1.7 to 1.9 g/cc) and high velocity (3000-3250 m/s) beds whereas Lithofacies 3 has high density ( 1.9-2.1g/cc) and low velocity ( 1700 m/s). Quantitative degassing was used to determine that Lithofacies II contains high hydrate saturation (66-87%) and Lithofacies III contains moderate saturation ( 18-30%). Gas samples were analyzed periodically in each experiment and were composed of primarily methane with an average of 94 ppm ethane and detectable, but not quantifiable, propane. The core data will provide a foundation for scientific exploration by the greater hydrate research community.
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Pre- and post-drill comparison of the Mount Elbert gas hydrate prospect, Alaska North Slope
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.
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NASA Astrophysics Data System (ADS)
Lu, H.; Hu, G.; Vanderveen, J.; Liu, C.; Ratcliffe, C.; Ripmeester, J.
2011-12-01
CO2 replacement of CH4 from methane hydrate has been proposed as a method to produce gas from natural gas hydrate by taking advantage of both the production of natural gas and the sequestration of CO2. To examine the validity of this method DOE/Conoco-Philips is considering having a field test in Alaska. The reaction of CO2 replacing CH4 from methane hydrate has been confirmed to be thermodynamically feasible, but concern is always raised about the reaction kinetics. Some kinetic studies in the system of methane hydrate and liquid or gaseous CO2 have found that the reaction proceeds at a very low rate. Natural gas hydrate occurs in sediments with multi-components and complex structure, so matters will be even more complicated. Up to now, few investigations have been carried out concerning the factors affecting the reaction process of CO2 replacing CH4 from methane hydrate. Experiments were implemented with sands, which were recovered from Mallik 5L-38 well, Mackenzie Delta, Northwest Territory, Canada, sediment that previously contained hydrate although it had been dried completely before our experiments. The water-saturated sands were tightly charged into a plastic bottle (90 mm deep and 60 mm wide), and then this test specimen was sealed in a pressure cell. After methane hydrate was synthesized in the test specimen for 108 days under a pressure of 11 to 8 MPa and a temperature of 3 degrees Celsius, liquid CO2 was introduced into the pressure cell. The conditions under which CO2 was reacted with methane hydrate were ~5.3 MPa and 5 degrees Celsius. After reacting for 15 days, the test specimen was recovered. The test specimen was cut into ~10 mm thick discs, and sub-samples were further taken from each of the discs. In addition to the determination of hydrate saturation and the gas composition, Raman spectroscopic studies were carried out for the sub-samples obtained. The results revealed: 1) less CO2 replacement in the bottom disc of the test specimen as compared with that in the top disc, implying that diffusion was a factor that controlled the movement of CO2 in the sediments, 2) an inhomogeneous replacement reaction even within the same disc, indicating that the contact area between methane hydrate and CO2 was a factor that determined the degree of replacement of CH4 from methane hydrate 3) the separate appearance of CO2 Raman intensities and CH4 Raman intensities in some portions of the test specimen, suggesting that CO2 was present in the form of CO2 hydrate in addition to being together with CH4 in other parts of the hydrate. Further analysis found that both CO2 diffusion and the contact area for reaction were associated with the pore structure of the sediments, which were heterogeneous both in pore size and in pore shape as observed with high resolution X-ray CT.
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Neutron diffraction from aligned stacks of lipid bilayers using the WAND instrument
Marquardt, Drew; Frontzek, Matthias D.; Zhao, Yu; ...
2018-02-06
Neutron diffraction from aligned stacks of lipid bilayers is examined using the Wide-Angle Neutron Diffractometer (WAND), located at the High Flux Isotope Reactor, Oak Ridge, Tennessee, USA. Data were collected at different levels of hydration and neutron contrast by varying the relative humidity (RH) and H 2O/D 2O ratio from multi-bilayers of dioleoylphosphatidylcholine and sunflower phosphatidylcholine extract aligned on single-crystal silicon substrates. This work highlights the capabilites of a newly fabricated sample hydration cell, which allows the lipid bilayers to be hydrated with varying H/D ratios from the RH generated by saturated salt solutions, and also demonstrates WAND's capability asmore » an instrument suitable for the study of aligned lipid multi-bilayers.« less
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Neutron diffraction from aligned stacks of lipid bilayers using the WAND instrument
DOE Office of Scientific and Technical Information (OSTI.GOV)
Marquardt, Drew; Frontzek, Matthias D.; Zhao, Yu
Neutron diffraction from aligned stacks of lipid bilayers is examined using the Wide-Angle Neutron Diffractometer (WAND), located at the High Flux Isotope Reactor, Oak Ridge, Tennessee, USA. Data were collected at different levels of hydration and neutron contrast by varying the relative humidity (RH) and H 2O/D 2O ratio from multi-bilayers of dioleoylphosphatidylcholine and sunflower phosphatidylcholine extract aligned on single-crystal silicon substrates. This work highlights the capabilites of a newly fabricated sample hydration cell, which allows the lipid bilayers to be hydrated with varying H/D ratios from the RH generated by saturated salt solutions, and also demonstrates WAND's capability asmore » an instrument suitable for the study of aligned lipid multi-bilayers.« less
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Electrical properties of methane hydrate + sediment mixtures: The σ of CH 4 Hydrate + Sediment
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
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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.
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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
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... provide complex carbohydrates. Avoid foods and beverages with high-fructose corn syrup, and limit consumption of naturally sweet fruit juices. Water. Stay well-hydrated by drinking water. Fats. Cut back on saturated ... fatty poultry and high-fat dairy products. Proteins. Focus on lean meat ...
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Prospecting for marine gas hydrate resources
Boswell, Ray; Shipp, Craig; Reichel, Thomas; Shelander, Dianna; Saeki, Tetsuo; Frye, Matthew; Shedd, William; Collett, Timothy S.; McConnell, Daniel R.
2016-01-01
As gas hydrate energy assessment matures worldwide, emphasis has evolved away from confirmation of the mere presence of gas hydrate to the more complex issue of prospecting for those specific accumulations that are viable resource targets. Gas hydrate exploration now integrates the unique pressure and temperature preconditions for gas hydrate occurrence with those concepts and practices that are the basis for conventional oil and gas exploration. We have aimed to assimilate the lessons learned to date in global gas hydrate exploration to outline a generalized prospecting approach as follows: (1) use existing well and geophysical data to delineate the gas hydrate stability zone (GHSZ), (2) identify and evaluate potential direct indications of hydrate occurrence through evaluation of interval of elevated acoustic velocity and/or seismic events of prospective amplitude and polarity, (3) mitigate geologic risk via regional seismic and stratigraphic facies analysis as well as seismic mapping of amplitude distribution along prospective horizons, and (4) mitigate further prospect risk through assessment of the evidence of gas presence and migration into the GHSZ. Although a wide range of occurrence types might ultimately become viable energy supply options, this approach, which has been tested in only a small number of locations worldwide, has directed prospect evaluation toward those sand-hosted, high-saturation occurrences that were presently considered to have the greatest future commercial potential.
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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.
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Electrical properties of methane hydrate + sediment mixtures
Du Frane, Wyatt L.; Stern, Laura A.; Constable, Steven; Weitemeyer, Karen A.; Smith, Megan M; Roberts, Jeffery J.
2015-01-01
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. Toward this goal, 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 EM field surveys. Here 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. 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.
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Role of naturally occurring gas hydrates in sediment transport
DOE Office of Scientific and Technical Information (OSTI.GOV)
McIver, R.D.
1982-06-01
Naturally occurring gas hydrates have the potential to store enormous volumes of both gas and water in semi-solid form in ocean-bottom sediments and then to release that gas and water when the hydrate's equilibrium condition are disturbed. Therefore, hydrates provide a potential mechanism for transporting large volumes of sediments. Under the combined low bottom-water temperatures and moderate hydrostatic pressures that exist over most of the continental slopes and all of the continental rises and abyssal plains, hydrocarbon gases at or near saturation in the interstitial waters of the near-bottom sediments will form hydrates. The gas can either be autochthonous, microbiallymore » produced gas, or allochthonous, catagenic gas from deeper sediments. Equilibrium conditions that stabilize hydrated sediments may be disturbed, for example, by continued sedimentation or by lowering of sea level. In either case, some of the solid gas-water matrix decomposes. Released gas and water volume exceeds the volume occupied by the hydrate, so the internal pressure rises - drastically if large volumes of hydrate are decomposed. Part of the once rigid sediment is converted to a gas- and water-rich, relatively low density mud. When the internal pressure, due to the presence of the compressed gas or to buoyancy, is sufficiently high, the overlying sediment may be lifted and/or breached, and the less dense, gas-cut mud may break through. Such hydrate-related phenomena can cause mud diapirs, mud volcanos, mud slides, or turbidite flows, depending on sediment configuration and bottom topography. 4 figures.« less
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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.
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Chloral hydrate for sedation of children with asthma during dental treatment.
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.
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Fratino, Lisa M; Daniel, Denise A; Cohen, Kenneth J; Chen, Allen R
2009-01-01
Our goal was to improve the efficiency of chemotherapy administration for pediatric oncology patients. We identified prechemotherapy hydration as the process that most often delayed chemotherapy administration. An aggressive hydration protocol, supported by fluid order sets, was developed for patients receiving planned chemotherapy. The mean interval from admission to achieving adequate hydration status was reduced significantly from 4.9 to 1.4 hours with a minor reduction in the time to initiate chemotherapy from 9.6 to 8.6 hours. Chemotherapy availability became the new rate-limiting process.
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New Methods for Evaluating Skin Injury from Sulfur Mustard in the Hairless Guinea Pig
1993-05-13
MUSTARD IN THE HAIRLESS GUINEA PIG Ernest H. Braue, Jr., Catherine R. Bangledorf, and Robert G. Rieder "U.S. Army Medical Research Institute of Chemical...evaluating the skin hydration state. The skin of anesthetized hairless guinea pigs was exposed to saturated HD vapor (1.4mg/ml) at 4 sites for 3, 5, 7, or 9...assessment of skin damage following cutaneous exposure to HD vapor. EXPERIMENTAL METHODS Each hairless guinea pig (HGP) was exposed to saturated HD vapor
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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.
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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.
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NASA Astrophysics Data System (ADS)
Jiang, Mingjing; He, Jie; Wang, Jianfeng; Zhou, Yaping; Zhu, Fangyuan
2017-12-01
Due to increasing global energy demands, research is being conducted on the mechanical properties of methane hydrate-bearing soils (MHBSs), from which methane hydrate (MH) will be explored. This paper presents a numerical approach to study the mechanical properties of MHBSs. The relationship between the level of MH saturation and the interparticle bond thickness is first obtained by analyzing the scanning electron microscope images of MHBS samples, in which is the bridge connecting the micromechanical behavior captured by the DEM with the macroscopic properties of MHBSs. A simplified thermal-hydromechanical (THM) bond model that considers the different bond thicknesses is then proposed to describe the contact behavior between the soil particles and those incorporated into the discrete element method (DEM). Finally, a series of biaxial compression tests are carried out with different MH saturations under different effective confining pressures to analyze the mechanical properties of deep-sea MHBSs. The results of the DEM numerical simulation are also compared with the findings from triaxial compression tests. The results show that the macromechanical properties of deep-sea MHBSs can be qualitatively captured by the proposed DEM. The shear strength, cohesion, and volumetric contraction of deep-sea MHBSs increase with increasing MH saturation, although its influence on the internal friction angle is obscure. The shear strength and volumetric contraction increase with increasing effective confining pressure. The peak shear strength and the dilation of MHBSs increase as the critical bond thickness increases, while the residual deviator stress largely remains the same at a larger axial strain. With increasing the axial strain, the percentage of broken bonds increases, along with the expansion of the shear band.
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NASA Astrophysics Data System (ADS)
Kida, Masato; Jin, Yusuke; Watanabe, Mizuho; Murayama, Tetsuro; Nagao, Jiro
2017-09-01
In this report, we describe the dissociation behavior of gas hydrate grains pressed at 1 and 6 MPa. Certain simple gas hydrates in powder form show anomalous preservation phenomenon under their thermodynamic unstable condition. Investigation of simple hydrates of methane, ethane, and propane reveals that high pressure applied to the gas hydrate particles enhances their preservation effects. Application of high pressure increases the dissociation temperature of methane hydrate and has a restrictive effect against the dissociation of ethane and propane hydrate grains. These improvements of gas hydrate preservation by increasing pressure to the initial gas hydrate particles imply that appropriate pressure applied to gas hydrate particles enhances gas hydrate preservation effects.
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Yang, Lei; Zhou, Weihua; Xue, Kaihua; Wei, Rupeng; Ling, Zheng
2018-05-01
The enormous potential as an alternative energy resource has made natural gas hydrates a material of intense research interest. Their exploration and sample characterization require a quick and effective analysis of the hydrate-bearing cores recovered under in situ pressures. Here a novel Pressure Core Ultrasonic Test System (PCUTS) for on-board analysis of sediment cores containing gas hydrates at in situ pressures is presented. The PCUTS is designed to be compatible with an on-board pressure core transfer device and a long gravity-piston pressure-retained corer. It provides several advantages over laboratory core analysis including quick and non-destructive detection, in situ and successive acoustic property acquisition, and remission of sample storage and transportation. The design of the unique assembly units to ensure the in situ detection is demonstrated, involving the U-type protecting jackets, transducer precession device, and pressure stabilization system. The in situ P-wave velocity measurements make the detection of gas hydrate existence in the sediments possible on-board. Performance tests have verified the feasibility and sensitivity of the ultrasonic test unit, showing the dependence of P-wave velocity on gas hydrate saturation. The PCUTS has been successfully applied for analysis of natural samples containing gas hydrates recovered from the South China Sea. It is indicated that on-board P-wave measurements could provide a quick and effective understanding of the hydrate occurrence in natural samples, which can assist further resource exploration, assessment, and subsequent detailed core analysis.
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NASA Astrophysics Data System (ADS)
Yang, Lei; Zhou, Weihua; Xue, Kaihua; Wei, Rupeng; Ling, Zheng
2018-05-01
The enormous potential as an alternative energy resource has made natural gas hydrates a material of intense research interest. Their exploration and sample characterization require a quick and effective analysis of the hydrate-bearing cores recovered under in situ pressures. Here a novel Pressure Core Ultrasonic Test System (PCUTS) for on-board analysis of sediment cores containing gas hydrates at in situ pressures is presented. The PCUTS is designed to be compatible with an on-board pressure core transfer device and a long gravity-piston pressure-retained corer. It provides several advantages over laboratory core analysis including quick and non-destructive detection, in situ and successive acoustic property acquisition, and remission of sample storage and transportation. The design of the unique assembly units to ensure the in situ detection is demonstrated, involving the U-type protecting jackets, transducer precession device, and pressure stabilization system. The in situ P-wave velocity measurements make the detection of gas hydrate existence in the sediments possible on-board. Performance tests have verified the feasibility and sensitivity of the ultrasonic test unit, showing the dependence of P-wave velocity on gas hydrate saturation. The PCUTS has been successfully applied for analysis of natural samples containing gas hydrates recovered from the South China Sea. It is indicated that on-board P-wave measurements could provide a quick and effective understanding of the hydrate occurrence in natural samples, which can assist further resource exploration, assessment, and subsequent detailed core analysis.
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Effects of hydrated lime on radionuclides stabilization of Hanford tank residual waste.
Wang, Guohui; Um, Wooyong; Cantrell, Kirk J; Snyder, Michelle M V; Bowden, Mark E; Triplett, Mark B; Buck, Edgar C
2017-10-01
Chemical stabilization of tank residual waste is part of a Hanford Site tank closure strategy to reduce overall risk levels to human health and the environment. In this study, a set of column leaching experiments using tank C-104 residual waste were conducted to evaluate the leachability of uranium (U) and technetium (Tc) where grout and hydrated lime were applied as chemical stabilizing agents. The experiments were designed to simulate future scenarios where meteoric water infiltrates through the vadose zones into the interior of the tank filled with layers of grout or hydrated lime, and then contacts the residual waste. Effluent concentrations of U and Tc were monitored and compared among three different packing columns (waste only, waste + grout, and waste + grout + hydrated lime). Geochemical modeling of the effluent compositions was conducted to determine saturation indices of uranium solid phases that could control the solubility of uranium. The results indicate that addition of hydrated lime strongly stabilized the uranium through transforming uranium to a highly insoluble calcium uranate (CaUO 4 ) or similar phase, whereas no significant stabilization effect of grout or hydrated lime was observed on Tc leachability. The result implies that hydrated lime could be a great candidate for stabilizing Hanford tank residual wastes where uranium is one of the main concerns. Published by Elsevier Ltd.
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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.
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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
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Probing methane hydrate nucleation through the forward flux sampling method.
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.
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NASA Astrophysics Data System (ADS)
Haines, S. S.; Hart, P. E.; Collett, T. S.; Shedd, W. W.; Frye, M.
2014-12-01
In 2013, the U.S. Geological Survey led a seismic acquisition expedition in the Gulf of Mexico, acquiring multicomponent data and high-resolution 2D multichannel seismic (MCS) data at Green Canyon 955 (GC955) and Walker Ridge 313 (WR313). Based on previously collected logging-while-drilling (LWD) borehole data, these gas hydrate study sites are known to include high concentrations of gas hydrate within sand layers. At GC955 our new 2D data reveal at least three features that appear to be fluid-flow pathways (chimneys) responsible for gas migration and thus account for some aspects of the gas hydrate distribution observed in the LWD data. Our new data also show that the main gas hydrate target, a Pleistocene channel/levee complex, has an areal extent of approximately 5.5 square kilometers and that a volume of approximately 3 x 107 cubic meters of this body lies within the gas hydrate stability zone. Based on LWD-inferred values and reasonable assumptions for net sand, sand porosity, and gas hydrate saturation, we estimate a total equivalent gas-in-place volume of approximately 8 x 108 cubic meters for the inferred gas hydrate within the channel/levee deposits. At WR313 we are able to map the thin hydrate-bearing sand layers in considerably greater detail than that provided by previous data. We also can map the evolving and migrating channel feature that persists in this area. Together these data and the emerging results provide valuable new insights into the gas hydrate systems at these two sites.
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Hydrogen speciation in hydrated layers on nuclear waste glass
DOE Office of Scientific and Technical Information (OSTI.GOV)
Aines, R.D.; Weed, H.C.; Bates, J.K.
1987-12-31
The hydration of an outer layer on nuclear waste glasses in known to occur during leaching, but the actual speciation of hydrogen (as water or hydroxyl groups) in these layers has not been determined. As part of the Nevada Nuclear Waste Storage Investigations Project, we have used infrared spectroscopy to determine hydrogen speciations in three nuclear waste glass compositions (SRL-131 & 165, and PNL 76-68), which were leached at 90{sup 0}C (all glasses) or hydrated in a vapor-saturated atmosphere at 202{sup 0}C (SRL-131 only). Hydroxyl groups were found in the surface layers of all the glasses. In addition, molecular watermore » was found in the surface of SRL-131 and PNL 76-68 glasses that had been leached for several months in deionized water, and in the vapor-hydrated sample. The water/hydroxyl ratio increases with increasing reaction time; molecular water makes up most of the hydrogen in the thick reaction layers on vapor-phase hydrated glass while only hydroxyl occurs in the least reacted samples. The hydrated layer on the nuclear waste glasses appears to be of relatively low water content (4 to 7% by weight) and is not substantially hydroxylated. Thus, these layers do not have many of the properties associated with gel layers.« less
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Analysis of factors influencing hydration site prediction based on molecular dynamics simulations.
Yang, Ying; Hu, Bingjie; Lill, Markus A
2014-10-27
Water contributes significantly to the binding of small molecules to proteins in biochemical systems. Molecular dynamics (MD) simulation based programs such as WaterMap and WATsite have been used to probe the locations and thermodynamic properties of hydration sites at the surface or in the binding site of proteins generating important information for structure-based drug design. However, questions associated with the influence of the simulation protocol on hydration site analysis remain. In this study, we use WATsite to investigate the influence of factors such as simulation length and variations in initial protein conformations on hydration site prediction. We find that 4 ns MD simulation is appropriate to obtain a reliable prediction of the locations and thermodynamic properties of hydration sites. In addition, hydration site prediction can be largely affected by the initial protein conformations used for MD simulations. Here, we provide a first quantification of this effect and further indicate that similar conformations of binding site residues (RMSD < 0.5 Å) are required to obtain consistent hydration site predictions.
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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.
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Martian CH(4): sources, flux, and detection.
Onstott, T C; McGown, D; Kessler, J; Lollar, B Sherwood; Lehmann, K K; Clifford, S M
2006-04-01
Recent observations have detected trace amounts of CH(4) heterogeneously distributed in the martian atmosphere, which indicated a subsurface CH(4) flux of ~2 x 10(5) to 2 x 10(9) cm(2) s(1). Four different origins for this CH(4) were considered: (1) volcanogenic; (2) sublimation of hydrate- rich ice; (3) diffusive transport through hydrate-saturated cryosphere; and (4) microbial CH(4) generation above the cryosphere. A diffusive flux model of the martian crust for He, H(2), and CH(4) was developed based upon measurements of deep fracture water samples from South Africa. This model distinguishes between abiogenic and microbial CH(4) sources based upon their isotopic composition, and couples microbial CH(4) production to H(2) generation by H(2)O radiolysis. For a He flux of approximately 10(5) cm(2) s(1) this model yields an abiogenic CH(4) flux and a microbial CH(4) flux of approximately 10(6) and approximately 10(9) cm(2) s(1), respectively. This flux will only reach the martian surface if CH(4) hydrate is saturated in the cryosphere; otherwise it will be captured within the cryosphere. The sublimation of a hydrate-rich cryosphere could generate the observed CH(4) flux, whereas microbial CH(4) production in a hypersaline environment above the hydrate stability zone only seems capable of supplying approximately 10(5) cm(2) s(1) of CH(4). The model predicts that He/H(2)/CH(4)/C(2)H(6) abundances and the C and H isotopic values of CH(4) and the C isotopic composition of C(2)H(6) could reveal the different sources. Cavity ring-down spectrometers represent the instrument type that would be most capable of performing the C and H measurements of CH(4) on near future rover missions and pinpointing the cause and source of the CH(4) emissions.
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The Exchange Reaction Between Methane Hydrate and Carbon Dioxide: An Oceanic Feasibility Test
NASA Astrophysics Data System (ADS)
Dunk, R. M.; Brewer, P. G.; Peltzer, E. T.; Walz, P. M.; Hester, K. C.; Sloan, E. D.
2006-12-01
The conversion of CH4 hydrate to CO2 hydrate offers, in principle, a way of sequestering CO2, with the additional recovery of CH4 gas as an energy source. We report results from the first in-situ oceanic experiment on this reaction, carried out in August 2006 at the massive thermogenic hydrate mounds in 850 m water depth, Barkley Canyon, offshore from Vancouver Island (48° 18.642' N, 126° 3.903' W), using MBARI's ROV Tiburon deployed from the R/V Western Flyer. Two small cores (10 cm length, 4 cm diameter) of white hydrate were collected from exposed outcrops using an ROV operated tool and hydraulically ejected into a glass walled, closed top, reaction chamber. Approximately 2 L of liquid CO2 were dispensed into the chamber, and the chamber transferred to an aluminium base plate to seal the system. Under ambient conditions (P = 870 dbar, T = 4.0 °C, S = 34.2), the densities of natural gas hydrate and liquid CO2 are closely matched and less than that of seawater, where the hydrate cores floated at the top of the chamber fully immersed within the buoyant liquid CO2. Over the following ~48 hours, the system was inspected periodically with the ROV HDTV camera prior to examination with the sea-going laser Raman spectrometer, DORISS II. For this, the chamber was transferred to a Precision Underwater Positioner (PUP) that enabled focusing of the laser beam with sub- mm precision. Our choice of where to focus the laser was based upon the need to explore all phases the cored natural gas hydrate, liquid CO2, any created CO2 hydrate, and any liberated CH4 gas. The natural gas hydrate was composed primarily of CH4, with minor amounts of C2H6 and C3H8, indicating the presence of Structure II hydrate. To date, laboratory experiments have focused on the reaction between pure Structure I CH4 hydrate and CO2 vapour, where the difference in free energy between the CH4 and CO2 hydrate states provides a thermodynamic argument in favour of conversion. However for a Structure II hydrate with a complex guest gas composition immersed in liquid CO2 there are multiple pathways for the reaction to proceed. If the hydrate cage occupancy is 100% then we suspect on thermodynamic grounds that the reaction may proceed slowly; nevertheless if cage occupancy is <100%, and/or a mixture of Structure I and II is present, then substitution could occur rapidly. In addition, dissolution of the natural gas hydrate in the unsaturated liquid CO2 will liberate water molecules that are then available to form CO2 hydrate. Obviously, grain size and porosity (surface area) will have profound effects on reaction rate and extent. We also note that the solubility of CH4 in CO2 is significant, and we may not expect liberation of a free CH4 gas phase until the saturation condition has been met. Given the complexity of this system, the only way to know what will occur is to do the experiment. Indeed, spectra were obtained of a commingled CO2 and CH4 hydrate. The CO2 fermi-diad peaks in the hydrate phase are distinguishable from the liquid, and are shifted to lower wavenumbers by ~~3 cm-1. We also observed the presence of dissolved CH4 within the liquid CO2, and free CH4 gas in a small but visually identifiable bubble layer at the top of the chamber. The initial success of this pilot study bodes well for future investigations both in the laboratory and in ROV based experiments.
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Initiation of Martian Outflow Channels: Related to the Dissociation of Gas Hydrate?
NASA Technical Reports Server (NTRS)
Max, Michael D.; Clifford, Stephen M.
2001-01-01
We propose that the disruption of subpermafrost aquifers on Mars by the thermal- or pressure-induced dissociation of methane hydrate may have been a frequent trigger for initiating outflow channel activity. This possibility is raised by recent work that suggests that significant amounts of methane and gas hydrate may have been produced within and beneath the planet's cryosphere. On Earth, the build-up of overpressured water and gas by the decomposition of hydrate deposits has been implicated in the formation of large blowout features on the ocean floor. These features display a remarkable resemblance (in both morphology and scale) to the chaotic terrain found at the source of many Martian channels. The destabilization of hydrate can generate pressures sufficient to disrupt aquifers confined by up to 5 kilometers of frozen ground, while smaller discharges may result from the water produced by the decomposition of near-surface hydrate alone.
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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.
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Water in volcanic glass: From volcanic degassing to secondary hydration
NASA Astrophysics Data System (ADS)
Seligman, Angela N.; Bindeman, Ilya N.; Watkins, James M.; Ross, Abigail M.
2016-10-01
Volcanic glass is deposited with trace amounts (0.1-0.6 wt.%) of undegassed magmatic water dissolved in the glass. After deposition, meteoric water penetrates into the glass structure mostly as molecular H2O. Due to the lower δD (‰) values of non-tropical meteoric waters and the ∼30‰ offset between volcanic glass and environmental water during hydration, secondary water imparts lighter hydrogen isotopic values during secondary hydration up to a saturation concentration of 3-4 wt.% H2O. We analyzed compositionally and globally diverse volcanic glass from 0 to 10 ka for their δD and H2Ot across different climatic zones, and thus different δD of precipitation, on a thermal conversion elemental analyzer (TCEA) furnace attached to a mass spectrometer. We find that tephrachronologically coeval rhyolite glass is hydrated faster than basaltic glass, and in the majority of glasses an increase in age and total water content leads to a decrease in δD (‰), while a few equatorial glasses have little change in δD (‰). We compute a magmatic water correction based on our non-hydrated glasses, and calculate an average 103lnαglass-water for our hydrated felsic glasses of -33‰, which is similar to the 103lnαglass-water determined by Friedman et al. (1993a) of -34‰. We also determine a smaller average 103lnαglass-water for all our mafic glasses of -23‰. We compare the δD values of water extracted from our glasses to local meteoric waters following the inclusion of a -33‰ 103lnαglass-water. We find that, following a correction for residual magmatic water based on an average δD and wt.% H2Ot of recently erupted ashes from our study, the δD value of water extracted from hydrated volcanic glass is, on average, within 4‰ of local meteoric water. To better understand the difference in hydration rates of mafic and felsic glasses, we imaged 6 tephra clasts ranging in age and chemical composition with BSE (by FEI SEM) down to a submicron resolution. Mafic tephra have more bubbles per unit area (25-77 mm-2) than felsic tephra (736 mm-2) and thicker average bubble walls (0.07 mm) than felsic tephra (0.02 mm). We use a simplified diffusion model to quantify the hydration rate of vesicular glass as a function of the diffusivity of water and the average bubble wall thickness. Based on fits to our hydration rate data, we estimate the initial low-temperature diffusivity at 0.1 wt.% H2Ot in volcanic glass (mafic and felsic) to be on the order of 10-3 to 10-4 μm2/year and find that differences in hydration rates between mafic and felsic tephra can be attributed primarily to differences in vesicularity, although slightly slower hydration of basalt cannot be precluded. We also observe no consistent temporal difference in secondary meteoric water uptake in wet versus dry and hot versus cold climates.
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Hydration of Atmospheric Molecular Clusters: Systematic Configurational Sampling.
Kildgaard, Jens; Mikkelsen, Kurt V; Bilde, Merete; Elm, Jonas
2018-05-09
We present a new systematic configurational sampling algorithm for investigating the potential energy surface of hydrated atmospheric molecular clusters. The algo- rithm is based on creating a Fibonacci sphere around each atom in the cluster and adding water molecules to each point in 9 different orientations. To allow the sam- pling of water molecules to existing hydrogen bonds, the cluster is displaced along the hydrogen bond and a water molecule is placed in between in three different ori- entations. Generated redundant structures are eliminated based on minimizing the root mean square distance (RMSD) of different conformers. Initially, the clusters are sampled using the semiempirical PM6 method and subsequently using density func- tional theory (M06-2X and ωB97X-D) with the 6-31++G(d,p) basis set. Applying the developed algorithm we study the hydration of sulfuric acid with up to 15 water molecules. We find that the additions of the first four water molecules "saturate" the sulfuric acid molecule and are more thermodynamically favourable than the addition of water molecule 5-15. Using the large generated set of conformers, we assess the performance of approximate methods (ωB97X-D, M06-2X, PW91 and PW6B95-D3) in calculating the binding energies and assigning the global minimum conformation compared to high level CCSD(T)-F12a/VDZ-F12 reference calculations. The tested DFT functionals systematically overestimates the binding energies compared to cou- pled cluster calculations, and we find that this deficiency can be corrected by a simple scaling factor.
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DOT National Transportation Integrated Search
2016-05-01
Using saturated lightweight fine aggregate (LWFA) in concrete mixtures : can replenish water that is depleted during cement hydration without : influencing the water-to-cement (w/c) ratio. This process, known as : internal curing (IC), can contribute...
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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.
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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
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Sun, Chang Q; Chen, Jiasheng; Gong, Yinyan; Zhang, Xi; Huang, Yongli
2018-01-25
We resolved the O:H-O bond transition from the mode of ordinary water to its hydration in terms of its phonon stiffness (vibration frequency shift Δω), order of fluctuation (line width), and number fraction (phonon abundance), f x (C) = N hyd /N total . The f x (C) follows f H (C) = 0, f Li (C) ∝ f OH (C) ∝ C, and f Br (C) ∝ 1 - exp(-C/C 0 ) toward saturation with C being the solute concentration. The invariant df x (C)/dC suggests that the solute forms a constantly sized hydration droplet without responding to interference of other ions because its hydrating H 2 O dipoles fully screen its electric field. However, the number inadequacy of the highly ordered hydration H 2 O dipoles partially screens the large Br - . The Br - then interacts repulsively with other Br - anions, which weakens its electric field and the f Br (C) approaches saturation at higher solute concentration. The consistency in the concentration trend of the f LiBr (C), the Jones-Dole viscosity η(C), and the surface stress of LiBr solution clarifies their common origin of ionic polarization. The resultant energy of the solvent H-O exothermic elongation by O: ⇔ :O repulsion and the solute H-O endothermic contraction by bond-order deficiency heats up the LiOH solution. An estimation of at least 0.15 eV (160% of the O:H cohesive energy of 0.1 eV) suggests that the H-O elongation is the main source heating up the solution, while the molecular motion, structure fluctuation, or even evaporation dissipates energy caped at 0.1 eV.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Briggs, Brandon R; Graw, Michael; Brodie, Eoin L
2013-11-01
The biogeochemical processes that occur in marine sediments on continental margins are complex; however, from one perspective they can be considered with respect to three geochemical zones based on the presence and form of methane: sulfate–methane transition (SMTZ), gas hydrate stability zone (GHSZ), and free gas zone (FGZ). These geochemical zones may harbor distinct microbial communities that are important in biogeochemical carbon cycles. The objective of this study was to describe the microbial communities in sediments from the SMTZ, GHSZ, and FGZ using molecular ecology methods (i.e. PhyloChip microarray analysis and terminal restriction fragment length polymorphism (T-RFLP)) and examining themore » results in the context of non-biological parameters in the sediments. Non-metric multidimensional scaling and multi-response permutation procedures were used to determine whether microbial community compositions were significantly different in the three geochemical zones and to correlate samples with abiotic characteristics of the sediments. This analysis indicated that microbial communities from all three zones were distinct from one another and that variables such as sulfate concentration, hydrate saturation of the nearest gas hydrate layer, and depth (or unmeasured variables associated with depth e.g. temperature, pressure) were correlated to differences between the three zones. The archaeal anaerobic methanotrophs typically attributed to performing anaerobic oxidation of methane were not detected in the SMTZ; however, the marine benthic group-B, which is often found in SMTZ, was detected. Within the GHSZ, samples that were typically closer to layers that contained higher hydrate saturation had indicator sequences related to Vibrio-type taxa. These results suggest that the biogeographic patterns of microbial communities in marine sediments are distinct based on geochemical zones defined by methane.« less
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Thermodynamic functions of hydration of hydrocarbons at 298.15 K and 0.1 MPa
NASA Astrophysics Data System (ADS)
Plyasunov, Andrey V.; Shock, Everett L.
2000-02-01
An extensive compilation of experimental data yielding the infinite dilution partial molar Gibbs energy of hydration Δ hGO, enthalpy of hydration Δ hHO, heat capacity of hydration Δ hCpO, and volume V2O, at the reference temperature and pressure, 298.15 K and 0.1 MPa, is presented for hydrocarbons (excluding polyaromatic compounds) and monohydric alcohols. These results are used in a least-squares procedure to determine the numerical values of the corresponding properties of the selected functional groups. The simple first order group contribution method, which in general ignores nearest-neighbors and steric hindrance effects, was chosen to represent the compiled data. Following the precedent established by Cabani et al. (1981), the following groups are considered: CH 3, CH 2, CH, C for saturated hydrocarbons; c-CH 2, c-CH, c-C for cyclic saturated hydrocarbons; CH ar, C ar for aromatic hydrocarbons (containing the benzene ring); C=C, C≡C for double and triple bonds in linear hydrocarbons, respectively; c-C=C for the double bond in cyclic hydrocarbons; H for a hydrogen atom attached to the double bond (both in linear and cyclic hydrocarbons) or triple bond; and OH for the hydroxyl functional group. In addition it was found necessary to include the "pseudo"-group I(C-C) to account for the specific interactions of the neighboring hydrocarbon groups attached to the benzene or cyclic ring (in the latter case only for cis-isomers). Results of this study, the numerical values of the group contributions, will allow in most cases reasonably accurate estimations of Δ hGO, Δ hHO, Δ hCpO, and V2O at 298.15 K, 0.1 MPa for many hydrocarbons involved in geochemical and environmental processes.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Hargis, Craig W.; Kirchheim, Ana Paula; Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu
Suspensions of synthetic ye'elimite (C{sub 4}A{sub 3}S{sup ¯}) in a saturated gypsum (CS{sup ¯}H{sub 2}) and calcium hydroxide (CH) solution were examined in-situ in a wet cell by soft X-ray transmission microscopy and ex-situ by scanning electron microscopy. The most voluminous hydration product observed was ettringite. Ettringite commonly displayed acicular, filiform, reticulated, and stellate crystal habits. Additionally, pastes with C{sub 4}A{sub 3}S{sup ¯}, 15% CS{sup ¯}H{sub 2}, and varying amounts of CH were prepared and examined with X-ray diffraction (XRD) and isothermal calorimetry. The XRD experiments showed that increasing CH content caused more solid solution (SO{sub 4}{sup 2−}/OH{sup −}) AFmmore » phases to form at early ages (< 1 d) and more monosulfate to form at later ages (> 1 d). Calorimetry indicated that the increased production of solid solution AFm was accompanied with an increase in the initial (< 30 min) rate of heat evolution, and increasing CH generally reduced the time till the second maximum rate of heat evolution due to the formation of ettringite and monosulfate.« less
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The big fat LARS - a LArge Reservoir Simulator for hydrate formation and gas production
NASA Astrophysics Data System (ADS)
Beeskow-Strauch, Bettina; Spangenberg, Erik; Schicks, Judith M.; Giese, Ronny; Luzi-Helbing, Manja; Priegnitz, Mike; Klump, Jens; Thaler, Jan; Abendroth, Sven
2013-04-01
Simulating natural scenarios on lab scale is a common technique to gain insight into geological processes with moderate effort and expenses. Due to the remote occurrence of gas hydrates, their behavior in sedimentary deposits is largely investigated on experimental set ups in the laboratory. In the framework of the submarine gas hydrate research project (SUGAR) a large reservoir simulator (LARS) with an internal volume of 425 liter has been designed, built and tested. To our knowledge this is presently a word-wide unique set up. Because of its large volume it is suitable for pilot plant scale tests on hydrate behavior in sediments. That includes not only the option of systematic tests on gas hydrate formation in various sedimentary settings but also the possibility to mimic scenarios for the hydrate decomposition and subsequent natural gas extraction. Based on these experimental results various numerical simulations can be realized. Here, we present the design and the experimental set up of LARS. The prerequisites for the simulation of a natural gas hydrate reservoir are porous sediments, methane, water, low temperature and high pressure. The reservoir is supplied by methane-saturated and pre-cooled water. For its preparation an external gas-water mixing stage is available. The methane-loaded water is continuously flushed into LARS as finely dispersed fluid via bottom-and-top-located sparger. The LARS is equipped with a mantle cooling system and can be kept at a chosen set temperature. The temperature distribution is monitored at 14 reasonable locations throughout the reservoir by Pt100 sensors. Pressure needs are realized using syringe pump stands. A tomographic system, consisting of a 375-electrode-configuration is attached to the mantle for the monitoring of hydrate distribution throughout the entire reservoir volume. Two sets of tubular polydimethylsiloxan-membranes are applied to determine gas-water ratio within the reservoir using the effect of permeability differences between gaseous and dissolved methane (Zimmer et al., 2011). Gas hydrate is formed using a confined pressure of 12-15 MPa and a fluid pressure of 8-11 MPa with a set temperature of 275 K. The duration of the formation process depends on the required hydrate saturation and is usually in a range of several weeks. The subsequent decomposition experiments aiming at testing innovative production scenarios such as the application of a borehole tool for thermal stimulation of hydrate via catalytic oxidation of methane within an autothermal catalytic reactor (Schicks et al. 2011). Furthermore, experiments on hydrate decomposition via pressure reduction are performed to mimic realistic scenarios such as found during the production test in Mallik (Yasuda and Dallimore, 2007). In the near future it is planned to scale up existing results on CH4-CO2 exchange efficiency (e.g. Strauch and Schicks, 2012) by feeding CO2 to the hydrate reservoir. All experiments are due to the gain of high-resolution spatial and temporal data predestined as a base for numerical modeling. References Schicks, J. M., Spangenberg, E., Giese, R., Steinhauer, B., Klump, J., Luzi, M., 2011. Energies, 4, 1, 151-172. Zimmer, M., Erzinger, J., Kujawa, C., 2011. Int. J. of Greenhouse Gas Control, 5, 4, 995-1001. Yasuda, M., Dallimore, S. J., 2007. Jpn. Assoc. Pet. Technol., 72, 603-607. Beeskow-Strauch, B., Schicks, J.M., 2012. Energies, 5, 420-437.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Juanes, Ruben
The overall goals of this research are: (1) to determine the physical fate of single and multiple methane bubbles emitted to the water column by dissociating gas hydrates at seep sites deep within the hydrate stability zone or at the updip limit of gas hydrate stability, and (2) to quantitatively link theoretical and laboratory findings on methane transport to the analysis of real-world field-scale methane plume data placed within the context of the degrading methane hydrate province on the US Atlantic margin. The project is arranged to advance on three interrelated fronts (numerical modeling, laboratory experiments, and analysis of field-basedmore » plume data) simultaneously. The fundamental objectives of each component are the following: Numerical modeling: Constraining the conditions under which rising bubbles become armored with hydrate, the impact of hydrate armoring on the eventual fate of a bubble’s methane, and the role of multiple bubble interactions in survival of methane plumes to very shallow depths in the water column. Laboratory experiments: Exploring the parameter space (e.g., bubble size, gas saturation in the liquid phase, “proximity” to the stability boundary) for formation of a hydrate shell around a free bubble in water, the rise rate of such bubbles, and the bubble’s acoustic characteristics using field-scale frequencies. Field component: Extending the results of numerical modeling and laboratory experiments to the field-scale using brand new, existing, public-domain, state-of-the-art real world data on US Atlantic margin methane seeps, without acquiring new field data in the course of this particular project. This component quantitatively analyzes data on Atlantic margin methane plumes and place those new plumes and their corresponding seeps within the context of gas hydrate degradation processes on this margin.« less
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Scientific objectives of the Gulf of Mexico gas hydrate JIP leg II drilling
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.
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Mapping the Fluid Pathways and Permeability Barriers of a Large Gas Hydrate Reservoir
NASA Astrophysics Data System (ADS)
Campbell, A.; Zhang, Y. L.; Sun, L. F.; Saleh, R.; Pun, W.; Bellefleur, G.; Milkereit, B.
2012-12-01
An understanding of the relationship between the physical properties of gas hydrate saturated sedimentary basins aids in the detection, exploration and monitoring one of the world's upcoming energy resources. A large gas hydrate reservoir is located in the MacKenzie Delta of the Canadian Arctic and geophysical logs from the Mallik test site are available for the gas hydrate stability zone (GHSZ) between depths of approximately 850 m to 1100 m. The geophysical data sets from two neighboring boreholes at the Mallik test site are analyzed. Commonly used porosity logs, as well as nuclear magnetic resonance, compressional and Stoneley wave velocity dispersion logs are used to map zones of elevated and severely reduced porosity and permeability respectively. The lateral continuity of horizontal permeability barriers can be further understood with the aid of surface seismic modeling studies. In this integrated study, the behavior of compressional and Stoneley wave velocity dispersion and surface seismic modeling studies are used to identify the fluid pathways and permeability barriers of the gas hydrate reservoir. The results are compared with known nuclear magnetic resonance-derived permeability values. The aim of investigating this heterogeneous medium is to map the fluid pathways and the associated permeability barriers throughout the gas hydrate stability zone. This provides a framework for an understanding of the long-term dissociation of gas hydrates along vertical and horizontal pathways, and will improve the knowledge pertaining to the production of such a promising energy source.
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NASA Astrophysics Data System (ADS)
Huang, Jun-Wei; Bellefleur, Gilles; Milkereit, Bernd
2012-02-01
We present a conditional simulation algorithm to parameterize three-dimensional heterogeneities and construct heterogeneous petrophysical reservoir models. The models match the data at borehole locations, simulate heterogeneities at the same resolution as borehole logging data elsewhere in the model space, and simultaneously honor the correlations among multiple rock properties. The model provides a heterogeneous environment in which a variety of geophysical experiments can be simulated. This includes the estimation of petrophysical properties and the study of geophysical response to the heterogeneities. As an example, we model the elastic properties of a gas hydrate accumulation located at Mallik, Northwest Territories, Canada. The modeled properties include compressional and shear-wave velocities that primarily depend on the saturation of hydrate in the pore space of the subsurface lithologies. We introduce the conditional heterogeneous petrophysical models into a finite difference modeling program to study seismic scattering and attenuation due to multi-scale heterogeneity. Similarities between resonance scattering analysis of synthetic and field Vertical Seismic Profile data reveal heterogeneity with a horizontal-scale of approximately 50 m in the shallow part of the gas hydrate interval. A cross-borehole numerical experiment demonstrates that apparent seismic energy loss can occur in a pure elastic medium without any intrinsic attenuation of hydrate-bearing sediments. This apparent attenuation is largely attributed to attenuative leaky mode propagation of seismic waves through large-scale gas hydrate occurrence as well as scattering from patchy distribution of gas hydrate.
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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.
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Investigation of hydrate formation in the system H2-CH4-H2O at a pressure up to 250 MPa.
Skiba, Sergei S; Larionov, Eduard G; Manakov, Andrey Y; Kolesov, Boris A; Kosyakov, Viktor I
2007-09-27
Phase equilibria in the system H2-CH4-H2O are investigated by means of differential thermal analysis within hydrogen concentration range 0-70 mol % and at a pressure up to 250 MPa. All the experiments were carried out under the conditions of gas excess. With an increase in hydrogen concentration in the initial gas mixture, decomposition temperature of the formed hydrates decreased. X-ray diffraction patterns and Raman spectra of the quenched hydrate samples obtained at a pressure of 20 MPA from a gas mixture containing 40 mol % hydrogen were recorded. It turned out that the hydrate has cubic structure I under these conditions. The Raman spectra showed that hydrogen molecules are not detected in the hydrate within the sensitivity of the method, that is, almost pure methane hydrate is formed. The general view of the phase diagram of the investigated system is proposed. A thermodynamic model was proposed to explain a decrease in hydrate decomposition temperature in the system with an increase in the concentration of hydrogen in the initial mixture.
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Analysis of Factors Influencing Hydration Site Prediction Based on Molecular Dynamics Simulations
2015-01-01
Water contributes significantly to the binding of small molecules to proteins in biochemical systems. Molecular dynamics (MD) simulation based programs such as WaterMap and WATsite have been used to probe the locations and thermodynamic properties of hydration sites at the surface or in the binding site of proteins generating important information for structure-based drug design. However, questions associated with the influence of the simulation protocol on hydration site analysis remain. In this study, we use WATsite to investigate the influence of factors such as simulation length and variations in initial protein conformations on hydration site prediction. We find that 4 ns MD simulation is appropriate to obtain a reliable prediction of the locations and thermodynamic properties of hydration sites. In addition, hydration site prediction can be largely affected by the initial protein conformations used for MD simulations. Here, we provide a first quantification of this effect and further indicate that similar conformations of binding site residues (RMSD < 0.5 Å) are required to obtain consistent hydration site predictions. PMID:25252619
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Method for the photocatalytic conversion of gas hydrates
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.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Tsukada, K., E-mail: tsukada@cc.okayama-u.ac.jp; Kusaka, T.; Saari, M. M.
2014-05-07
We developed a magnetic measurement method to measure the moisture content and hydration condition of mortar as a magnetic mixture material. Mortar is a mixture of Portland cement, sand, and water, and these materials exhibit different magnetic properties. The magnetization–magnetic field curves of these components and of mortars with different moisture contents were measured, using a specially developed high-temperature-superconductor superconducting quantum interference device. Using the differences in magnetic characteristics, the moisture content of mortar was measured at the ferromagnetic saturation region over 250 mT. A correlation between magnetic susceptibility and moisture content was successfully established. After Portland cement and water aremore » mixed, hydration begins. At the early stage of the hydration/gel, magnetization strength increased over time. To investigate the magnetization change, we measured the distribution between bound and free water in the mortar in the early stage by magnetic resonance imaging (MRI). The MRI results suggest that the amount of free water in mortar correlates with the change in magnetic susceptibility.« less
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NASA Astrophysics Data System (ADS)
Lucero, Catherine L.; Bentz, Dale P.; Hussey, Daniel S.; Jacobson, David L.; Weiss, W. Jason
Air entrainment is commonly added to concrete to help in reducing the potential for freeze thaw damage. It is hypothesized that the entrained air voids remain unsaturated or partially saturated long after the smaller pores fill with water. Small gel and capillary pores in the cement matrix fill quickly on exposure to water, but larger pores (entrapped and entrained air voids) require longer times or other methods to achieve saturation. As such, it is important to quantitatively determine the water content and degree of saturation in air entrained cementitious materials. In order to further investigate properties of cement-based mortar, a model based on Beer's Law has been developed to interpret neutron radiographs. This model is a powerful tool for analyzing images acquired from neutron radiography. A mortar with a known volume of aggregate, water to cement ratio and degree of hydration can be imaged and the degree of saturation can be estimated.
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Electrons initiate efficient formation of hydroperoxides from cysteine.
Gebicki, Janusz M
2016-09-01
Amino acid and protein hydroperoxides can constitute a significant hazard if formed in vivo. It has been suggested that cysteine can form hydroperoxides after intramolecular hydrogen transfer to the commonly produced cysteine sulfur-centered radical. The resultant cysteine-derived carbon-centered radicals can react with oxygen at almost diffusion-controlled rate, forming peroxyl radicals which can oxidize other molecules and be reduced to hydroperoxides in the process. No cysteine hydroperoxides have been found so far. In this study, dilute air-saturated cysteine solutions were exposed to radicals generated by ionizing radiation and the hydroperoxides measured by an iodide assay. Of the three primary radicals present, the hydroxyl, hydrogen atoms and hydrated electrons, the first two were ineffective. However, electrons did initiate the generation of hydroperoxides by removing the -SH group and forming cysteine-derived carbon radicals. Under optimal conditions, 100% of the electrons reacting with cysteine produced the hydroperoxides with a 1:1 stoichiometry. Maximum hydroperoxide yields were at pH 5.5, with fairly rapid decline under more acid or alkaline conditions. The hydroperoxides were stable between pH 3 and 7.5, and decomposed in alkaline solutions. The results suggest that formation of cysteine hydroperoxides initiated by electrons is an unlikely event under physiological conditions.
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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).
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Laboratory formation of non-cementing, methane hydrate-bearing sands
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.
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Lee, M.W.; Collett, T.S.; Lewis, K.A.
2012-01-01
Through the use of 3-D seismic amplitude mapping, several gashydrate prospects were identified in the Alaminos Canyon (AC) area of the Gulf of Mexico. Two locations were drilled as part of the Gulf of MexicoGasHydrate Joint Industry Project Leg II (JIP Leg II) in May of 2009 and a comprehensive set of logging-while-drilling (LWD) logs were acquired at each well site. LWD logs indicated that resistivity in the range of ~2 ohm-m and P-wave velocity in the range of ~1.9 km/s were measured in the target sand interval between 515 and 645 feet below sea floor. These values were slightly elevated relative to those measured in the sediment above and below the target sand. However, the initial well log analysis was inconclusive regarding the presence of gashydrate in the logged sand interval, mainly because largewashouts caused by drilling in the target interval degraded confidence in the well log measurements. To assess gashydratesaturations in the sedimentary section drilled in the Alaminos Canyon 21B (AC21-B) well, a method of compensating for the effect of washouts on the resistivity and acoustic velocities was developed. The proposed method models the washed-out portion of the borehole as a vertical layer filled with sea water (drilling fluid) and the apparent anisotropic resistivity and velocities caused by a vertical layer are used to correct the measured log values. By incorporating the conventional marine seismic data into the well log analysis, the average gashydratesaturation in the target sand section in the AC21-Bwell can be constrained to the range of 8–28%, with 20% being our best estimate.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Loring, John S.; Schaef, Herbert T.; Thompson, Christopher J.
2013-01-01
Injection of supercritical CO2 (scCO2) for the geologic storage of carbon dioxide will displace formation water, and the pore space adjacent to overlying caprocks could eventually be dominated by dry to water-saturated scCO2. Wet scCO2 is highly reactive and capable of carbonating and hydrating certain minerals, whereas anhydrous scCO2 can dehydrate water-containing minerals. Because these geochemical processes affect solid volume and thus porosity and permeability, they have the potential to affect the long-term integrity of the caprock seal. In this study, we investigate the swelling and shrinkage of an expandable clay found in caprock formations, montmorillonite (Ca-STx-1), when exposed tomore » variable water-content scCO2 at 50 °C and 90 bar using a combination of in situ probes, including X-ray diffraction (XRD), in situ magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR), and in situ attenuated total reflection infrared spectroscopy (ATR-IR). We show that the extent of montmorillonite clay swelling/shrinkage is dependent not only on water hydration/dehydration, but also on CO2 intercalation reactions. Our results also suggest a competition between water and CO2 for interlayer residency where increasing concentrations of intercalated water lead to decreasing concentrations of intercalated CO2. Overall, this paper demonstrates the types of measurements required to develop fundamental knowledge that will enhance modeling efforts and reduce risks associated with subsurface storage of CO2.« less
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Geologic controls on gas hydrate occurrence in the Mount Elbert prospect, Alaska North Slope
Boswell, R.; Rose, K.; Collett, T.S.; Lee, M.; Winters, W.; Lewis, K.A.; Agena, W.
2011-01-01
Data acquired at the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well, drilled in the Milne Point area of the Alaska North Slope in February, 2007, indicates two zones of high gas hydrate saturation within the Eocene Sagavanirktok Formation. Gas hydrate is observed in two separate sand reservoirs (the D and C units), in the stratigraphically highest portions of those sands, and is not detected in non-sand lithologies. In the younger D unit, gas hydrate appears to fill much of the available reservoir space at the top of the unit. The degree of vertical fill with the D unit is closely related to the unit reservoir quality. A thick, low-permeability clay-dominated unit serves as an upper seal, whereas a subtle transition to more clay-rich, and interbedded sand, silt, and clay units is associated with the base of gas hydrate occurrence. In the underlying C unit, the reservoir is similarly capped by a clay-dominated section, with gas hydrate filling the relatively lower-quality sands at the top of the unit leaving an underlying thick section of high-reservoir quality sands devoid of gas hydrate. Evaluation of well log, core, and seismic data indicate that the gas hydrate occurs within complex combination stratigraphic/structural traps. Structural trapping is provided by a four-way fold closure augmented by a large western bounding fault. Lithologic variation is also a likely strong control on lateral extent of the reservoirs, particularly in the D unit accumulation, where gas hydrate appears to extend beyond the limits of the structural closure. Porous and permeable zones within the C unit sand are only partially charged due most likely to limited structural trapping in the reservoir lithofacies during the period of primary charging. The occurrence of the gas hydrate within the sands in the upper portions of both the C and D units and along the crest of the fold is consistent with an interpretation that these deposits are converted free gas accumulations formed prior to the imposition of gas hydrate stability conditions. ?? 2009.
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Majid, Ahmad A A; Wu, David T; Koh, Carolyn A
2017-10-24
In situ rheological measurements for clathrate hydrate slurries were performed using a high pressure rheometer to determine the effect of hydrate particles on the viscosity and transportability of these slurries. These measurements were conducted using a well-characterized model water-in-oil emulsion ( Delgado-Linares et al. Model Water in-Oil Emulsions for Gas Hydrate Studies in Oil Continuous Systems . Energy Fuels 2013 , 27 , 4564 - 4573 ). The emulsion consists of a model liquid hydrocarbon, water, and a surfactant mixture of sorbitane monooleate 80 (Span 80) and sodium di-2-ethylhexylsulfosuccinate (Aerosol OT, AOT). This emulsion was used as an analog to water-in-crude oil (w/o) emulsions and provides reproducible results. The flow properties of the model w/o emulsion prior to hydrate formation were investigated in terms of several parameters including water percentage, temperature and pressure. A general equation that describes the viscosity of the emulsion as a function of the aforementioned parameters was developed. This general equation was able to predict the viscosity of a saturated emulsion at various temperatures and water percentages to within ±13% error. The general equation was then used to analyze the effect of hydrate formation on the transportability of gas hydrate slurries. As for hydrate slurries investigation, measurements were performed using methane gas as the hydrate former and a straight vane impeller as a stirring system. Tests were conducted at constant temperature and pressure (1 °C and 1500 psig of methane) and water percentages ranging from 5 to 30 vol %. Results of this work were analyzed and presented in terms of relative values, i.e., viscosities of the slurries relative to the viscosities of the continuous phase at similar temperature and pressure. In this work, a correlation to predict the relative viscosity of a hydrate slurry at various hydrate volume fractions was developed. Analysis of the developed correlation showed that the model was able to predict the relative viscosity of a hydrate slurry to within ±17% error.
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Ferric citrate hydrate for the treatment of hyperphosphatemia in nondialysis-dependent CKD.
Yokoyama, Keitaro; Hirakata, Hideki; Akiba, Takashi; Fukagawa, Masafumi; Nakayama, Masaaki; Sawada, Kenichi; Kumagai, Yuji; Block, Geoffrey A
2014-03-01
Ferric citrate hydrate is a novel iron-based phosphate binder being developed for hyperphosphatemia in patients with CKD. A phase 3, multicenter, randomized, double blind, placebo-controlled study investigated the efficacy and safety of ferric citrate hydrate in nondialysis-dependent patients with CKD. Starting in April of 2011, 90 CKD patients (eGFR=9.21±5.72 ml/min per 1.73 m(2)) with a serum phosphate≥5.0 mg/dl were randomized 2:1 to ferric citrate hydrate or placebo for 12 weeks. The primary end point was change in serum phosphate from baseline to the end of treatment. Secondary end points included the percentage of patients achieving target serum phosphate levels (2.5-4.5 mg/dl) and change in fibroblast growth factor-23 at the end of treatment. The mean change in serum phosphate was -1.29 mg/dl (95% confidence interval, -1.63 to -0.96 mg/dl) in the ferric citrate hydrate group and 0.06 mg/dl (95% confidence interval, -0.20 to 0.31 mg/dl) in the placebo group (P<0.001 for difference between groups). The percentage of patients achieving target serum phosphate levels was 64.9% in the ferric citrate hydrate group and 6.9% in the placebo group (P<0.001). Fibroblast growth factor-23 concentrations were significantly lower in patients treated with ferric citrate hydrate versus placebo (change from baseline [median], -142.0 versus 67.0 pg/ml; P<0.001). Ferric citrate hydrate significantly increased serum iron, ferritin, and transferrin saturation compared with placebo (P=0.001 or P<0.001). Five patients discontinued active treatment because of treatment-emergent adverse events with ferric citrate hydrate treatment versus one patient with placebo. Overall, adverse drug reactions were similar in patients receiving ferric citrate hydrate or placebo, with gastrointestinal disorders occurring in 30.0% of ferric citrate hydrate patients and 26.7% of patients receiving placebo. In patients with nondialysis-dependent CKD, 12-week treatment with ferric citrate hydrate resulted in significant reductions in serum phosphate and fibroblast growth factor-23 while simultaneously increasing serum iron parameters.
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Pathways through equilibrated states with coexisting phases for gas hydrate formation
DOE Office of Scientific and Technical Information (OSTI.GOV)
Malolepsza, Edyta; Keyes, Tom
Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces themore » initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Furthermore, free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation.« less
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Pathways through equilibrated states with coexisting phases for gas hydrate formation
Malolepsza, Edyta; Keyes, Tom
2015-12-01
Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces themore » initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Furthermore, free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation.« less
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Buchanan, Piers; Soper, Alan K; Thompson, Helen; Westacott, Robin E; Creek, Jefferson L; Hobson, Greg; Koh, Carolyn A
2005-10-22
Neutron diffraction with HD isotope substitution has been used to study the formation and decomposition of the methane clathrate hydrate. Using this atomistic technique coupled with simultaneous gas consumption measurements, we have successfully tracked the formation of the sI methane hydrate from a water/gas mixture and then the subsequent decomposition of the hydrate from initiation to completion. These studies demonstrate that the application of neutron diffraction with simultaneous gas consumption measurements provides a powerful method for studying the clathrate hydrate crystal growth and decomposition. We have also used neutron diffraction to examine the water structure before the hydrate growth and after the hydrate decomposition. From the neutron-scattering curves and the empirical potential structure refinement analysis of the data, we find that there is no significant difference between the structure of water before the hydrate formation and the structure of water after the hydrate decomposition. Nor is there any significant change to the methane hydration shell. These results are discussed in the context of widely held views on the existence of memory effects after the hydrate decomposition.
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NASA Astrophysics Data System (ADS)
Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim; Yusoff, Siti Fairus M.
2015-09-01
Liquid natural rubber (LNR) with molecular weight of lower than 105 and shorter polymeric chain than natural rubber was prepared. LNR was then hydrogenated via diimide reduction by oxidation of hydrazine hydrate with hydrogen peroxide. The unsaturated units of the rubber were converted into saturated hydrocarbon to strengthen the backbone of the polymer so it was able to resist thermal degradation. The results indicated that hydrogenation degree of the product (HLNR) could be extended to 91.2% conversion under appropriate conditions. The hydrogenated LNR (HLNR) was characterized using Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The physical characteristics of HLNR were analyzed with Termogravimetric Analysis (TGA).
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Reservoir characterization combining elastic velocities and electrical resistivity measurements
NASA Astrophysics Data System (ADS)
Gomez, Carmen Teresa
2009-12-01
The elastic and electric parameters of rocks that can be obtained from seismic and electromagnetic data depend on porosity, texture, mineralogy, and fluid. However, seismic data seldom allow us to accurately quantify hydrocarbon saturation. On the other hand, in the case of common reservoir rocks (i.e., sandstones and carbonates), resistivity strongly depends on porosity and saturation. Therefore, the recent progress of controlled-source-electromagnetic (CSEM) methods opens new possibilities in identifying and quantifying potential hydrocarbon reservoirs, although its resolution is much lower than that of seismic data. Hence, a combination of seismic and CSEM data arguably offers a powerful means of finally resolving the problem of remote sensing of saturation. The question is how to combine the two data sources (elastic data and electrical resistivity data) to better characterize a reservoir. To address this question, we introduce the concept of P-wave impedance and resistivity templates as a tool to estimate porosity and saturation from well log data. Adequate elastic and resistivity models, according to the lithology, cementation, fluid properties must be chosen to construct these templates. These templates can be upscaled to seismic and CSEM scale using Backus average for seismic data, and total resistance for CSEM data. We also measured velocity and resistivity in Fontainebleau samples in the laboratory. Fontainebleau formation corresponds to clean sandstones (i.e., low clay content). We derived an empirical relation between these P-wave velocity and resistivity at 40MPa effective pressure, which is around 3 km depth at normal pressure gradients. We were not able to test if this relation could be used at well or field data scales (once appropriate upscaling was applied), since we did not have a field dataset over a stiff sandstone reservoir. A relationship between velocity and resistivity laboratory data was also found for a set of carbonates. This expression was quadratic, and not linear as in the case of Fontainebleau sandstones. There are other factors that influence this relationship in the case of these carbonates, which include pore geometry, and amount of micritic cement. We observed that the expression is almost linear, but it deviates as we approach lower resistivities. This deviation can be explained by the presence of stiff pores such as moldic or intra-granular pores, which causes high velocity but low resistivity values when water-saturated. In the same way, the effect of micrite cement on velocity is stronger than its effect on resistivity, and that also is responsible for some of the scatter that we observe. We also modeled both velocity and resistivity using self-consistent approximation with the same pore or inclusion geometries in both carbonate and sandstone laboratory datasets. In the case of carbonates, we found that we had to include needle-like pores to explain the low resistivity but high velocities. Needle is one of the geometries that allow us to have connected stiff pores. However, we also found that a fraction of compliant pores also had to be included in order to explain the velocity measurements on the carbonate dataset. The self-consistent model also approximated well the velocity and resistivity laboratory measurements on the Fontainebleau sandstones, using similar aspect ratios for both the velocity and the resistivity. As far as semi-empirical and empirical models, we observed how the stiff-sand model fit well the Fontainebleau data at 40MPa, including S-wave velocities. The Raymer-Hunt-Gardner relation also did a good job at predicting P-wave velocity. Archie's equation with cementation exponent between 1.6 and 2.1 fits the resistivity measurements on the Fontainebleau sandstones. These two relationships can be combined to create a resistivity---P-wave velocity transform for this dataset. When we attempted to use CSEM data to limit the shallow and low-frequency acoustic impedance trend for seismic inversion, we found that appropriate elastic and resistivity models must be chosen in order to have a good prediction of acoustic impedance, given resistivity. These expressions can be calibrated using well data with particular emphasis to the overburden. If no well log data are available in the shallow section, using the CSEM-derived resistivity data and an adequate cross-property relation (for example, one based on soft-sand model and Archie's equation) can be a good approach to predict the initial low frequency shallow acoustic impedance model. Validation tests showed that using the background trend from CSEM data as a constraint in impedance inversion can give a better fit to the acoustic impedance. As part of our analysis of gas hydrate bearing sandstones, we found that normalized resistivity versus P-wave impedance templates can also be useful to predict reservoir properties, such as porosity and saturation for a gas-hydrate reservoir at well log scale. Porosity and saturation prediction of the hydrate-bearing layer from seismic data alone is highly dependent on its thickness and the properties of the overburden, and requires well-control data that can point to appropriate models and properties to use for the overburden. However, it would be interesting to test, using a resistivity model obtained from seismic data as the initial input, a CSEM inversion on a gas-hydrate-bearing sandstone.
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Haines, Seth S.; Lee, Myung W.; Collett, Timothy S.; Hardage, Bob A.
2011-01-01
In-situ characterization and quantification of natural gas hydrate occurrences remain critical research directions, whether for energy resource, drilling hazard, or climate-related studies. Marine multicomponent seismic data provide the full seismic wavefield including partial redundancy, and provide a promising set of approaches for gas hydrate characterization. Numerous authors have demonstrated the possibilities of multicomponent data at study sites around the world. We expand on this work by investigating the utility of very densely spaced (10’s of meters) multicomponent receivers (ocean-bottom cables, OBC, or ocean-bottom seismometers, OBS) for gas hydrate studies in the Gulf of Mexico and elsewhere. Advanced processing techniques provide high-resolution compressional-wave (PP) and converted shearwave (PS) reflection images of shallow stratigraphy, as well as P-wave and S-wave velocity estimates at each receiver position. Reflection impedance estimates can help constrain velocity and density, and thus gas hydrate saturation. Further constraint on velocity can be determined through identification of the critical angle and associated phase reversal in both PP and PS wideangle data. We demonstrate these concepts with examples from OBC data from the northeast Green Canyon area and numerically simulated OBS data that are based on properties of known gas hydrate occurrences in the southeast (deeper water) Green Canyon area. These multicomponent data capabilities can provide a wealth of characterization and quantification information that is difficult to obtain with other geophysical methods.
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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.
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Boswell, Ray; Yamamoto, Koji; Lee, Sung-Rock; Collett, Timothy S.; Kumar, Pushpendra; Dallimore, Scott
2008-01-01
Gas hydrate is a solid, naturally occurring substance consisting predominantly of methane gas and water. Recent scientific drilling programs in Japan, Canada, the United States, Korea and India have demonstrated that gas hydrate occurs broadly and in a variety of forms in shallow sediments of the outer continental shelves and in Arctic regions. Field, laboratory and numerical modelling studies conducted to date indicate that gas can be extracted from gas hydrates with existing production technologies, particularly for those deposits in which the gas hydrate exists as pore-filling grains at high saturation in sand-rich reservoirs. A series of regional resource assessments indicate that substantial volumes of gas hydrate likely exist in sand-rich deposits. Recent field programs in Japan, Canada and in the United States have demonstrated the technical viability of methane extraction from gas-hydrate-bearing sand reservoirs and have investigated a range of potential production scenarios. At present, basic reservoir depressurisation shows the greatest promise and can be conducted using primarily standard industry equipment and procedures. Depressurisation is expected to be the foundation of future production systems; additional processes, such as thermal stimulation, mechanical stimulation and chemical injection, will likely also be integrated as dictated by local geological and other conditions. An innovative carbon dioxide and methane swapping technology is also being studied as a method to produce gas from select gas hydrate deposits. In addition, substantial additional volumes of gas hydrate have been found in dense arrays of grain-displacing veins and nodules in fine-grained, clay-dominated sediments; however, to date, no field tests, and very limited numerical modelling, have been conducted with regard to the production potential of such accumulations. Work remains to further refine: (1) the marine resource volumes within potential accumulations that can be produced through exploratory drilling programs; (2) the tools for gas hydrate detection and characterisation from remote sensing data; (3) the details of gas hydrate reservoir production behaviour through additional, well-monitored and longer duration field tests and (4) the understanding of the potential environmental impacts of gas hydrate resource development. The results of future production tests, in the context of varying market and energy supply conditions around the globe, will be the key to determine the ultimate timing and scale of the commercial production of natural gas from gas hydrates.
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Dissociation behavior of methane--ethane mixed gas hydrate coexisting structures I and II.
Kida, Masato; Jin, Yusuke; Takahashi, Nobuo; Nagao, Jiro; Narita, Hideo
2010-09-09
Dissociation behavior of methane-ethane mixed gas hydrate coexisting structures I and II at constant temperatures less than 223 K was studied with use of powder X-ray diffraction and solid-state (13)C NMR techniques. The diffraction patterns at temperatures less than 203 K showed both structures I and II simultaneously convert to Ih during the dissociation, but the diffraction pattern at temperatures greater than 208 K showed different dissociation behavior between structures I and II. Although the diffraction peaks from structure II decreased during measurement at constant temperatures greater than 208 K, those from structure I increased at the initial step of dissociation and then disappeared. This anomalous behavior of the methane-ethane mixed gas hydrate coexisting structures I and II was examined by using the (13)C NMR technique. The (13)C NMR spectra revealed that the anomalous behavior results from the formation of ethane-rich structure I. The structure I hydrate formation was associated with the dissociation rate of the initial methane-ethane mixed gas hydrate.
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NASA Astrophysics Data System (ADS)
Mondal, Sukanta; Goswami, Tamal; Jana, Gourhari; Misra, Anirban; Chattaraj, Pratim Kumar
2018-01-01
In this letter, a possible reason behind selective host-guest organization in the initial stage of sI methane hydrate nucleation is provided, through density functional theory based calculations. In doing so, we have connected earlier experimental and theoretical observations on the structure and energetics of sI methane hydrate to our findings. Geometry and relative stability of small (H2O)5 and (H2O)6 clusters, presence of CH4 guest, integrity and cavity radius of (H2O)20 and (H2O)24, as well as the weak van der Waals type of forces, particularly dispersion interaction, are major factors responsible for initial formation of methane encapsulated dodecahedron cavity over tetrakaidecahedron.
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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.
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Brewer, P.G.; Orr, F.M.; Friederich, G.; Kvenvolden, K.A.; Orange, D.L.
1998-01-01
We have utilized a remotely operated vehicle (ROV) to initiate a program of research into gas hydrate formation in the deep sea by controlled release of hydrocarbon gases and liquid CO2 into natural sea water and marine sediments. Our objectives were to investigate the formation rates and growth patterns of gas hydrates in natural systems and to assess the geochemical stability of the reaction products over time. The novel experimental procedures used the carrying capacity, imaging capability, and control mechanisms of the ROV to transport gas cylinders to depth and to open valves selectively under desired P-T conditions to release the gas either into contained natural sea water or into sediments. In experiments in Monterey Bay, California, at 910 m depth and 3.9??C water temperature we find hydrate formation to be nearly instantaneous for a variety of gases. In sediments the pattern of hydrate formation is dependent on the pore size, with flooding of the pore spaces in a coarse sand yielding a hydrate cemented mass, and gas channeling in a fine-grained mud creating a veined hydrate structure. In experiments with liquid CO2 the released globules appeared to form a hydrate skin as they slowly rose in the apparatus. An initial attempt to leave the experimental material on the sea floor for an extended period was partially successful; we observed an apparent complete dissolution of the liquid CO2 mass, and an apparent consolidation of the CH4 hydrate, over a period of about 85 days.
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Enhanced sorption of trichloroethene by smectite clay exchanged with Cs+.
Aggarwal, Vaneet; Li, Hui; Boyd, Stephen A; Teppen, Brian J
2006-02-01
Trichloroethene (TCE) is one of the most common pollutants in groundwater, and Cs+ can be a cocontaminant at nuclear facilities. Smectite clays have large surface areas, are common in soils, have high affinities for some organic contaminants, and hence can potentially influence the transport of organic pollutants entering soils and sediments. The exchangeable cations present near smectite clay surfaces can radically influence the sorption of organic pollutants by soil clays. This research was undertaken to determine the effect of Cs+, and other common interlayer cations, such as K+ and Ca2+, on the sorption of TCE by a reference smectite clay saponite. Cs-saturated clay sorbed the most TCE, up to 3500 mg/kg, while Ca-saturated smectite sorbed the least. We hypothesize that the stronger sorption of TCE by the Cs-smectite can be attributed to the lower hydration energy and hence smaller hydrated radius of Cs+, which expands the lateral clay surface domains available for sorption. Also, Cs-smectite interlayers are only one or two water layers thick, which may drive capillary condensation of TCE. Our results implicate enhanced retention of TCE in aquifer materials containing smectites accompanied by Cs+ cocontamination.
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NASA Astrophysics Data System (ADS)
Hamada, Y.; Yamada, Y.; Sanada, Y.; Nakamura, Y.; Kido, Y. N.; Moe, K.
2017-12-01
Gas hydrates bearing layer can be normally identified by a basement simulating reflector (BSR) or well logging because of their high acoustic- and electric impedance compared to the surrounding formation. These characteristics of the gas hydrate can also represent contrast of in-situ formation strength. We here attempt to describe gas hydrate bearing layers based on the equivalent strength (EST). The Indian National Gas Hydrate Program (NGHP) Expedition 02 was executed 2015 off the eastern margin of the Indian Peninsula to investigate distribution and occurrence of gas hydrates. From 25 drill sites, downhole logging data, cored samples, and drilling performance data were collected. Recorded drilling performance data was converted to the EST, which is a developed mechanical strength calculated only by drilling parameters (top drive torque, rotation per minute , rate of penetration , and drill bit diameter). At a representative site, site 23, the EST shows constant trend of 5 to 10 MPa, with some positive peaks at 0 - 270 mbsf interval, and sudden increase up to 50 MPa above BSR depth (270 - 290 mbsf). Below the BSR, the EST stays at 5-10 MPa down to the bottom of the hole (378 mbsf). Comparison of the EST with logging data and core sample description suggests that the depth profiles of the EST reflect formation lithology and gas hydrate content: the EST increase in the sand-rich layer and the gas hydrate bearing zone. Especially in the gas hydrate zone, the EST curve indicates approximately the same trend with that of P-wave velocity and resistivity measured by downhole logging. Cross plot of the increment of the EST and resistivity revealed the relation between them is roughly logarithmic, indicating the increase and decrease of the EST strongly depend on the saturation factor of gas hydrate. These results suggest that the EST, proxy of in-situ formation strength, can be an indicator of existence and amount of the gas-hydrate layer. Although the EST was calculated after drilling utilizing recorded surface drilling parameter in this study, the EST can be acquired during drilling by using real-time drilling parameters. In addition, the EST only requires drilling performance parameters without any additional tools or measurements, making it a simplified and economical tool for the exploration of gas hydrates.
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NASA Astrophysics Data System (ADS)
Han, G.; Kwon, T. H.; Lee, J. Y.
2016-12-01
As gas and water flows induced by depressurization of hydrate-bearing sediments exert seepage forces on fines in sediments, such as clay particles, depressurization is reported to accompany the transport of fine particles through sediment pores, i.e., fines migration. Because such fines migration can cause pore clogging, the fines migration is considered as one of the critical phenomena contributing to the transport of fluids among various pore-scale processes associated with depressurization. However, quantification of fines migration during depressurization still remains poorly understood. This study thus investigated fines migration caused by depressurization using X-ray computerized tomography(X-ray CT) imaging. A host sediment was prepared by mixing fine sand with kaolinite clay minerals to achieve 10% mass fraction of fines (less than 75 um). Then, methane hydrate was synthesized in the host clayey sand, and thereafter water was injected to saturate the hydrate-bearing sediment sample. Step-wise depressurization was applied while the produced gas was collected through an outlet fluid port. X-ray CT imaging was conducted on the sediment sample over the courses of the experiment to monitor the sample preparation, hydrate formation, depressurization, and fines migration. Based on the calibration tests, the amount and locations of methane hydrate formed in the sample was estimated, and the gas migration path was also identified. Finally, the spatial distribution of fines after completion of depressurization was first assessed using the obtained X-ray images and then compared with the post-mortem mine-back results.Notably, we found that the middle part of the sample was clogged possibly by fines or by re-formed hydrate, leading to a big pressure difference between the inlet and outlet fluid port of the sample by 3 MPa. Owing to this clogging and the lost in pressure communication, hydrate dissociation first occurred at the bottom half and the hydrate dissociation in the top half part followed later. Our study demonstrates that X-ray CT imaging can be a useful tool to visualize and quantify the fines migration during hydrate depressurization, and our results present an experimental evidence that depressurization can cause pore clogging in sediments containing more than 10% fines fraction.
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NASA Astrophysics Data System (ADS)
Behseresht, J.; Prodanović, M.; Bryant, S. L.
2007-12-01
A spectrum of behavior is encountered in ocean sediments bearing methane hydrates, ranging from essentially static accumulations where hydrate and brine co-exist, to active cold seeps where hydrate and a methane gas phase co-exist in the hydrate stability zone (HSZ). In this and a companion paper (Jain and Juanes) we describe methods to test the following hypothesis: the coupling between drainage and fracturing, both induced by pore pressure, determines whether methane gas entering the HSZ is converted completely to hydrate. Here we describe a novel implementation of the level set method (LSM) to determine the capillarity-controlled displacement of brine by gas from sediment and from fractures within the sediment. Predictions of fluid configurations in infinite-acting model sediments indicate that the brine in drained sediment (after invasion by methane gas) is better connected than previously believed. This increases the availability of water and the rate of counter-diffusion of salinity ions, thus relaxing the limit on hydrate build-up within gas- invaded grain matrix. Simulated drainage of a fracture in sediment shows that points of contact between fracture faces are crucial. They allow residual water saturation to remain within an otherwise gas-filled fracture. Simulations of imbibition, which can occur for example after drainage into surrounding sediment reduces gas phase pressure in the fracture, indicate that the gas/water interfaces at contact points significantly shifts the threshold pressures for withdrawal of gas. During both drainage and imbibition, the contact points greatly increase water availability for hydrate formation within the fracture. We discuss coupling this capillarity-controlled displacement model with a discrete element model for grain-scale mechanics. The coupled model provides a basis for evaluating the macroscopic conditions (thickness of gas accumulation below the hydrate stability zone; average sediment grain size; principal earth stresses) favoring co- existence of methane gas and hydrate in the HSZ. Explaining the range of behavior is useful in assessing resource volumes and evaluating pore-to-core scale flow paths in production strategies.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim
Liquid natural rubber (LNR) with molecular weight of lower than 10{sup 5} and shorter polymeric chain than natural rubber was prepared. LNR was then hydrogenated via diimide reduction by oxidation of hydrazine hydrate with hydrogen peroxide. The unsaturated units of the rubber were converted into saturated hydrocarbon to strengthen the backbone of the polymer so it was able to resist thermal degradation. The results indicated that hydrogenation degree of the product (HLNR) could be extended to 91.2% conversion under appropriate conditions. The hydrogenated LNR (HLNR) was characterized using Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The physical characteristicsmore » of HLNR were analyzed with Termogravimetric Analysis (TGA)« less
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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.
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Nonequilibrium Thermodynamics of Hydrate Growth on a Gas-Liquid Interface.
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.
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Chen, Mei-Lian; Chen, Qiang; Xu, Fan; Zhang, Jia-Xin; Su, Xiao-Ying; Tu, Xiao-Zhen
2017-01-01
This study evaluates the safety and efficacy of chloral hydrate administration for the conscious sedation of infants in the pediatric cardiovascular intensive care unit (PCICU).We conducted a retrospective review of the charts of 165 infants with congenital heart disease who received chloral hydrate in our PCICU between January 2014 and December 2014. Chloral hydrate was administered orally or rectally to infants using doses of 50 mg/kg. We collected and analyzed relevant clinical parameters.The overall length of time to achieve sedation was ranged from 5 to 35 min (10.8 ± 6.2 min); the overall mean duration of sedation was ranged from 15 to 60 min (33.5 ± 11.3 min); and the overall mean length of time to return to normal activity was 10 min to 6 h (34.3 ± 16.2 min). The length of the PCICU stay was ranged from 3 to 30 days (8.2 ± 7.1 days). Physiologically, there were no clinically significant changes in heart rate, mean arterial pressure, respiratory rate, or peripheral oxygen saturation before, during, or after use of the chloral hydrate. There were no significant differences regarding sedative effects in the subgroups (cyanotic vs acyanotic group, with pulmonary infection vs without pulmonary infection group, and with pulmonary hypertension vs without pulmonary hypertension group).Our experience suggests that chloral hydrate is a safe and efficacious agent for conscious sedation of infants in the PCICU.
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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.
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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.
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NASA Astrophysics Data System (ADS)
Lorenson, T. D.; Collett, T. S.; Ignik Sikumi, S.
2012-12-01
Hydrocarbon gases, nitrogen, carbon dioxide and water were collected from production streams at the Ignik Sikumi gas hydrate production test well (TD, 791.6 m), drilled on the Alaska North Slope. The well was drilled to test the feasibility of producing methane by carbon dioxide injection that replaces methane in the solid gas hydrate. The Ignik Sikumi well penetrated a stratigraphically-bounded prospect within the Eileen gas hydrate accumulation. Regionally, the Eileen gas hydrate accumulation overlies the more deeply buried Prudhoe Bay, Milne Point, and Kuparuk River oil fields and is restricted to the up-dip portion of a series of nearshore deltaic sandstone reservoirs in the Sagavanirktok Formation. Hydrate-bearing sandstones penetrated by Ignik Sikumi well occur in three primary horizons; an upper zone, ("E" sand, 579.7 - 597.4 m) containing 17.7 meters of gas hydrate-bearing sands, a middle zone ("D" sand, 628.2 - 648.6 m) with 20.4 m of gas hydrate-bearing sands and a lower zone ("C" sand, 678.8 - 710.8 m), containing 32 m of gas hydrate-bearing sands with neutron porosity log-interpreted average gas hydrate saturations of 58, 76 and 81% respectively. A known volume mixture of 77% nitrogen and 23% carbon dioxide was injected into an isolated section of the upper part of the "C" sand to start the test. Production flow-back part of the test occurred in three stages each followed by a period of shut-in: (1) unassisted flowback; (2) pumping above native methane gas hydrate stability conditions; and (3) pumping below the native methane gas hydrate stability conditions. Methane production occurred immediately after commencing unassisted flowback. Methane concentration increased from 0 to 40% while nitrogen and carbon dioxide concentrations decreased to 48 and 12% respectively. Pumping above the hydrate stability phase boundary produced gas with a methane concentration climbing above 80% while the carbon dioxide and nitrogen concentrations fell to 2 and 18% respectively. Pumping below the gas hydrate stability phase boundary occurred in two periods with the composition of the produced gases continually increasing in methane reaching an excess of 96%, along with carbon dioxide decreasing to <1% and nitrogen to ~3%. The isotopic composition of all the gases was monitored. Methane carbon and hydrogen isotopic compositions remained stable throughout the test, while the carbon dioxide carbon became isotopically heavier. Nitrogen isotopic composition remained stable or became slightly isotopically depleted at the later phase of the test. These results imply that the produced methane was not isotopically fractionated, whereas carbon dioxide was fractionated becoming isotopically heavier at the end of each production phase. In addition, water samples were analyzed during the production phase documenting an increase in salinity.
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Watanabe, Yuuya; Ohnaka, Kenji; Fujita, Saki; Kishi, Midori; Yuchi, Akio
2011-10-01
The spaces (voids) available for cations in the five exchange resins with varying exchange capacities and cross-linking degrees were estimated, on the basis of the additivity of molar volumes of the constituents. Tetraalkylammonium ions (NR(4)(+); R: Me, Et, Pr) may completely exchange potassium ion on the resin having a larger void radius. In contrast, the ratio of saturated adsorption capacity to exchange capacity of the resin having a smaller void radius decreased with an increase in size of NR(4)(+) ions, due to the interionic contacts. Alkali metal ions could be exchanged quantitatively. While the hydration numbers of K(+), Rb(+), and Cs(+) were independent of the void radius, those of Li(+) and Na(+), especially Na(+), decreased with a decrease in void radius. Interionic contacts between the hydrated ions enhance the dehydration. Multivalent metal ions have the hydration numbers, comparable to or rather greater than those in water. A greater void volume available due to exchange stoichiometry released the interionic contacts and occasionally promoted the involvement of water molecules other than directly bound molecules. The close proximity between ions in the conventional ion-exchange resins having higher exchange capacities may induce varying interactions.
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Ovipositional site selection by Anopheles gambiae: influences of substrate moisture and texture.
Huang, J; Walker, E D; Giroux, P Y; Vulule, J; Miller, J R
2005-12-01
The influence of substrate moisture (hydration) and grain size (texture) on oviposition was quantified in choice tests using Anopheles gambiae sensu stricto Giles (Diptera: Culicidae) laboratory strains and gravid An. gambiae sensu lato from a natural population in Western Kenya. A strong, positive correlation was found between moisture content and the degree of egg-laying, which peaked at saturation with standing water. Soil moisture quantified as surface conductivity, was measured with an electronic leaf-wetness sensor slightly modified from a unit available commercially. Although An. gambiae females were sensitive to measurable differences in substrate moisture, they distributed eggs on both fully hydrated and less hydrated substrates. In contrast, An. gambiae females showed little response to substrate texture: they oviposited with equal frequency on all silica substrates of eight particle size classes, ranging from small pebbles (850 microm diameter) to very fine grains (< 38 microm diameter), when all were moist. Female An. gambiae laid more eggs on dark than white substrates against a light background, but did not discriminate between moist, pulverized black soapstone and moist black Kenyan soil taken from typical An. gambiae larval habitats. We conclude that hydration and visual contrast are critical ovipositional site qualities for An. gambiae, but substrate texture is not.
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NASA Astrophysics Data System (ADS)
Kannberg, P. K.; Constable, S.
2014-12-01
Methane hydrate, an ice-like clathrate of water and methane, forms in shallow continental slope sediments, and is both a potential energy source and geologic hazard. Hydrates presence is traditionally inferred from the presence of the bottom simulating reflector (BSR), a seismic velocity inversion resulting from free gas pooling at the base of the hydrate stability field. The BSR is not a measure of hydrate, but rather a proxy for free gas presence. Whereas seismic methods are sensitive to velocity anomalies, controlled-source electromagnetic (CSEM) methods are sensitive to conductivity anomalies. The electrically resistive methane hydrate makes a favorable target for CSEM surveys, which are capable of detecting and potentially quantifying the presence of methane hydrate directly. Building on previous work 100km to the south in the San Nicolas Basin, we present initial results from a 6-day June 2014 survey in the Santa Cruz Basin, located 100km west of Los Angeles. CSEM surveys are performed by deep-towing an EM source that is transmitting a known signal; this signal is detected by towed and seafloor receivers. The initial EM source signal is altered by the electrical properties of the surrounding environment. Conductors such as brine and seawater are attenuating mediums, while resistors such as methane hydrate, gas, and oil are preservative of the original signal. Twenty-one seafloor receivers, as well as a 4 receiver towed array were deployed to image the resistivity structure of the Santa Cruz Basin. Using 30-year-old 2D seismic profiles as a guide, potential hydrate targets were identified, and the transmitter and array were towed over 150 km on 6 lines with 5 seafloor receivers each. The 6 towed lines were coincident with legacy seismic lines. The towed array is sensitive to sediment depths less than 1km, allowing for high data density through the hydrate stability field. The larger transmitter-receiver offsets of the seafloor receivers allow sensitivity to at least 3km below the seafloor. Combining the two data sets allows for both high resolution in the near-seafloor hydrate accumulations as well as imaging the potential gas-source regions of the hydrate field.
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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.
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New hydrate formation methods in a liquid-gas medium.
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.
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New hydrate formation methods in a liquid-gas medium
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
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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.
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Simulation of subsea gas hydrate exploitation
NASA Astrophysics Data System (ADS)
Janicki, Georg; Schlüter, Stefan; Hennig, Torsten; Deerberg, Görge
2014-05-01
The recovery of methane from gas hydrate layers that have been detected in several subsea sediments and permafrost regions around the world is a promising perspective to overcome future shortages in natural gas supply. Being aware that conventional natural gas resources are limited, research is going on to develop technologies for the production of natural gas from such new sources. Thus various research programs have started since the early 1990s in Japan, USA, Canada, India, and Germany to investigate hydrate deposits and develop required technologies. In recent years, intensive research has focussed on the capture and storage of CO2 from combustion processes to reduce climate impact. While different natural or man-made reservoirs like deep aquifers, exhausted oil and gas deposits or other geological formations are considered to store gaseous or liquid CO2, the storage of CO2 as hydrate in former methane hydrate fields is another promising alternative. Due to beneficial stability conditions, methane recovery may be well combined with CO2 storage in the form of hydrates. Regarding technological implementation many problems have to be overcome. Especially mixing, heat and mass transfer in the reservoir are limiting factors causing very long process times. Within the scope of the German research project »SUGAR« different technological approaches for the optimized exploitation of gas hydrate deposits are evaluated and compared by means of dynamic system simulations and analysis. Detailed mathematical models for the most relevant chemical and physical processes are developed. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into simulation programs. Simulations based on geological field data have been carried out. The studies focus on the potential of gas production from turbidites and their fitness for CO2 storage. The effects occurring during gas production and CO2 storage within a hydrate deposit are identified and described for various scenarios. The behavior of relevant process parameters such as pressure, temperature and phase saturations is discussed and compared for different strategies: simple depressurization, simultaneous and subsequent methane production together with CO2 injection.
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Winters, W.; Walker, M.; Hunter, R.; Collett, T.; Boswell, R.; Rose, K.; Waite, W.; Torres, M.; Patil, S.; Dandekar, A.
2011-01-01
This study characterizes cored and logged sedimentary strata from the February 2007 BP Exploration Alaska, Department of Energy, U.S. Geological Survey (BPXA-DOE-USGS) Mount Elbert Gas Hydrate Stratigraphic Test Well on the Alaska North Slope (ANS). The physical-properties program analyzed core samples recovered from the well, and in conjunction with downhole geophysical logs, produced an extensive dataset including grain size, water content, porosity, grain density, bulk density, permeability, X-ray diffraction (XRD) mineralogy, nuclear magnetic resonance (NMR), and petrography.This study documents the physical property interrelationships in the well and demonstrates their correlation with the occurrence of gas hydrate. Gas hydrate (GH) occurs in three unconsolidated, coarse silt to fine sand intervals within the Paleocene and Eocene beds of the Sagavanirktok Formation: Unit D-GH (614.4. m-627.9. m); unit C-GH1 (649.8. m-660.8. m); and unit C-GH2 (663.2. m-666.3. m). These intervals are overlain by fine to coarse silt intervals with greater clay content. A deeper interval (unit B) is similar lithologically to the gas-hydrate-bearing strata; however, it is water-saturated and contains no hydrate.In this system it appears that high sediment permeability (k) is critical to the formation of concentrated hydrate deposits. Intervals D-GH and C-GH1 have average "plug" intrinsic permeability to nitrogen values of 1700 mD and 675 mD, respectively. These values are in strong contrast with those of the overlying, gas-hydrate-free sediments, which have k values of 5.7. mD and 49 mD, respectively, and thus would have provided effective seals to trap free gas. The relation between permeability and porosity critically influences the occurrence of GH. For example, an average increase of 4% in porosity increases permeability by an order of magnitude, but the presence of a second fluid (e.g., methane from dissociating gas hydrate) in the reservoir reduces permeability by more than an order of magnitude. ?? 2010.
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Winters, William J.; Walker, Michael; Hunter, Robert; Collett, Timothy S.; Boswell, Ray M.; Rose, Kelly K.; Waite, William F.; Torres, Marta; Patil, Shirish; Dandekar, Abhijit
2011-01-01
This study characterizes cored and logged sedimentary strata from the February 2007 BP Exploration Alaska, Department of Energy, U.S. Geological Survey (BPXA-DOE-USGS) Mount Elbert Gas Hydrate Stratigraphic Test Well on the Alaska North Slope (ANS). The physical-properties program analyzed core samples recovered from the well, and in conjunction with downhole geophysical logs, produced an extensive dataset including grain size, water content, porosity, grain density, bulk density, permeability, X-ray diffraction (XRD) mineralogy, nuclear magnetic resonance (NMR), and petrography. This study documents the physical property interrelationships in the well and demonstrates their correlation with the occurrence of gas hydrate. Gas hydrate (GH) occurs in three unconsolidated, coarse silt to fine sand intervals within the Paleocene and Eocene beds of the Sagavanirktok Formation: Unit D-GH (614.4 m-627.9 m); unit C-GH1 (649.8 m-660.8 m); and unit C-GH2 (663.2 m-666.3 m). These intervals are overlain by fine to coarse silt intervals with greater clay content. A deeper interval (unit B) is similar lithologically to the gas-hydrate-bearing strata; however, it is water-saturated and contains no hydrate. In this system it appears that high sediment permeability (k) is critical to the formation of concentrated hydrate deposits. Intervals D-GH and C-GH1 have average "plug" intrinsic permeability to nitrogen values of 1700 mD and 675 mD, respectively. These values are in strong contrast with those of the overlying, gas-hydrate-free sediments, which have k values of 5.7 mD and 49 mD, respectively, and thus would have provided effective seals to trap free gas. The relation between permeability and porosity critically influences the occurrence of GH. For example, an average increase of 4% in porosity increases permeability by an order of magnitude, but the presence of a second fluid (e.g., methane from dissociating gas hydrate) in the reservoir reduces permeability by more than an order of magnitude.
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Chlorite Stability in the Mantle Wedge and its Role in Subduction Zone Melting Processes
NASA Astrophysics Data System (ADS)
Grove, T. L.; Chatterjee, N.; Medard, E.; Parman, S. W.
2006-12-01
New experimental constraints on the H2O-saturated melting behavior of mantle peridotite (Grove et al., 2006, EPSL 249: 74 - 89) show that chlorite is a stable phase on the vapor-saturated solidus of peridotite at a pressure of 2 GPa and higher. Hydrous melting in the presence of chlorite begins at 860 °C at 2 GPa and the solidus temperature decreases continuously to 800 °C at 3.2 GPa. The solidus phases include olivine, orthopyroxene, high-Ca clinopyroxene and spinel + chlorite over the pressure range of 2 to 2.4 GPa. Garnet + chlorite + ilmenite are present above 2.4 GPa. At 2.8 to 3.2 GPa, chlorite is stable on the vapor- saturated solidus, but it reacts out 20 to 40 °C above the solidus. The temperature-pressure range for chlorite stability and vapor-saturated melting behavior involving chlorite are similar to those inferred for the mantle wedge above the subducted slab by geodynamic thermal models. Thus, chlorite may be a stable phase within the mantle wedge and may play a role in the onset of hydrous mantle melting. The factors that lead to the initiation of melting in subduction zones have remained enigmatic. The occurrence of volcanic fronts above the mantle wedge-subducted slab interface near a depth of 100 km in most arcs has not been conclusively explained. Melting must somehow be linked to processes that involve the release of water from the slab into the overlying mantle wedge, but why does melting always begin at or below 100 km? A potential melt triggering mechanism is that H2O released from dehydration reactions in the subducted oceanic lithosphere at pressures > 2 GPa rises into the overlying mantle and reacts with peridotite to form chlorite. This chloritized peridotite is pulled down by mantle flow to pressures of 3 to 3.5 GPa. Increases in temperature in the mantle wedge above the subducted slab lead to chlorite breakdown and/or vapor-saturated melting initiation. When mantle peridotite is hydrated ~ 13 wt. % chlorite is produced for a bulk H2O content of 2 wt. %. This is a large amount of H2O sufficient to produce melts with elevated H2O contents observed in primitive arc magmas (6 wt. % H2O) by flux melting. Thus, the uniform depth of 100 km from slab/wedge interface to overlying volcanic arc may be related to melting of chloritized mantle.
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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.
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Natural gas hydrate in oceanic and permafrost environments
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.
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[Lateral diffusion of saturated phosphatidylcholines in cholesterol-containing bilayers].
Filippov, A V; Rudakova, M A; Oradd, G; Lindblom, J
2007-01-01
Lateral diffusion in oriented bilayers of saturated cholesterol-containing phosphatidylcholines, dipalmitoylphosphatidylcholine and dimyrilstoylphosphatidylcholine upon their limiting hydration has been studied by NMR with impulse gradient of magnetic field. For both systems, similar dependences of the coefficient of lateral diffusion on temperature and cholesterol concentration were observed, which agree with the phase diagram showing the presence of regions of ordered and unordered liquid-crystalline phases and a two-phase region. Under similar conditions, the coefficient of lateral diffusion for dipalmytoylphosphatidylcholine has lower values, which is in qualitative agreement with its greater molecular mass. A comparison of data for dipalmytoylphosphatidylcholine with the results obtained earlier for dipalmytoylsphyngomyelin/cholesterol under the same conditions shows, despite a similarity in phase diagrams, greater (two- to threefold) differences in the values of the coefficient of lateral diffusion and a different mode of dependence of the coefficient on cholesterol concentration. A comparison of data for dimyrilstoylphosphatidylcholine with the results obtained previously shows that the values of the coefficient of lateral diffusion and the mode of its dependence on cholesterol concentration coincide in the region of higher concentrations (more than 15 mole %) and differ in the region of lower concentrations (below 15 mole %). The discrepancies may be explained by different contents of water in the systems during the measurements. At a limiting hydration (more than 35%) of water, the coefficient of lateral diffusion decreases with increasing cholesterol concentration. If the content of water is about 25% (as a result of equilibrium hydration from vapors), the coefficient of lateral diffusion of phosphatidylcholine is probably independent of cholesterol concentration. This results from a denser packing of molecules in the bilayer at a lower water concentration, an effect that competes with the ordering effect of cholesterol.
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Zhang, Zhengcai; Walsh, Matthew R; Guo, Guang-Jun
2015-04-14
The results of six high-precision constant energy molecular dynamics (MD) simulations initiated from methane-water systems equilibrated at 80 MPa and 250 K indicate that methane hydrates can nucleate via multiple pathways. Five trajectories nucleate to an amorphous solid. One trajectory nucleates to a structure-I hydrate template with long-range order which spans the simulation box across periodic boundaries despite the presence of several defects. While experimental and simulation data for hydrate nucleation with different time- and length-scales suggest that there may exist multiple pathways for nucleation, including metastable intermediates and the direct formation of the globally-stable phase, this work provides the most compelling evidence that direct formation to the globally stable crystalline phase is one of the multiple pathways available for hydrate nucleation.
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Miller, Jeff; Xue, Bin; Hossain, Md; Zhang, Ma-Zhong; Loepke, Andreas; Kurth, Dean
2016-03-01
Procedural sedation using chloral hydrate is used in many institutions to improve the quality of transthoracic echocardiograms (TTE) in infants and young children. Chloral hydrate has limited availability in some countries, creating the need for alternative effective sedatives. The aim of our study was to compare the effectiveness of two doses of intranasal dexmedetomidine vs oral chloral hydrate sedation for transthoracic echocardiography. This is a randomized, prospective study of 150 children under the age of 3 years with known or suspected congenital heart disease scheduled for transthoracic echocardiography with sedation. Group CH received oral chloral hydrate 70 mg · kg(-1), group DEX2 received 2 μg · kg(-1) intranasal dexmedetomidine, and group DEX3 received 3 μg · kg(-1) intranasal dexmedetomidine. Acceptance of drug administration, sedation onset and duration, heart rate, and oxygen saturation, sonographer and parent satisfaction were recorded. All patients were successfully sedated for TTE. A second sedative dose (rescue) for failed single-dose sedation was required for 4% of patients after CH, none of the patients after DEX2, and 4% of patients after DEX3. Patients in group CH had an average heart rate decline of 22% during sedation, while group DEX2 decreased 27%, and group DEX3 23% (P = 0.2180). Mean time from administration of the sedative to final patient discharge was 96 min after CH, 83 min after DEX2, and 94 min after DEX3 (P = 0.1826). Intranasal dexmedetomidine 2 and 3 μg · kg(-1) were found to be as effective for TTE sedation as oral chloral hydrate with similar sedation onset and recovery time and heart rate changes in this study population. © 2015 John Wiley & Sons Ltd.
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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.
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Equilibrium, Kinetics, and Spectroscopic Studies of SF6 Hydrate in NaCl Electrolyte Solution.
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.
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NASA Astrophysics Data System (ADS)
Dallimore, S. R.; Collett, T. S.; Uchida, T.; Weber, M.
2003-04-01
With the completion of scientific studies undertaken as part of the 1998 Mallik 2L-38 gas hydrate research well, an international research site was established for the study of Arctic natural gas hydrates in the Mackenzie Delta of northwestern Canada. Quantitative well log analysis and core studies reveal multiple gas hydrate layers from 890 m to 1106 m depth, exceeding 110 m in total thickness. High gas hydrate saturation values, which in some cases exceed 80% of the pore volume, establish the Mallik gas hydrate field as one of the most concentrated gas hydrate reservoirs in the world. Beginning in December 2001 and continuing to the middle of March 2002, two 1188 m deep science observation wells were drilled and instrumented and a 1166 m deep production research well program was carried out. The program participants include 8 partners; The Geological Survey of Canada (GSC), The Japan National Oil Corporation (JNOC), GeoForschungsZentrum Potsdam (GFZ), United States Geological Survey (USGS), United States Department of the Energy (USDOE), India Ministry of Petroleum and Natural Gas (MOPNG)/Gas Authority of India (GAIL) and the Chevron-BP-Burlington joint venture group. In addition the project has been accepted as part of the International Scientific Continental Drilling Program. The Geological Survey of Canada is coordinating the science program for the project and JAPEX Canada Ltd. acted as the designated operator for the fieldwork. Primary objectives of the research program are to advance fundamental geological, geophysical and geochemical studies of the Mallik gas hydrate field and to undertake advanced production testing of a concentrated gas hydrate reservoir. Full-scale field experiments in the production well monitored the physical behavior of the hydrate deposits in response to depressurization and thermal stimulation. The observation wells facilitated cross-hole tomography and vertical seismic profile experiments (before and after production) as well as the measurement of in situ formation conditions. A wide- ranging science and engineering research program included the collection of gas-hydrate-bearing core samples and downhole geophysical logging. Laboratory and modeling studies undertaken during the field program, and subsequently as part of a post-field research program, will document the sedimentology, physical/petrophysical properties, geochemistry, geophysics, reservoir characteristics and production behavior of the Mallik gas hydrate accumulation. The research team, including some 100 participant scientists from over 20 institutes in 7 countries, expects to publish the scientific results in 2004.
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Mamedov, Ilgar; Canals, Santiago; Henig, Jörg; Beyerlein, Michael; Murayama, Yusuke; Mayer, Hermann A; Logothetis, Nikos K; Angelovski, Goran
2010-12-15
Contrast agents for magnetic resonance imaging (MRI) that exhibit sensitivity toward specific ions or molecules represent a challenging but attractive direction of research. Here a Gd(3+) complex linked to an aminobis(methylenephosphonate) group for chelating Ca(2+) was synthesized and investigated. The longitudinal relaxivity (r(1)) of this complex decreases during the relaxometric titration with Ca(2+) from 5.76 to 3.57 mM(-1) s(-1) upon saturation. The r(1) is modulated by changes in the hydration number, which was confirmed by determination of the luminescence emission lifetimes of the analogous Eu(3+) complex. The initial in vivo characterization of this responsive contrast agent was performed by means of electrophysiology and MRI experiments. The investigated complex is fully biocompatible, having no observable effect on neuronal function after administration into the brain ventricles or parenchyma. Distribution studies demonstrated that the diffusivity of this agent is significantly lower compared with that of gadolinium-diethylenetriaminepentaacetic acid (Gd-DTPA).
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Mapping hydration dynamics around a protein surface
Zhang, Luyuan; Wang, Lijuan; Kao, Ya-Ting; Qiu, Weihong; Yang, Yi; Okobiah, Oghaghare; Zhong, Dongping
2007-01-01
Protein surface hydration is fundamental to its structure and activity. We report here the direct mapping of global hydration dynamics around a protein in its native and molten globular states, using a tryptophan scan by site-specific mutations. With 16 tryptophan mutants and in 29 different positions and states, we observed two robust, distinct water dynamics in the hydration layer on a few (≈1–8 ps) and tens to hundreds of picoseconds (≈20–200 ps), representing the initial local relaxation and subsequent collective network restructuring, respectively. Both time scales are strongly correlated with protein's structural and chemical properties. These results reveal the intimate relationship between hydration dynamics and protein fluctuations and such biologically relevant water–protein interactions fluctuate on picosecond time scales. PMID:18003912
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Use of vertical temperature gradients for prediction of tidal flat sediment characteristics
Miselis, Jennifer L.; Holland, K. Todd; Reed, Allen H.; Abelev, Andrei
2012-01-01
Sediment characteristics largely govern tidal flat morphologic evolution; however, conventional methods of investigating spatial variability in lithology on tidal flats are difficult to employ in these highly dynamic regions. In response, a series of laboratory experiments was designed to investigate the use of temperature diffusion toward sediment characterization. A vertical thermistor array was used to quantify temperature gradients in simulated tidal flat sediments of varying compositions. Thermal conductivity estimates derived from these arrays were similar to measurements from a standard heated needle probe, which substantiates the thermistor methodology. While the thermal diffusivities of dry homogeneous sediments were similar, diffusivities for saturated homogeneous sediments ranged approximately one order of magnitude. The thermal diffusivity of saturated sand was five times the thermal diffusivity of saturated kaolin and more than eight times the thermal diffusivity of saturated bentonite. This suggests that vertical temperature gradients can be used for distinguishing homogeneous saturated sands from homogeneous saturated clays and perhaps even between homogeneous saturated clay types. However, experiments with more realistic tidal flat mixtures were less discriminating. Relationships between thermal diffusivity and percent fines for saturated mixtures varied depending upon clay composition, indicating that clay hydration and/or water content controls thermal gradients. Furthermore, existing models for the bulk conductivity of sediment mixtures were improved only through the use of calibrated estimates of homogeneous end-member conductivity and water content values. Our findings suggest that remotely sensed observations of water content and thermal diffusivity could only be used to qualitatively estimate tidal flat sediment characteristics.
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Hunter, R.B.; Collett, T.S.; Boswell, R.; Anderson, B.J.; Digert, S.A.; Pospisil, G.; Baker, R.; Weeks, M.
2011-01-01
The Mount Elbert Gas Hydrate Stratigraphic Test Well was drilled within the Alaska North Slope (ANS) Milne Point Unit (MPU) from February 3 to 19, 2007. The well was conducted as part of a Cooperative Research Agreement (CRA) project co-sponsored since 2001 by BP Exploration (Alaska), Inc. (BPXA) and the U.S. Department of Energy (DOE) in collaboration with the U.S. Geological Survey (USGS) to help determine whether ANS gas hydrate can become a technically and commercially viable gas resource. Early in the effort, regional reservoir characterization and reservoir simulation modeling studies indicated that up to 0.34 trillion cubic meters (tcm; 12 trillion cubic feet, tcf) gas may be technically recoverable from 0.92 tcm (33 tcf) gas-in-place within the Eileen gas hydrate accumulation near industry infrastructure within ANS MPU, Prudhoe Bay Unit (PBU), and Kuparuk River Unit (KRU) areas. To further constrain these estimates and to enable the selection of a test site for further data acquisition, the USGS reprocessed and interpreted MPU 3D seismic data provided by BPXA to delineate 14 prospects containing significant highly-saturated gas hydrate-bearing sand reservoirs. The "Mount Elbert" site was selected to drill a stratigraphic test well to acquire a full suite of wireline log, core, and formation pressure test data. Drilling results and data interpretation confirmed pre-drill predictions and thus increased confidence in both the prospect interpretation methods and in the wider ANS gas hydrate resource estimates. The interpreted data from the Mount Elbert well provide insight into and reduce uncertainty of key gas hydrate-bearing reservoir properties, enable further refinement and validation of the numerical simulation of the production potential of both MPU and broader ANS gas hydrate resources, and help determine viability of potential field sites for future extended term production testing. Drilling and data acquisition operations demonstrated that gas hydrate scientific research programs can be safely, effectively, and efficiently conducted within ANS infrastructure. The program success resulted in a technical team recommendation to project management to drill and complete a long-term production test within the area of existing ANS infrastructure. If approved by stakeholders, this long-term test would build on prior arctic research efforts to better constrain the potential gas rates and volumes that could be produced from gas hydrate-bearing sand reservoirs. ?? 2010 Elsevier Ltd.
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Molecular modeling of the dissociation of methane hydrate in contact with a silica surface.
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
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Apparatus investigates geological aspects of gas hydrates
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.
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NASA Astrophysics Data System (ADS)
Oyanagi, Ryosuke; Okamoto, Atsushi; Hirano, Nobuo; Tsuchiya, Noriyoshi
2015-09-01
Serpentinization occurs via interactions between mantle peridotite and water that commonly passes through the crust. Given that such a fluid has a high silica activity compared with mantle peridotite, it is thought that serpentinization and silica metasomatism occur simultaneously at the crust-mantle boundary. In this study, we conducted hydrothermal experiments in the olivine (Ol)-quartz (Qtz)-H2O system at 250 °C and vapor-saturated pressure under highly alkaline conditions (NaOHaq, pH = 13.8 at 25 °C) to clarify the mechanism of silica metasomatism at the crust-mantle boundary. Composite powders consisting of a Qtz layer and an Ol layer were set in tube-in-tube vessels. After the experiments, the extents of serpentinization and metasomatic reactions were evaluated as a function of distance from the Ol-Qtz boundary. The mineralogy of the reaction products in the Ol-hosted region changed with increasing distance from the Ol-Qtz boundary, from smectite + serpentine (Smc zone) to serpentine + brucite + magnetite (Brc zone). Olivine hydration proceeded in both zones, but the total H2O content in the products was greater in the Brc zone than in the Smc zone. Mass balance calculations revealed that olivine hydration occurred without any supply of silica in the brucite zone. In contrast, the Smc zone was formed by silica metasomatism via competitive hydration and dehydration reactions. In the Smc zone, smectite formed via the simultaneous progress of olivine hydration and serpentine dehydration, and around the boundary of the Smc and Brc zones, serpentine formation occurred by olivine hydration and brucite dehydration. The relative extent of hydration and dehydration reactions controlled the along-tube variation in the rate of H2O production/consumption and the rate of volume increase. Our findings suggest that the competitive progress of serpentinization and silica metasomatic reactions would cause fluctuations in pore fluid pressure, possibly affecting the mechanical behavior of the crust-mantle boundary.
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Influence of Sodium Chloride on the Formation and Dissociation Behavior of CO2 Gas Hydrates.
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.
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Data for exploring the effect of parameters on decomposition of gas hydrate structure I.
Kheshty, Mohammad Fani; Varaminian, Farshad; Farhadian, Nafiseh
2018-06-01
This article describes initial and final configurations of methane hydrate structure I as PDB file at various cage occupancies and different temperatures. Cage occupancies from full occupancy to 75% at three temperatures of 290 K, 300 K and 310 K are presented. Dissociation behavior of gas hydrate structure I at the temperature of 300 K is shown in changing the potential energy and radial distribution function.
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How Properties of Solid Surfaces Modulate the Nucleation of Gas Hydrate
Bai, Dongsheng; Chen, Guangjin; Zhang, Xianren; Sum, Amadeu K.; Wang, Wenchuan
2015-01-01
Molecular dynamics simulations were performed for CO2 dissolved in water near silica surfaces to investigate how the hydrophilicity and crystallinity of solid surfaces modulate the local structure of adjacent molecules and the nucleation of CO2 hydrates. Our simulations reveal that the hydrophilicity of solid surfaces can change the local structure of water molecules and gas distribution near liquid-solid interfaces, and thus alter the mechanism and dynamics of gas hydrate nucleation. Interestingly, we find that hydrate nucleation tends to occur more easily on relatively less hydrophilic surfaces. Different from surface hydrophilicity, surface crystallinity shows a weak effect on the local structure of adjacent water molecules and on gas hydrate nucleation. At the initial stage of gas hydrate growth, however, the structuring of molecules induced by crystalline surfaces are more ordered than that induced by amorphous solid surfaces. PMID:26227239
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Effect of water on the composition of partial melts of greenstone and amphibolite
NASA Technical Reports Server (NTRS)
Beard, James S.; Lofgren, Gary E.
1989-01-01
Closed-system partial melts of hydrated, metamorphosed arc basalts and andesites (greenstones and amphibolites), where only water structurally bound in metamorphic minerals is available for melting (dehydration melting), are generally water-undersaturated, coexist with plagioclase-rich, anhydrous restites, and have compositions like island arc tonalites. In contrast, water-saturated melting at water pressures of 3 kilobars yields strongly peraluminous, low iron melts that coexist with an amphibole-bearing, plagioclase-poor restite. These melt compositions are unlike those of most natural silicic rocks. Thus, dehydration melting over a range of pressures in the crust of island arcs is a plausible mechanism for the petrogenesis of islands arc tonalite, whereas water-saturated melting at pressure of 3 kilobars and above is not.
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Remediation of Cr(VI)-Contaminated Soil Using the Acidified Hydrazine Hydrate.
Ma, Yameng; Li, Fangfang; Jiang, Yuling; Yang, Weihua; Lv, Lv; Xue, Haotian; Wang, Yangyang
2016-09-01
Acidified hydrazine hydrate was used to remediate Cr(VI)-contaminated soil. The content of water-soluble Cr(VI) in contaminated soil was 4977.53 mg/kg. The optimal initial pH of hydrazine hydrate solution, soil to solution ratio and molar ratio of Cr(VI) to hydrazine hydrate for remediation of Cr(VI)-contaminated soil were 5.0, 3:1 and 1:3, respectively. Over 99.50 % of water-soluble Cr(VI) in the contaminated soil was reduced at the optimal condition within 30 min. The remediated soil can keep stable within 4 months. Meanwhile the total phosphorus increased from 0.47 to 4.29 g/kg, indicating that using of acidified hydrazine hydrate is an effective method to remediate Cr(VI)-contaminated soil.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Bahafid, Sara; Ghabezloo, Siavash; Duc, Myriam
Curing temperature has a significant influence on cement paste microstructure and the properties of its principal hydrate C-S-H. In this paper, the effect of the hydration temperature in the range of 7 °C to 90 °C on the microstructure of a class G oil-well cement is studied. This is done by combining various experimental methods, including X-ray diffraction associated with the Rietveld analysis, thermo-gravimetric analysis, mercury intrusion porosimetry and porosity evaluation by drying. The experimental results show an increase of the capillary porosity and a decrease of the gel porosity by increasing the hydration temperature. This is attributed to amore » decrease of the C-S-H intrinsic porosity and a corresponding increase of the C-S-H density for higher curing temperatures. The experimental results are used in a simple analysis method to evaluate the density of C-S-H, as well as its C/S ratio and H/S ratio in dry and saturated conditions. The evaluated C-S-H density varies from 1.88 g/cm{sup 3} at 7 °C to 2.10 g/cm{sup 3} at 90 °C. The results also show a decrease of molar C/S ratio with increasing hydration temperature from 1.93 at 7 °C to 1.71 at 90 °C and of the H/S ratio from 5.1 at 7 °C to 2.66 at 90 °C.« less
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Lee, Myung W.
2006-01-01
Elastic properties of gas hydrate-bearing sediments (GHBS) are important for identifying and quantifying gas hydrate as well as discriminating the effects of free gas on velocity from that due to overpressure. Elastic properties of GHBS sediments can be estimated from elastic inversion using the elastic impedance. The accuracy of elastic inversion can be increased by using the predicted S-wave velocity (Vs) in the parameter k, which is k = (Vs / Vp)2. However, when Vs is less than about 0.6 kilometer per second, the inversion is inaccurate, partly because of the difficulty in accurately predicting low S-wave velocities and partly because of the large error associated with small k values. A new formula that leads to estimates of only the high-frequency part of velocity is proposed by decomposing Vs into low- and high-frequency parts. This new inversion formula is applied to a variety of well logs, and the results demonstrate its effectiveness for all ranges of Vs as long as the deviation of Vs from the low-frequency part of Vs is small. For GHBS, the deviation of Vs from the low-frequency part of Vs can be large for moderate to high gas hydrate saturations. Therefore, the new formula is not effective for elastic inversion for GHBS unless the gas hydrate effect is incorporated into the low-frequency part of Vs. For inversion of GHBS with Vs greater than about 0.6 kilometer per second, the original formulation is preferable.
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Measurement of chain tilt angle in fully hydrated bilayers of gel phase lecithins.
Tristram-Nagle, S; Zhang, R; Suter, R M; Worthington, C R; Sun, W J; Nagle, J F
1993-01-01
The tilt angle theta tilt of the hydrocarbon chains has been determined for fully hydrated gel phase of a series of saturated lecithins. Oriented samples were prepared on glass substrates and hydrated with supersaturated water vapor. Evidence for full hydration was the same intensity pattern of the low angle lamellar peaks and the same lamellar repeat D as unoriented multilamellar vesicles. Tilting the sample permitted observation of all the wide angle arcs necessary to verify the theoretical diffraction pattern corresponding to tilting of the chains towards nearest neighbors. The length of the scattering unit corresponds to two hydrocarbon chains, requiring each bilayer to scatter coherently rather than each monolayer. For DPPC, theta tilt was determined to be 32.0 +/- 0.5 degrees at 19 degrees C, slightly larger than previous direct determinations and considerably smaller than the value required by recent gravimetric measurements. This new value allows more accurate determinations of a variety of structural parameters, such as area per lipid molecule, A = 47.2 +/- 0.5 A2, and number of water molecules of hydration, nw = 11.8 +/- 0.7. As the chain length n of the lipids was increased from 16 to 20 carbons, the parameters A and nw remained constant, suggesting that the headgroup packing is at its excluded volume limit for this range. However, theta tilt increased by 3 degrees and the chain area Ac decreased by 0.5 A2. This behavior is explained in terms of a competition between a bulk free energy term and a finite or end effect term. Images FIGURE 6 FIGURE 7 PMID:8494973
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Riedel, Michael; Collett, Timothy S.; Kim, H.-S.; Bahk, J.-J.; Kim, J.-H.; Ryu, B.-J.; Kim, G.-Y.
2013-01-01
Gas hydrate saturation estimates were obtained from an Archie-analysis of the Logging-While-Drilling (LWD) electrical resistivity logs under consideration of the regional geological framework of sediment deposition in the Ulleung Basin, East Sea, of Korea. Porosity was determined from the LWD bulk density log and core-derived values of grain density. In situ measurements of pore-fluid salinity as well as formation temperature define a background trend for pore-fluid resistivity at each drill site. The LWD data were used to define sets of empirical Archie-constants for different depth-intervals of the logged borehole at all sites drilled during the second Ulleung Basin Gas Hydrate Drilling Expedition (UBGH2). A clustering of data with distinctly different trend-lines is evident in the cross-plot of porosity and formation factor for all sites drilled during UBGH2. The reason for the clustering is related to the difference between hemipelagic sediments (mostly covering the top ∼100 mbsf) and mass-transport deposits (MTD) and/or the occurrence of biogenic opal. For sites located in the north-eastern portion of the Ulleung Basin a set of individual Archie-parameters for a shallow depth interval (hemipelagic) and a deeper MTD zone was achieved. The deeper zone shows typically higher resistivities for the same range of porosities seen in the upper zone, reflecting a shift in sediment properties. The presence of large amounts of biogenic opal (up to and often over 50% as defined by XRD data) was especially observed at Sites UBGH2-2_1 and UBGH2-2_2 (as well as UBGH1-9 from a previous drilling expedition in 2007). The boundary between these two zones can also easily be identified in gamma-ray logs, which also show unusually low readings in the opal-rich interval. Only by incorporating different Archie-parameters for the different zones a reasonable estimate of gas hydrate saturation was achieved that also matches results from other techniques such as pore-fluid freshening, velocity-based calculations, and pressure-core degassing experiments. Seismically, individual boundaries between zones were determined using a grid of regional 2D seismic data. Zoning from the Archie-analysis for sites in the south-western portion of the Ulleung Basin was also observed, but at these sites it is linked to individually stacked MTDs only and does not reflect a mineralogical occurrence of biogenic opal or hemipelagic sedimentation. The individual MTD events represent differently compacted material often associated with a strong decrease in porosity (and increase in density), warranting a separate set of empirical Archie-parameters.
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Electrical anisotropy of gas hydrate-bearing sand reservoirs in the Gulf of Mexico
Cook, Anne E.; Anderson, Barbara I.; Rasmus, John; Sun, Keli; Li, Qiming; Collett, Timothy S.; Goldberg, David S.
2012-01-01
We present new results and interpretations of the electricalanisotropy and reservoir architecture in gashydrate-bearingsands using logging data collected during the Gulf of MexicoGasHydrate Joint Industry Project Leg II. We focus specifically on sandreservoirs in Hole Alaminos Canyon 21 A (AC21-A), Hole Green Canyon 955 H (GC955-H) and Hole Walker Ridge 313 H (WR313-H). Using a new logging-while-drilling directional resistivity tool and a one-dimensional inversion developed by Schlumberger, we resolve the resistivity of the current flowing parallel to the bedding, R| and the resistivity of the current flowing perpendicular to the bedding, R|. We find the sandreservoir in Hole AC21-A to be relatively isotropic, with R| and R| values close to 2 Ω m. In contrast, the gashydrate-bearingsandreservoirs in Holes GC955-H and WR313-H are highly anisotropic. In these reservoirs, R| is between 2 and 30 Ω m, and R| is generally an order of magnitude higher. Using Schlumberger's WebMI models, we were able to replicate multiple resistivity measurements and determine the formation resistivity the gashydrate-bearingsandreservoir in Hole WR313-H. The results showed that gashydrate saturations within a single reservoir unit are highly variable. For example, the sand units in Hole WR313-H contain thin layers (on the order of 10-100 cm) with varying gashydrate saturations between 15 and 95%. Our combined modeling results clearly indicate that the gashydrate-bearingsandreservoirs in Holes GC955-H and WR313-H are highly anisotropic due to varying saturations of gashydrate forming in thin layers within larger sand units.
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Airflow accelerates bovine and human articular cartilage drying and chondrocyte death.
Paterson, S I; Amin, A K; Hall, A C
2015-02-01
Exposure of articular cartilage to static air results in changes to the extracellular matrix (ECM) and stimulates chondrocyte death, which may cause joint degeneration. However during open orthopaedic surgery, cartilage is often exposed to laminar airflow, which may exacerbate these damaging effects. We compared drying in static and moving air in terms of cartilage appearance, hydration and chondrocyte viability, and tested the ability of saline-saturated gauze to limit the detrimental effects of air exposure. Articular cartilage from bovine metatarsophalangeal joints (N = 50) and human femoral heads (N = 6) was exposed for 90 min to (1) static air (2) airflow (up to 0.34 m/s), or (3) airflow (0.18 m/s), covered with gauze. Following air exposure, cartilage was also rehydrated (0.9% saline; 120 min) to determine the reversibility of drying effects. The influence of airflow was assessed by studying macroscopic appearance, and quantifying superficial zone (SZ) chondrocyte viability and cartilage hydration. Airflow caused advanced changes to cartilage appearance, accelerated chondrocyte death, and increased dehydration compared to static air. These effects were prevented if cartilage was covered by saline-saturated gauze. Cartilage rehydration reversed macroscopic changes associated with drying but the chondrocyte death was not altered. Chondrocytes at the cut edge of cartilage were more sensitive to drying compared to cells distant from the edge. Airflow significantly increased articular cartilage dehydration and chondrocyte death compared to static air. As laminar airflow is routinely utilised in operating theatres, it is essential that articular cartilage is kept wet via irrigation or by covering with saline-saturated gauze to prevent chondrocyte death. Copyright © 2014 Osteoarthritis Research Society International. Published by Elsevier Ltd. All rights reserved.
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Effect of Sleep on the Central Nervous System.
1981-03-30
carrier buffer) for 2 hours. After osmication the tissue was thoroughly rinsed in buffer, de- hydrated in alcohol changes and embedded either in...stained in 5% urahyl acetate in 50% alcohol and saturated with lead citrate. 12 Morphometric analysis was performed by taking low power (5,600x...Biol. 70L 190-92, 1911. 203, 215, 352. 10. Legeadre, R. et H. Pieron. Destruction par oxydation de la pro- priete hypnotoxique des humeurs
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Influence of Sodium Chloride on the Formation and Dissociation Behavior of CO2 Gas Hydrates
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
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Le, Peisi; Fratini, Emiliano; Ito, Kanae; ...
2016-01-28
We present the hypothesis that the mechanical properties of cement pastes depend strongly on their porosities. In a saturated paste, the porosity links to the free water volume after hydration. Structural water, constrained water, and free water have different dynamical behavior. Hence, it should be possible to extract information on pore system by exploiting the water dynamics. With our experiments we investigated the slow dynamics of hydration water confined in calcium- and magnesium-silicate-hydrate (C-S-H and M-S-H) gels using high-resolution quasi-elastic neutron scattering (QENS) technique. C-S-H and M-S-H are the chemical binders present in calcium rich and magnesium rich cements. Wemore » measured three M-S-H samples: pure M-S-H, M-S-H with aluminum-silicate nanotubes (ASN), and M-S-H with carboxyl group functionalized ASN (ASN-COOH). A C-S-H sample with the same water content (i.e. 0.3) is also studied for comparison. We found that structural water in the gels contributes to the elastic component of the QENS spectrum, while constrained water and free water contribute the quasi-elastic component. The quantitative analysis suggests that the three components vary for different samples and indicate the variance in the system porosity, which controls the mechanical properties of cement pastes.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Le, Peisi; Fratini, Emiliano; Ito, Kanae
We present the hypothesis that the mechanical properties of cement pastes depend strongly on their porosities. In a saturated paste, the porosity links to the free water volume after hydration. Structural water, constrained water, and free water have different dynamical behavior. Hence, it should be possible to extract information on pore system by exploiting the water dynamics. With our experiments we investigated the slow dynamics of hydration water confined in calcium- and magnesium-silicate-hydrate (C-S-H and M-S-H) gels using high-resolution quasi-elastic neutron scattering (QENS) technique. C-S-H and M-S-H are the chemical binders present in calcium rich and magnesium rich cements. Wemore » measured three M-S-H samples: pure M-S-H, M-S-H with aluminum-silicate nanotubes (ASN), and M-S-H with carboxyl group functionalized ASN (ASN-COOH). A C-S-H sample with the same water content (i.e. 0.3) is also studied for comparison. We found that structural water in the gels contributes to the elastic component of the QENS spectrum, while constrained water and free water contribute the quasi-elastic component. The quantitative analysis suggests that the three components vary for different samples and indicate the variance in the system porosity, which controls the mechanical properties of cement pastes.« less
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Geologic and Site Survey Setting for JIP Gulf of Mexico Gas Hydrate Drilling
NASA Astrophysics Data System (ADS)
Hutchinson, D. R.; Snyder, F.; Hart, P. E.; Ruppel, C. D.; Pohlman, J.; Wood, W. T.; Coffin, R. B.; Edwards, K. M.
2005-12-01
The JIP Gulf of Mexico drilling program targeted two contrasting geologic settings to understand natural gas hydrates: a salt-withdrawal minibasin and a mound/seep site, both at mid-slope water depths of about 1300 m. The minibasin site (lease block Keathley Canyon 151) contains a Bottom Simulating Reflection (BSR) that deepens from 260 m below the sea floor near the edge of the basin to 500 mbsf towards the center of the basin. Drilling was conducted at a site in which the BSR is about 415 mbsf. Seismic stratigraphy of the minibasin consists of continuous laminated sequences of variable thicknesses alternating with more massive units of discontinuous reflections. These sequences represent uniform hemipelagic deposition, which drapes the basin, and turbidite deposition, which pinches out along the basin edges. The BSR crosses several of these sequences. A map of amplitude values at the BSR shows a strong banding pattern indicative of the layering, with the highest amplitudes interpreted to be trapped gas in the coarser-grained units. Prior to drilling, piston-core data indicated extensive shallow mass wasting near the edges of the minibasin. Heat flow data indicated thermal gradients that in general predicted a BSR deeper than observed in the seismic data. Full-waveform inversion of 3D multichannel data indicated a probable thick zone of low-saturation hydrate immediately above the BSR. There is little coherent seismic stratigraphy at the mound/seep site in the Mississippi Canyon (lease blocks Atwater Valley 13/14), as the canyon fill is dominated by a complex mix of turbidite and mass-wasting deposits. Hints of a possible BSR that is warped upwards beneath the mound can be seen in both 3D and 2D multichannel seismic data, but it cannot be traced laterally away from the mound with any certainty. A seismic pull-down pseudo-structure beneath the mound suggests the presence of a free-gas low-velocity zone at shallow depths. Pore-water analyses from shallow piston cores and closely-spaced heat-flow data indicate the mound is a site of probable fluid venting. A transect of bottom photographs crosses a possible mud flow and numerous bacterial mats, consistent with features seen in fluid venting at other sites in the Gulf. Prestack inversion of the multichannel data did not predict significant gas hydrate at the site on the edge of the mound. However, at the control site off the mound, predictions were more favorable for low hydrate saturations in the deeper part of the drill hole.
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The hydration dependence of CaCO3 absorption lines in the Far IR
NASA Astrophysics Data System (ADS)
Powell, Johnny; Emery, Logan P
2014-06-01
The far infrared (FIR) absorption lines of CaCO3 have been measured at a range of relative humidities (RH) between 33 and 92% RH using a Bruker 66v/S spectrometer. Hydration measurements on CaCO3 have been made in the mid-infrared (MIR) by [Al-Hosney, H.A. and Grassian, V.H., 2005, Phys. Chem. Chem. Phys., 7, 1266], and astrophysically-motivated temperature-dependent FIR measurements of CaCO3 in vacuum have also been reported [Posch, T., et al., 2007, Ap. J., 668, 993]. The custom sample cell constructed for these hydrated-FIR spectra is required because the 66v/S bench is under vacuum (3 mbar) during typical measurements. Briefly, the sample cell consists of two Thalium Bromoiodide (KRS-5) windows, four O-rings, a plastic ring for separating the windows and providing a volume for the saturated atmosphere. CaCO3 was deposited on KRS-5 windows using doubly-distilled water as an intermediary. The KRS-5 window with sample and assembled sample cell were placed in a desiccator with the appropriated saturated salt solution [Washburn, E.W. (Ed.), International Critical Tables of Numerical Data, Physics Chemistry and Technology, Vol. 1, (McGraw-Hill, New York, 1926), p. 67-68] and allowed to hydrate for 23 hours. For spectroscopy the desiccator was quickly opened and the second KRS-5 window placed in the cell to seal the chamber. A spectrum was then taken of the sample at the appropriate RH. The spectra taken characterize the adsorption of water vapor and CaCO3 that might occur in circumstellar environments [Melnick, G.J., et al. 2001, Nature, 412, 160].The MIR and FIR reflectance spectra of calcite (CaCO3) have been thoroughly studied by [Hellwege, K.H., et al., 1970, Z. Physik, 232, 61]. Five Lorentzian curves were fit to our data in the range from 378-222 cm-1/SUP> and each was able to be assigned to a known mode of CaCO3. The data does not support the conclusion of a hydration effect on these modes of CaCO3, but it does suggest a possible broadening of three modes peaked at 281 cm-1. The goal of this work is to bridge the body of work on CaCO3 in physical chemistry and previous laboratory astrophysical observations to aid interpretation of FIR spectra obtained by observatories such as the Spitzer Space Telescope.
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Simulating the gas hydrate production test at Mallik using the pilot scale pressure reservoir LARS
NASA Astrophysics Data System (ADS)
Heeschen, Katja; Spangenberg, Erik; Schicks, Judith M.; Priegnitz, Mike; Giese, Ronny; Luzi-Helbing, Manja
2014-05-01
LARS, the LArge Reservoir Simulator, allows for one of the few pilot scale simulations of gas hydrate formation and dissociation under controlled conditions with a high resolution sensor network to enable the detection of spatial variations. It was designed and built within the German project SUGAR (submarine gas hydrate reservoirs) for sediment samples with a diameter of 0.45 m and a length of 1.3 m. During the project, LARS already served for a number of experiments simulating the production of gas from hydrate-bearing sediments using thermal stimulation and/or depressurization. The latest test simulated the methane production test from gas hydrate-bearing sediments at the Mallik test site, Canada, in 2008 (Uddin et al., 2011). Thus, the starting conditions of 11.5 MPa and 11°C and environmental parameters were set to fit the Mallik test site. The experimental gas hydrate saturation of 90% of the total pore volume (70 l) was slightly higher than volumes found in gas hydrate-bearing formations in the field (70 - 80%). However, the resulting permeability of a few millidarcy was comparable. The depressurization driven gas production at Mallik was conducted in three steps at 7.0 MPa - 5.0 MPa - 4.2 MPa all of which were used in the laboratory experiments. In the lab the pressure was controlled using a back pressure regulator while the confining pressure was stable. All but one of the 12 temperature sensors showed a rapid decrease in temperature throughout the sediment sample, which accompanied the pressure changes as a result of gas hydrate dissociation. During step 1 and 2 they continued up to the point where gas hydrate stability was regained. The pressure decreases and gas hydrate dissociation led to highly variable two phase fluid flow throughout the duration of the simulated production test. The flow rates were measured continuously (gas) and discontinuously (liquid), respectively. Next to being discussed here, both rates were used to verify a model of gas hydrate dissociation applying the foamy oil approach, a method earlier adopted to model the Mallik production test (see abstract Abendroth et al., this volume). Combined with a dense set of data from a cylindrical electrical resistance tomography (ERT) array (see abstract Priegnitz et al., this volume), very valuable information were gained on the spatial as well as temporal formation and dissociation of gas hydrates as well as changes in permeability and resulting pathways for the fluid flow. Here we present the set-up and execution of the experiment and discuss the results from temperature and flow measurements with respect to the gas hydrate dissociation and characteristics of resulting fluid flow. Uddin, M., Wright, F., and Coombe, D. 2011. Numerical Study of Gas Evolution and Transport Behaviours in Natural Gas-Hydrate Reservoirs. Journal of Canadian Petroleum Technology 50, 70-89.
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NASA Astrophysics Data System (ADS)
Janicki, Georg; Schlüter, Stefan; Hennig, Torsten; Deerberg, Görge
2013-04-01
The recovery of methane from gas hydrate layers that have been detected in several submarine sediments and permafrost regions around the world so far is considered to be a promising measure to overcome future shortages in natural gas as fuel or raw material for chemical syntheses. Being aware that natural gas resources that can be exploited with conventional technologies are limited, research is going on to open up new sources and develop technologies to produce methane and other energy carriers. Thus various research programs have started since the early 1990s in Japan, USA, Canada, South Korea, India, China and Germany to investigate hydrate deposits and develop technologies to destabilize the hydrates and obtain the pure gas. In recent years, intensive research has focussed on the capture and storage of carbon dioxide from combustion processes to reduce climate change. While different natural or manmade reservoirs like deep aquifers, exhausted oil and gas deposits or other geological formations are considered to store gaseous or liquid carbon dioxide, the storage of carbon dioxide as hydrate in former methane hydrate fields is another promising alternative. Due to beneficial stability conditions, methane recovery may be well combined with CO2 storage in form of hydrates. This has been shown in several laboratory tests and simulations - technical field tests are still in preparation. Within the scope of the German research project »SUGAR«, different technological approaches are evaluated and compared by means of dynamic system simulations and analysis. Detailed mathematical models for the most relevant chemical and physical effects are developed. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into simulation programs like CMG STARS and COMSOL Multiphysics. New simulations based on field data have been carried out. The studies focus on the evaluation of the gas production potential from turbidites and their ability for carbon dioxide storage. The effects occurring during gas production and CO2 storage within a hydrate deposit are identified and described for various scenarios. The behaviour of relevant process parameters such as pressure, temperature and phase saturations is discussed and compared for different production strategies: depressurization, CO2 injection after depressurization and simultaneous methane production and CO2 injection.
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Growth Kinetics and Mechanics of Hydrate Films by Interfacial Rheology.
Leopércio, Bruna C; de Souza Mendes, Paulo R; Fuller, Gerald G
2016-05-03
A new approach to study and understand the kinetics and mechanical properties of hydrates by interfacial rheology is presented. This is made possible using a "double wall ring" interfacial rheology cell that has been designed to provide the necessary temperature control. Cyclopentane and water are used to form hydrates, and this model system forms these structures at ambient pressures. Different temperature and water/hydrocarbon contact protocols are explored. Of particular interest is the importance of first contacting the hydrocarbon against ice crystals in order to initiate hydrate formation. Indeed, this is found to be the case, even though the hydrates may be created at temperatures above the melting point of ice. Once hydrates completely populate the hydrocarbon/water interface, strain sweeps of the interfacial elastic and viscous moduli are conducted to interrogate the mechanical response and fragility of the hydrate films. The dependence on temperature, Tf, by the kinetics of formation and the mechanical properties is reported, and the cyclopentane hydrate dissociation temperature was found to be between 6 and 7 °C. The formation time (measured from the moment when cyclopentane first contacts ice crystals) as well as the elastic modulus and the yield strain increase as Tf increases.
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Helgerud, M.B.; Waite, W.F.; Kirby, S.H.; Nur, A.
2009-01-01
We used ultrasonic pulse transmission to measure compressional, P, and shear, S, wave speeds in laboratory-formed polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate. From the wave speed's linear dependence on temperature and pressure and from the sample's calculated density, we derived expressions for bulk, shear, and compressional wave moduli and Poisson's ratio from -20 to 15??C and 22.4 to 32.8 MPa for ice Ih, -20 to 15??C and 30.5 to 97.7 MPa for si methane hydrate, and -20 to 10??C and 30.5 to 91.6 MPa for sll methane-ethane hydrate. All three materials had comparable P and S wave speeds and decreasing shear wave speeds with increasing applied pressure. Each material also showed evidence of rapid intergranular bonding, with a corresponding increase in wave speed, in response to pauses in sample deformation. There were also key differences. Resistance to uniaxial compaction, indicated by the pressure required to compact initially porous samples, was significantly lower for ice Ih than for either hydrate. The ice Ih shear modulus decreased with increasing pressure, in contrast to the increase measured in both hydrates ?? 2009.
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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.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Gillams, Richard J.; McLain, Sylvia E., E-mail: sylvia.mclain@bioch.ox.ac.uk; Lorenz, Christian D., E-mail: chris.lorenz@kcl.ac.uk
2016-06-14
Previous studies have used neutron diffraction to elucidate the hydration of the ceramide and the phosphatidylcholine headgroup in solution. These solution studies provide bond-length resolution information on the system, but are limited to liquid samples. The work presented here investigates how the hydration of ceramide and phosphatidylcholine headgroups in a solution compares with that found in a lipid bilayer. This work shows that the hydration patterns seen in the solution samples provide valuable insight into the preferential location of hydrating water molecules in the bilayer. There are certain subtle differences in the distribution, which result from a combination of themore » lipid conformation and the lipid-lipid interactions within the bilayer environment. The lipid-lipid interactions in the bilayer will be dependent on the composition of the bilayer, whereas the restricted exploration of conformational space is likely to be applicable in all membrane environments. The generalized description of hydration gathered from the neutron diffraction studies thus provides good initial estimation for the hydration pattern, but this can be further refined for specific systems.« less
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Relation of submarine landslide to hydrate occurrences in Baiyun Depression, South China Sea
NASA Astrophysics Data System (ADS)
Sun, Yunbao; Zhang, Xiaohua; Wu, Shiguo; Wang, Lei; Yang, Shengxiong
2018-02-01
Submarine landslides have been observed in the Baiyun Depression of the South China Sea. The occurrence of hydrates below these landslides indicates that these slope instabilities may be closely related to the massive release of methane. In this study, we used a simple Monte-Carlo model to determine the first-order deformation pattern of a gravitationally destabilizing slope. The results show that a stress concentration occurs due to hydrate dissociation on the nearby glide surface and on top of a gas chimney structure. Upon the dissolution of the gas hydrate, slope failure occurs due to the excess pore pressure generated by the dissociation of the gas hydrates. When gas hydrates dissociate at shallow depths, the excess pore pressure generated can be greater than the total stress acting at those points, along with the forces that resist sliding. Initially, the failure occurs at the toe of the slope, then extends to the interior. Although our investigation focused only on the contribution of hydrate decomposition to submarine landslide, this process is also affected by both the slope material properties and topography.
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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.
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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.
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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.
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Water-wetting surfaces as hydrate promoters during transport of carbon dioxide with impurities.
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.
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NASA Astrophysics Data System (ADS)
Ballarini, E.; Graupner, B.; Bauer, S.
2015-12-01
For deep geological repositories of high-level radioactive waste (HLRW), bentonite and sand bentonite mixtures are investigated as buffer materials to form a a sealing layer. This sealing layer surrounds the canisters and experiences an initial drying due to the heat produced by HLRW and a successive re-saturation with fluid from the host rock. These complex thermal, hydraulic and mechanical processes interact and were investigated in laboratory column experiments using MX-80 clay pellets as well as a mixture of 35% sand and 65% bentonite. The aim of this study is to both understand the individual processes taking place in the buffer materials and to identify the key physical parameters that determine the material behavior under heating and hydrating conditions. For this end, detailed and process-oriented numerical modelling was applied to the experiments, simulating heat transport, multiphase flow and mechanical effects from swelling. For both columns, the same set of parameters was assigned to the experimental set-up (i.e. insulation, heater and hydration system), while the parameters of the buffer material were adapted during model calibration. A good fit between model results and data was achieved for temperature, relative humidity, water intake and swelling pressure, thus explaining the material behavior. The key variables identified by the model are the permeability and relative permeability, the water retention curve and the thermal conductivity of the buffer material. The different hydraulic and thermal behavior of the two buffer materials observed in the laboratory observations was well reproduced by the numerical model.
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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.
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Analysis of gene network robustness based on saturated fixed point attractors
2014-01-01
The analysis of gene network robustness to noise and mutation is important for fundamental and practical reasons. Robustness refers to the stability of the equilibrium expression state of a gene network to variations of the initial expression state and network topology. Numerical simulation of these variations is commonly used for the assessment of robustness. Since there exists a great number of possible gene network topologies and initial states, even millions of simulations may be still too small to give reliable results. When the initial and equilibrium expression states are restricted to being saturated (i.e., their elements can only take values 1 or −1 corresponding to maximum activation and maximum repression of genes), an analytical gene network robustness assessment is possible. We present this analytical treatment based on determination of the saturated fixed point attractors for sigmoidal function models. The analysis can determine (a) for a given network, which and how many saturated equilibrium states exist and which and how many saturated initial states converge to each of these saturated equilibrium states and (b) for a given saturated equilibrium state or a given pair of saturated equilibrium and initial states, which and how many gene networks, referred to as viable, share this saturated equilibrium state or the pair of saturated equilibrium and initial states. We also show that the viable networks sharing a given saturated equilibrium state must follow certain patterns. These capabilities of the analytical treatment make it possible to properly define and accurately determine robustness to noise and mutation for gene networks. Previous network research conclusions drawn from performing millions of simulations follow directly from the results of our analytical treatment. Furthermore, the analytical results provide criteria for the identification of model validity and suggest modified models of gene network dynamics. The yeast cell-cycle network is used as an illustration of the practical application of this analytical treatment. PMID:24650364
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Molloy, C Johnston; Gandy, J; Cunningham, C; Slattery, Glennon
2008-10-01
Inadequate hydration has been linked to many factors that may impact on children's education and health. Teachers play an important role in the education and behaviour of children. Previous research has demonstrated low water intake amongst children and negative teachers' attitudes to water in the classroom. The present study aimed to explore teachers' knowledge about water and the perceived barriers to allowing children access to water during lesson time. In-depth interviews were conducted with 12 teachers from primary schools in the Midlands of Ireland. Interviews were continued until there was saturation of the data. Thematic analysis of the data was conducted. Participants had a poor knowledge of hydration requirements and the associated health benefits and effect on concentration. Low water intake amongst teachers and pupils, and barriers such as disruption to class and increased need to urinate, were reported. Teachers identified the hydration effect on learning as the education message most likely to influence the decision to allow water in the classroom. The issues, opinions and perceived barriers raised by teachers as part of this qualitative research provide a basis for future health promotion around water.
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Liu, Xiao; Guan, Jianan; Lai, Guanghong; Wang, Ziming; Zhu, Jie; Cui, Suping; Lan, Mingzhang; Li, Huiqun
2017-10-15
A novel star-shaped polycarboxylate superplasticizer (SPCE) was synthesized through a simple two-step method. 1 H Nuclear Magnetic Resonance ( 1 H NMR) and Infrared Spectroscopy (IR) measurements were used for structural characterization. SPCE and comb-shaped polycarboxylate superplasticizer (CPCE) with same molecular weights were designed and synthesized. The cement paste containing SPCE exhibited better fluidity, fluidity retention, water reduction, 25% lower saturated dosage of PCE, 10% longer setting time, lower hydration heat, more delayed hydration heat evolution and lower amount of hydration products at early ages. Furthermore, the adsorption behavior of SPCE and CPCE in cement pastes and the zeta potential were investigated, and then the working mechanism of SPCE was theoretically explained. It is interesting that changing topological structure from comb-shape to star-shape can achieve the optimization of dispersion effect, and further improve the working effectiveness. The aims of this study are to provide a new avenue to synthesize superplasticizer with novel structure achieving the chemical diversity of superplasticizer structure, and to verify the contribution of optimizing molecular shape. This new type of superplasticizer can be used as a rheology modifying agent in fresh cement-based materials. Copyright © 2017 Elsevier Inc. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Jung, Hun Bok; Um, Wooyong
2013-08-16
Hydrated Portland cement was reacted with carbon dioxide (CO2) in supercritical, gaseous, and aqueous phases to understand the potential cement alteration processes along the length of a wellbore, extending from deep CO2 storage reservoir to the shallow subsurface during geologic carbon sequestration. The 3-D X-ray microtomography (XMT) images displayed that the cement alteration was significantly more extensive by CO2-saturated synthetic groundwater than dry or wet supercritical CO2 at high P (10 MPa)-T (50°C) conditions. Scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) analysis also exhibited a systematic Ca depletion and C enrichment in cement matrix exposed to CO2-saturated groundwater. Integratedmore » XMT, XRD, and SEM-EDS analyses identified the formation of extensive carbonated zone filled with CaCO3(s), as well as the porous degradation front and the outermost silica-rich zone in cement after exposure to CO2-saturated groundwater. The cement alteration by CO2-saturated groundwater for 2-8 months overall decreased the porosity from 31% to 22% and the permeability by an order of magnitude. Cement alteration by dry or wet supercritical CO2 was slow and minor compared to CO2-saturated groundwater. A thin single carbonation zone was formed in cement after exposure to wet supercritical CO2 for 8 months or dry supercritical CO2 for 15 months. Extensive calcite coating was formed on the outside surface of a cement sample after exposure to wet gaseous CO2 for 1-3 months. The chemical-physical characterization of hydrated Portland cement after exposure to various phases of carbon dioxide indicates that the extent of cement carbonation can be significantly heterogeneous depending on CO2 phase present in the wellbore environment. Both experimental and geochemical modeling results suggest that wellbore cement exposure to supercritical, gaseous, and aqueous phases of CO2 during geologic carbon sequestration is unlikely to damage the wellbore integrity because cement alteration by all phases of CO2 is dominated by carbonation reaction. This is consistent with previous field studies of wellbore cement with extensive carbonation after exposure to CO2 for 3 decades. However, XMT imaging indicates that preferential cement alteration by supercritical CO2 or CO2-saturated groundwater can occur along the cement-steel or cement-rock interfaces. This highlights the importance of further investigation of cement degradation along the interfaces of wellbore materials to ensure permanent geologic carbon storage.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Kirchheim,, A. P.; Dal Molin, D.C.; Emwas, Abdul-Hamid
2010-12-01
This study details the differences in real-time hydration between pure tricalcium aluminate (cubic C{sub 3}A or 3CaO {center_dot} Al{sub 2}O{sub 3}) and Na-doped tricalcium aluminate (orthorhombic C{sub 3}A or Na{sub 2}Ca{sub 8}Al{sub 6}O{sub 18}), in aqueous solutions containing sulfate ions. Pure phases were synthesized in the laboratory to develop an independent benchmark for the reactions, meaning that their reactions during hydration in a simulated early age cement pore solution (saturated with respect to gypsum and lime) were able to be isolated. Because the rate of this reaction is extremely rapid, most microscopy methods are not adequate to study the earlymore » phases of the reactions in the early stages. Here, a high-resolution full-field soft X-ray imaging technique operating in the X-ray water window, combined with solution analysis by {sup 27}Al nuclear magnetic resonance (NMR) spectroscopy, was used to capture information regarding the mechanism of C{sub 3}A hydration during the early stages. There are differences in the hydration mechanism between the two types of C{sub 3}A, which are also dependent on the concentration of sulfate ions in the solution. The reactions with cubic C{sub 3}A (pure) seem to be more influenced by higher concentrations of sulfate ions, forming smaller ettringite needles at a slower pace than the orthorhombic C{sub 3}A (Na-doped) sample. The rate of release of aluminate species into the solution phase is also accelerated by Na doping.« less
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Formation and Restacking of Disordered Smectite Osmotic Hydrates
Gilbert, Benjamin; Comolli, Luis R.; Tinnacher, Ruth M.; ...
2015-12-01
Clay swelling, an important phenomenon in natural systems, can dramatically affect the properties of soils and sediments. Something of particular interest in low-salinity, saturated systems are osmotic hydrates, forms of smectite in which the layer separation greatly exceeds the thickness of a single smectite layer due to the intercalation of water. In situ X-ray diffraction (XRD) studies have shown a strong link between ionic strength and average interlayer spacing in osmotic hydrates but also indicate the presence of structural disorder that has not been fully described. In the present study the structural state of expanded smectite in sodium chloride solutionsmore » was investigated by combining very low electron dose, high-resolution cryogenic-transmission electron microscopy observations with XRD experiments. Wyoming smectite (SWy-2) was embedded in vitreous ice to evaluate clay structure in aqua. Lattice-fringe images showed that smectite equilibrated in aqueous, low-ionic-strength solutions, exists as individual smectite layers, osmotic hydrates composed of parallel layers, as well as disordered layer conformations. There was no evidence found here for edge-to-sheet attractions, but significant variability in interlayer spacing was observed. Whether this variation could be explained by a dependence of the magnitude of long-range cohesive (van der Waals) forces on the number of layers in a smectite particle was investigated here. Calculations of the Hamaker constant for layer-layer interactions showed that van der Waals forces may span at least five layers plus the intervening water and confirmed that forces vary with layer number. The drying of the disordered osmotic hydrates induced re-aggregation of the smectite to form particles that exhibited coherent scattering domains. Clay disaggregation and restacking may be considered as an example of oriented attachment, with the unusual distinction that it may be cycled repeatedly by changing solution conditions.« less
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Structural charge site influence on the interlayer hydration of expandable three-sheet clay minerals
Kerns, Raymond L.; Mankin, Charles J.
1968-01-01
Previous investigations have demonstrated the influences of interlayer cation composition, relative humidity, temperature, and magnitude of interlayer surface charge on the interlayer hydration of montmorillonites and vermiculites. It has been suggested that the sites of layer charge deficiencies may also have an influence upon the amount of hydration that can take place in the interlayers of expandable clay minerals. If the interlayer cation-to-layer bonds are considered as ideally electrostatic, the magnitude of the forces resisting expansion may be expressed as a form of Coulomb's law. If this effect is significant, expandable structures in which the charge-deficiency sites are predominantly in the tetrahedral sheet should have less pronounced swelling properties than should structures possessing charge deficiencies located primarily in the octahedral sheet.Three samples that differed in location of layer charge sites were selected for study. An important selection criterion was a non-correlation between tetrahedral charge sites and high surface-charge density, and between octahedral charge sites and low surface-charge density.The effects of differences in interlayer cation composition were eliminated by saturating portions of each sample with the same cations. Equilibrium (001) d values at controlled constant humidities were used as a measure of the relative degree of interlayer hydration.Although no correlation could be made between the degree of interlayer hydration and total surface-charge density, the investigation does not eliminate total surface-charge density as being significant to the swelling properties of three-sheet clay-mineral structures. The results do indicate a correlation between more intense expandability and predominance of charge deficiencies in the octahedral sheet. Conversely, less intense swelling behavior is associated with predominantly tetrahedral charge deficiencies.
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Formation and Restacking of Disordered Smectite Osmotic Hydrates
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gilbert, Benjamin; Comolli, Luis R.; Tinnacher, Ruth M.
Clay swelling, an important phenomenon in natural systems, can dramatically affect the properties of soils and sediments. Something of particular interest in low-salinity, saturated systems are osmotic hydrates, forms of smectite in which the layer separation greatly exceeds the thickness of a single smectite layer due to the intercalation of water. In situ X-ray diffraction (XRD) studies have shown a strong link between ionic strength and average interlayer spacing in osmotic hydrates but also indicate the presence of structural disorder that has not been fully described. In the present study the structural state of expanded smectite in sodium chloride solutionsmore » was investigated by combining very low electron dose, high-resolution cryogenic-transmission electron microscopy observations with XRD experiments. Wyoming smectite (SWy-2) was embedded in vitreous ice to evaluate clay structure in aqua. Lattice-fringe images showed that smectite equilibrated in aqueous, low-ionic-strength solutions, exists as individual smectite layers, osmotic hydrates composed of parallel layers, as well as disordered layer conformations. There was no evidence found here for edge-to-sheet attractions, but significant variability in interlayer spacing was observed. Whether this variation could be explained by a dependence of the magnitude of long-range cohesive (van der Waals) forces on the number of layers in a smectite particle was investigated here. Calculations of the Hamaker constant for layer-layer interactions showed that van der Waals forces may span at least five layers plus the intervening water and confirmed that forces vary with layer number. The drying of the disordered osmotic hydrates induced re-aggregation of the smectite to form particles that exhibited coherent scattering domains. Clay disaggregation and restacking may be considered as an example of oriented attachment, with the unusual distinction that it may be cycled repeatedly by changing solution conditions.« less
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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.
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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.
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Rezaee, Mohammad; Sanche, Léon; Hunting, Darel J
2013-03-01
The synergistic interaction of cisplatin with ionizing radiation is the clinical rationale for the treatment of several cancers including head and neck, cervical and lung cancer. The underlying molecular mechanism of the synergy has not yet been identified, although both DNA damage and repair processes are likely involved. Here, we investigate the indirect effect of γ rays on strand break formation in a supercoiled plasmid DNA (pGEM-3Zf-) covalently modified by cisplatin. The yields of single- and double-strand breaks were determined by irradiation of DNA and cisplatin/DNA samples with (60)Co γ rays under four different scavenging conditions to examine the involvement of hydrated electrons and hydroxyl radicals in inducing the DNA damage. At 5 mM tris in an N2 atmosphere, the presence of an average of two cisplatins per plasmid increased the yields of single- and double-strand breaks by factors of 1.9 and 2.2, respectively, relative to the irradiated unmodified DNA samples. Given that each plasmid of 3,200 base pairs contained an average of two cisplatins, this represents an increase in radiosensitivity of 3,200-fold on a per base pair basis. When hydrated electrons were scavenged by saturating the samples with N2O, these enhancement factors decreased to 1.5 and 1.2, respectively, for single- and double-strand breaks. When hydroxyl radicals were scavenged using 200 mM tris, the respective enhancement factors were 1.2 and 1.6 for single- and double-strand breaks, respectively. Furthermore, no enhancement in DNA damage by cisplatin was observed after scavenging both hydroxyl radicals and hydrated electrons. These findings show that hydrated electrons can induce both single- and double-strand breaks in the platinated DNA, but not in unmodified DNA. In addition, cisplatin modification is clearly an extremely efficient means of increasing the formation of both single- and double-strand breaks by the hydrated electrons and hydroxyl radicals created by ionizing radiation.
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NASA Astrophysics Data System (ADS)
Osegovic, J. P.; Max, M. D.
2012-12-01
Saturn's moon Enceladus appear to have liquid water under its thin icy surface that has venting water and complex hydrocarbons. Jupiter's moon Europa is locked under a very thick layer of surface ice. Because Saturn's moon Titan contains abundant hydrocarbon gasses and liquids and both Saturn and Jupiter contain abundant hydrocarbon gases, it is likely that Europa also may have significant quantities of hydrocarbon gases in their water-ice systems. Both of these moons have the potential for life. We have begun to explore the impact that gas hydrate, which is a crystalline material composed of water and gas molecules, has on the availability of liquid water on a planet's surface: what conditions need to be present to initiate hydrate formation from a primordial selection of gases, salts, and water, how isolated hydrate systems evolve under the condition of mass transfer from ex-hydrate stability conditions to pro-hydrate stability conditions, the timespan of conditions that hydrate formation can host liquid solutions in an otherwise cooling regime; and the impact that additional chemistry, such as primitive chemosynthesis, may have on the sequestered hydrocarbon gases in hydrate. The analog for gas hydrate on these moons is the Permafrost hydrate system of Earth. Gas hydrate and water ice are stable in a compound cryosphere with ice extending downward from cold surface conditions to about the 273 K isotherm. Hydrate, depending on the mixture of gases in it, is stable from some depth below the surface to some isotherm that could be considerably in excess of 273 K. Salinity may strongly affect stability conditions. In order to estimate the thickness of the gas hydrate stability zone and its effect on 'planetary' heat flow, we model heat production as a function of mass flow. Variables are gravity, ice thickness, temperature of the surrounding medium (space, ice, and water), the thickness of the "ocean", the and the thermophysical properties of the gas being transferred. The model is constrained by the molecular diffusion rate of gas approaching the hydrate phase boundary. The heat produced or consumed by the hydrate system will affect the ice system and phase boundary. Fick's law can be used to model steady state diffusion. Flux is related to the diffusivity of the component and as a function of concentration and the distance over which the reactions take place. Initial model calculations indicate that in some cases, methane (ΔH = -56 kJ/mol for small molecules (CH4, N2, CO2, H2S) may affect the water-ice energy balance sufficiently to contribute to the maintenance of a deep ocean below ice. The effect of the presence of higher density hydrocarbons (ΔH = -72 kJ/mol for ethane and -126 kJ/mol for propane) accentuate the thermal transfer effect but may diffuse too slowly to be a thermal forcing agent in the hydrate system.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Nole, Michael; Daigle, Hugh; Mohanty, Kishore
We have developed a 3D methane hydrate reservoir simulator to model marine methane hydrate systems. Our simulator couples highly nonlinear heat and mass transport equations and includes heterogeneous sedimentation, in-situ microbial methanogenesis, the influence of pore size contrast on solubility gradients, and the impact of salt exclusion from the hydrate phase on dissolved methane equilibrium in pore water. Using environmental parameters from Walker Ridge in the Gulf of Mexico, we first simulate hydrate formation in and around a thin, dipping, planar sand stratum surrounded by clay lithology as it is buried to 295mbsf. We find that with sufficient methane beingmore » supplied by organic methanogenesis in the clays, a 200x pore size contrast between clays and sands allows for a strong enough concentration gradient to significantly drop the concentration of methane hydrate in clays immediately surrounding a thin sand layer, a phenomenon that is observed in well log data. Building upon previous work, our simulations account for the increase in sand-clay solubility contrast with depth from about 1.6% near the top of the sediment column to 8.6% at depth, which leads to a progressive strengthening of the diffusive flux of methane with time. By including an exponentially decaying organic methanogenesis input to the clay lithology with depth, we see a decrease in the aqueous methane supplied to the clays surrounding the sand layer with time, which works to further enhance the contrast in hydrate saturation between the sand and surrounding clays. Significant diffusive methane transport is observed in a clay interval of about 11m above the sand layer and about 4m below it, which matches well log observations. The clay-sand pore size contrast alone is not enough to completely eliminate hydrate (as observed in logs), because the diffusive flux of aqueous methane due to a contrast in pore size occurs slower than the rate at which methane is supplied via organic methanogenesis. Therefore, it is likely that additional mechanisms are at play, notably bound water activity reduction in clays. Three-dimensionality allows for inclusion of lithologic heterogeneities, which focus fluid flow and subsequently allow for heterogeneity in the methane migration mechanisms that dominate in marine sediments at a local scale. Incorporating recently acquired 3D seismic data from Walker Ridge to inform the lithologic structure of our modeled reservoir, we show that even with deep adjective sourcing of methane along highly permeable pathways, local hydrate accumulations can be sourced either by diffusive or advective methane flux; advectively-sourced hydrates accumulate evenly in highly permeable strata, while diffusively-sourced hydrates are characterized by thin strata-bound intervals with high clay-sand pore size contrasts.« less
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NASA Astrophysics Data System (ADS)
Heeschen, Katja U.; Spangenberg, Erik; Schicks, Judith M.; Deusner, Christian; Priegnitz, Mike; Strauch, Bettina; Bigalke, Nikolaus; Luzi-Helbing, Manja; Kossel, Elke; Haeckel, Matthias; Wang, Yi
2017-04-01
Methane (CH4) hydrates are considered as a player in the field of energy supply and - if applied as such - as a possible sink for the greenhouse gas carbon dioxide (CO2). Next to the more conventional production methods depressurization and thermal stimulation, an extraction of CH4 by means of CO2 injection is investigated. The method is based on the chemical potential gradient between the CH4 hydrate phase and the injected CO2 phase. Results from small-scale laboratory experiments on the replacement method indicate recovery ratios of up to 66% CH4 but also encounter major discrepancies in conversion rates. So far it has not been demonstrated with certainty that the process rates are sufficient for an energy and cost effective production of CH4 with a concurrent sequestration of CO2. In a co-operation of GFZ and GEOMAR we used LARS (Large Scale Reservoir Simulator) to investigate the CO2-CH4-replacement method combined with thermal stimulation. LARS accommodates a sample volume of 210 l and allows for the simulation of in situ conditions typically found in gas hydrate reservoirs. Based on the sample size, diverse transport mechanisms could be simulated, which are assumed to significantly alter process yields. Temperature and pressure data complemented by a high resolution electrical resistivity tomography (ERT), gas chromatography, and flow measurements serve to interpret the experiments. In two experiments 50 kg heated CO2 was injected into sediments with CH4 hydrate saturations of 50%. While in the first experiment the CO2 was injected discontinuously in a so called "huff'n puff" manner, the second experiment saw a continuous injection. Conditions within LARS were set to 13 MPa and 8˚ C, which allow for stability of pure CO2 and CH4 hydrates as well as mixed hydrates. The CO2 was heated and entered the sediment sample with temperatures of approximately 30˚ C. In this presentation we will discuss the results from the large-scale experiments and compare them with data from small-scale experiments.
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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.
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Kinetic studies of methane-ethane mixed gas hydrates by neutron diffraction and Raman spectroscopy.
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.
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Bustos-Fierro, C; Olivera, M E; Manzo, P G; Jiménez-Kairuz, Álvaro F
2013-01-01
To evaluate the stability of an extemporaneously prepared 7% chloral hydrate syrup under different conditions of storage and dispensing. Three batches of 7% chloral hydrate syrup were prepared. Each batch was stored in 50 light-resistant glass containers of 60 mL with child-resistant caps and in two bottles of 1000 mL to simulate two forms of dispensing, mono and multi-dose, respectively. Twenty five mono-dose bottles and a multi-dose bottle of each batch were stored under room conditions (20 ± 1 °C) and the rest of the samples were stored in the fridge (5 ± 2 °C). The physical, chemical and microbiological stability was evaluated for 180 days. Stability was defined as retention of at least 95% of the initial concentration of chloral hydrate, the absence of both visible particulate matter, or color and/or odor changes and the compliance with microbiological attributes of non-sterile pharmaceutical products. At least 98% of the initial chloral hydrate concentration remained throughout the 180-day study period. There were no detectable changes in color, odor, specific gravity and pH and no visible microbial growth. These results were not affected by storage, room or refrigeration conditions or by the frequent opening or closing of the multi-dose containers. Extemporaneously compounded 7% chloral hydrate syrup was stable for at least 180 days when stored in mono or multi-dose light-resistant glass containers at room temperature and under refrigeration. Copyright © 2013 SEFH. Published by AULA MEDICA. All rights reserved.
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Optical-cell evidence for superheated ice under gas-hydrate-forming conditions
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.
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Tan, Grace; Xu, Peng; Lawson, Louise B.; He, Jibao; Freytag, Lucia C.; Clements, John D.; John, Vijay T.
2010-01-01
Although hydration is long known to improve the permeability of skin, penetration of macromolecules such as proteins is limited and the understanding of enhanced transport is based on empirical observations. This study uses high-resolution cryo-scanning electron microscopy to visualize microstructural changes in the stratum corneum (SC) and enable a mechanistic interpretation of biomacromolecule penetration through highly hydrated porcine skin. Swollen corneocytes, separation of lipid bilayers in the SC intercellular space to form cisternae, and networks of spherical particulates are observed in porcine skin tissue hydrated for a period of 4–10 h. This is explained through compaction of skin lipids when hydrated, a reversal in the conformational transition from unilamellar liposomes in lamellar granules to lamellae between keratinocytes when the SC skin barrier is initially established. Confocal microscopy studies show distinct enhancement in penetration of fluorescein isothiocyanate-bovine serum albumin (FITC-BSA) through skin hydrated for 4–10 h, and limited penetration of FITC-BSA once skin is restored to its natively hydrated structure when exposed to the environment for 2–3 h. These results demonstrate the effectiveness of a 4–10 h hydration period to enhance transcutaneous penetration of large biomacromolecules without permanently damaging the skin. PMID:19582754
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[Lipoproteins as a specific circulatory transport system].
Titov, V N
1998-01-01
In accordance with the systemic approach, each circulatory transport system is highly specific and transports an elementary substance from cell to cell in the hydrated medium. In the author's opinion, the lipoprotein system has also a functional specificity and carries the elementary substance fatty acid in the blood stream. A great variety of fatty acids, the individuality of their physicochemical properties, great stereochemic differences of saturated and polyenic fatty acids make their transport virtually impossible. The steric individuality of fatty acids can be reduced if the acids are covalently bonded by a matrix as complex lipids. For formation of complex lipids, nature prefers esterification of fatty acids with alcohols which have a varying hydrophoby, such as glycerol, sphingosine, cholesterol, cetyl alcohol. The steric differences of saturated and polyenic fatty acids form a basis for their being structurized in different lipids. Triacyl glycerides are a transport form of saturated, monounsaturated fatty acids and their transforms and give rise to a crystalline phase. Phospholipids and cholesterol esters are a transport form of mainly polyunsaturated fatty acids in the polar phase in the former case and in the crystalline phase in the latter one. The individual apolipoproteins structure complex lipids into individual lipoprotein particles and transport them in the hydrated medium of blood flow. Saturated fatty acids chiefly transport lipoprotein particles formed by apoB-48- and apoB-100-isoproteins. Polyenic acids transport mainly high-density apoA-1-lipoprotein particles, which makes up a main physiological function of the latter. Cholesterol is nothing more than a matrix; it reesterifies polyenic fatty acids from the polar transport form of phospholipids into the unpolar transport form of cholesterol esters. Cholesterol esterification of polyenic fatty acids may structure complex lipid in the unpolar phase and transport it to the cells via apoB-100-ligand-receptor interaction, which is considered to be a key stage in the multistage process of active transport to the cells of polyenic fatty acids. However, the significant differences of active and inactive transport of polyenic fatty acids in the blood stream await a separate consideration.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Ngala, V.T.; Page, C.L.; Parrott, L.J.
1995-05-01
Steady-state diffusion of dissolved oxygen and chloride ions in hydrated OPC and OPC/30%PFA pastes, hydrated for 2 weeks at 20 C and 10 weeks at 38 C, was studied at water/binder (w/s) ratios 0.4, 0.5, 0.6 and 0.7. Total porosity and a simple measure of capillary porosity, the volume fractions of the water lost in specimens from a saturated surface dry condition to a near-constant weight at 90.7% relative humidity, were also determined. The diffusion rate of chloride ions diminished markedly, to very low values, as the capillary porosity approached zero. For a given w/s ratio or capillary porosity themore » chloride ion diffusion coefficient for OPC/30%PFA pastes was about one order of magnitude smaller than that to OPC pastes. The rate of diffusion of dissolved oxygen also diminished as the capillary porosity reduced but it was still significant as the capillary porosity approached zero. For a given capillary porosity the oxygen diffusion coefficient for OPC/30%PFA pastes was about 30% smaller than that for OPC pastes. The results support the view that chloride ion diffusion in pastes of low capillary porosity is retarded by the surface charge of the hydrated cement gel. In contrast, the hydrated cement gel is much more permeable to the similarly-sized, neutral oxygen molecule.« less
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A reusable PZT transducer for monitoring initial hydration and structural health of concrete.
Yang, Yaowen; Divsholi, Bahador Sabet; Soh, Chee Kiong
2010-01-01
During the construction of a concrete structure, strength monitoring is important to ensure the safety of both personnel and the structure. Furthermore, to increase the efficiency of in situ casting or precast of concrete, determining the optimal time of demolding is important for concrete suppliers. Surface bonded lead zirconate titanate (PZT) transducers have been used for damage detection and parameter identification for various engineering structures over the last two decades. In this work, a reusable PZT transducer setup for monitoring initial hydration of concrete and structural health is developed, where a piece of PZT is bonded to an enclosure with two bolts tightened inside the holes drilled in the enclosure. An impedance analyzer is used to acquire the admittance signatures of the PZT. Root mean square deviation (RMSD) is employed to associate the change in concrete strength with changes in the PZT admittance signatures. The results show that the reusable setup is able to effectively monitor the initial hydration of concrete and the structural health. It can also be detached from the concrete for future re-use.
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A Reusable PZT Transducer for Monitoring Initial Hydration and Structural Health of Concrete
Yang, Yaowen; Divsholi, Bahador Sabet; Soh, Chee Kiong
2010-01-01
During the construction of a concrete structure, strength monitoring is important to ensure the safety of both personnel and the structure. Furthermore, to increase the efficiency of in situ casting or precast of concrete, determining the optimal time of demolding is important for concrete suppliers. Surface bonded lead zirconate titanate (PZT) transducers have been used for damage detection and parameter identification for various engineering structures over the last two decades. In this work, a reusable PZT transducer setup for monitoring initial hydration of concrete and structural health is developed, where a piece of PZT is bonded to an enclosure with two bolts tightened inside the holes drilled in the enclosure. An impedance analyzer is used to acquire the admittance signatures of the PZT. Root mean square deviation (RMSD) is employed to associate the change in concrete strength with changes in the PZT admittance signatures. The results show that the reusable setup is able to effectively monitor the initial hydration of concrete and the structural health. It can also be detached from the concrete for future re-use. PMID:22399929
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Hydrate-bearing Submarine Landslides in the Orca Basin, Gulf of Mexico
NASA Astrophysics Data System (ADS)
Sawyer, D.; Mason, A.; Cook, A.; Portnov, A.; Hillman, J.
2017-12-01
The co-occurrence of submarine landslides and hydrate-bearing sediment suggests that hydrates may play a role in landslide triggering and/or the mobility and dynamic characteristics of the submarine landslide. In turn, the removal of large sections of seafloor perturbs the hydrate stability field by removing overburden pressure and disturbing the temperature field. These potential hydrate-landslide feedbacks are not well understood. Here we combine three-dimensional seismic and petrophysical logs to characterize the deposits of submarine landslides that failed from hydrate-bearing sediments in the Orca Basin in the northern Gulf of Mexico. The Orca Basin contains a regionally mappable bottom simulating reflector, hydrate saturations within sands and muds, as well as numerous landslides. In addition, the Orca Basin features a well-known 123 km2 anoxic hypersaline brine pool that is actively being fed by outcropping salt. Lying at the bottom of the brine pool are deposits of submarine landslides. Slope instability in the Orca Basin is likely associated with near-seafloor salt tectonics. The most prominent landslide scar observable on the seafloor has a correlative deposit that now lies at the bottom of the brine pool 11.6 km away. The headwall is amphitheater-shaped with an average height of 80 meters and with only a minor amount of rubble remaining near the headwall. A total of 8.7 km3 of material was removed and deposited between the lower slopes of the basin and the base of the brine pool. Around the perimeter of the landslide headwall, two industry wells were drilled and well logs show elevated resistivity that are likely caused by gas hydrate. The slide deposits have a chaotic seismic facies with large entrained blocks and the headwall area does not retain much original material, which together suggests a relatively mobile style of landslide and therefore may have generated a wave upon impacting the brine pool. Such a slide-induced wave may have sloshed hypersaline water along the basin walls and potentially out of the confining basin. Local chemosynthetic marine communities could have been affected as they were bathed in the brine, which has been previously measured to be a factor of eight higher than normal seawater salinity.
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Formation of methane nano-bubbles during hydrate decomposition and their effect on hydrate growth.
Bagherzadeh, S Alireza; Alavi, Saman; Ripmeester, John; Englezos, Peter
2015-06-07
Molecular dynamic simulations are performed to study the conditions for methane nano-bubble formation during methane hydrate dissociation in the presence of water and a methane gas reservoir. Hydrate dissociation leads to the quick release of methane into the liquid phase which can cause methane supersaturation. If the diffusion of methane molecules out of the liquid phase is not fast enough, the methane molecules agglomerate and form bubbles. Under the conditions of our simulations, the methane-rich quasi-spherical bubbles grow to become cylindrical with a radius of ∼11 Å. The nano-bubbles remain stable for about 35 ns until they are gradually and homogeneously dispersed in the liquid phase and finally enter the gas phase reservoirs initially set up in the simulation box. We determined that the minimum mole fraction for the dissolved methane in water to form nano-bubbles is 0.044, corresponding to about 30% of hydrate phase composition (0.148). The importance of nano-bubble formation to the mechanism of methane hydrate formation, growth, and dissociation is discussed.
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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.
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X-ray Computed Tomography Observation of Methane Hydrate Dissociation
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.
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"Self-preservation" of CO(2) gas hydrates--surface microstructure and ice perfection.
Falenty, Andrzej; Kuhs, Werner F
2009-12-10
Gas hydrates can exhibit an anomalously slow decomposition outside their thermodynamic stability field; the phenomenon is called "self-preservation" and is mostly studied at ambient pressure and at temperatures between approximately 240 K and the melting point of ice. Here, we present a combination of in situ neutron diffraction studies, pVT work, and ex situ scanning electron microscopy (SEM) on CO(2) clathrates covering a much broader p-T field, stretching from 200 to 270 K and pressures between the hydrate stability limit and 0.6 kPa (6 mbar), a pressure far outside stability. The self-preservation regime above 240 K is confirmed over a broad pressure range and appears to be caused by the annealing of an ice cover formed in the initial hydrate decomposition. Another, previously unknown regime of the self-preservation exists below this temperature, extending however only over a rather narrow pressure range. In this case, the initial ice microstructure is dominated by a fast two-dimensional growth covering rapidly the clathrate surface. All observations lend strong support to the idea that the phenomenon of self-preservation is linked to the permeability of the ice cover governed by (1) the initial microstructure of ice and/or (2) the subsequent annealing of this ice coating. The interplay of the microstructure of newly formed ice and its annealing with the ongoing decomposition reaction leads to various decomposition paths and under certain conditions to a very pronounced preservation anomaly.
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Gas hydrate dissociation via in situ combustion of methane - lab studies and field tests
NASA Astrophysics Data System (ADS)
Luzi-Helbing, Manja; Schicks, Judith M.; Spangenberg, Erik; Giese, Ronny
2013-04-01
In general, three different methods for gas hydrate production are known: thermal stimulation, pressure reduction, and chemical stimulation. In the framework of the German joint project SUGAR (Submarine Gas Hydrate Reservoirs: exploration, extraction and transport) a countercurrent heat exchange reactor was developed at GFZ which has been designed to decompose gas hydrates in sediments via thermal stimulation. The heat is produced by the catalytic oxidation of methane. The advantage of this method is that the heat is generated in place i.e. within the borehole on the same level like the hydrate-bearing sediments. The system is closed which means that there is no contact between the products or catalyst and the environment. The power output and the temperature of the reactor are regulated via the volume flow of the feed gases air and methane. Therefore, the catalytic reaction runs temperature-controlled, autothermic and safe. So far, a lab-scale prototype of the reactor (outer diameter 40 mm, length 457 mm) was successfully tested in a large reservoir simulator (LARS) which was set up at GFZ. Pt, Pd and Ir on ZrO2 as carrier material turned out to be a robust and reliable catalyst. This work presents results of the latest reactor test for which LARS was filled with sand, and ca. 80 % of the pore space was saturated with methane hydrate. To form hydrates the pore pressure and the confining pressure were kept at 8 MPa and 12 MPa, respectively, and the temperature was set to 278 K. During the start sequence the reactor was ignited at room temperature with hydrogen. By the time the reactor temperature reached ca. 523 K (ca. 15 min after hydrogen ignition) the fuel flow was changed to methane. After 9 hours all temperature sensors which are spatially distributed in LARS showed a temperature above the equilibrium temperature of 282 K at 8 MPa. All in all, the reactor was run for 12 h at 723 K. The data analysis showed that 15 % of the methane gas released from hydrates would have to be used for the catalytic combustion of methane. However, only a part of the hydrate-bound methane gas could be produced during the experiment. The residual gas remained in the pore space. Currently the pilot-scale reactor is developed to a borehole tool with an outer diameter of 90 mm and ca. 5 m length. The first field test is planned for summer 2013 at the continental deep drilling KTB in Windischeschenbach, Germany. In future, we aim for a field test in hydrate-bearing sediments.
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Cisplatin intrastrand adducts sensitize DNA to base damage by hydrated electrons.
Behmand, B; Wagner, J R; Sanche, L; Hunting, D J
2014-05-08
The oligonucleotide TTTTTGTGTTT with or without a cisplatin adduct was reacted with hydrated electrons generated by ionizing radiation. Hydroxyl radicals were quenched with ethylenediaminetetraacetic acid (EDTA), and the solutions were bubbled with wet nitrogen to eliminate oxygen, a scavenger of hydrated electrons. Prior to irradiation, the structure of the initial cisplatin adduct was identified by mass spectrometry as G-cisplatin-G. Radiation damage to DNA bases was quantified by high-performance liquid chromatography (HPLC), after enzymatic digestion of the TTTTTGTGTTT-cisplatin complex to deoxyribonucleosides. The masses of the platinum adducts following digestion and separation by HPLC were measured by mass spectrometry. Our results demonstrate that hydrated electrons induce damage to thymines as well as detachment of the cisplatin moiety from both guanines in the oligonucleotide. This detachment regenerates both unmodified guanine and damaged guanine, in equimolar amounts. At 1000 Gy, a net average of 2.5 thymines and 1 guanine are damaged for each platinum lost from the oligonucleotide. Given the extensive base damage that occurs for each cisplatin adduct lost, it is clear that, prior to undergoing detachment, these adducts must catalyze several cycles of reactions of hydrated electrons with DNA bases. It is likely that a single reaction leads to the loss of the cisplatin adduct and the damage observed on the guanine base; however, the damage to the thymine bases must require the continued presence of the cisplatin adduct, acting as a catalyst. To our knowledge, this is the first time that platinum-DNA adducts have been shown to have catalytic activity. We propose two pathways for the interaction of hydrated electrons with TTTTTGTGTTT-cisplatin: (1) the hydrated electron is initially captured by a thymine base and transferred by base to base electron hopping to the guanine site, where the cisplatin moiety detaches from the oligonucleotide via dissociative electron attachment, and (2) the hydrated electron interacts directly with the platinum-guanine adduct and induces detachment of the cisplatin moiety via dissociative electron attachment. Although the precise mechanism remains to be elucidated, our results provide important insights into the radiosensitization of DNA by cisplatin.
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Cisplatin Intrastrand Adducts Sensitize DNA to Base Damage by Hydrated Electrons
Behmand, B.; Wagner, J. R.; Sanche, L.; Hunting, D. J.
2015-01-01
The oligonucleotide TTTTTGTGTTT with or without a cisplatin adduct was reacted with hydrated electrons generated by ionizing radiation. Hydroxyl radicals were quenched with ethylenediaminetetraacetic acid (EDTA), and the solutions were bubbled with wet nitrogen to eliminate oxygen, a scavenger of hydrated electrons. Prior to irradiation, the structure of the initial cisplatin adduct was identified by mass spectrometry as G-cisplatin-G. Radiation damage to DNA bases was quantified by high-performance liquid chromatography (HPLC), after enzymatic digestion of the TTTTTGTGTTT-cisplatin complex to deoxyribonucleosides. The masses of the platinum adducts following digestion and separation by HPLC were measured by mass spectrometry. Our results demonstrate that hydrated electrons induce damage to thymines as well as detachment of the cisplatin moiety from both guanines in the oligonucleotide. This detachment regenerates both unmodified guanine and damaged guanine, in equimolar amounts. At 1000 Gy, a net average of 2.5 thymines and 1 guanine are damaged for each platinum lost from the oligonucleotide. Given the extensive base damage that occurs for each cisplatin adduct lost, it is clear that, prior to undergoing detachment, these adducts must catalyze several cycles of reactions of hydrated electrons with DNA bases. It is likely that a single reaction leads to the loss of the cisplatin adduct and the damage observed on the guanine base; however, the damage to the thymine bases must require the continued presence of the cisplatin adduct, acting as a catalyst. To our knowledge, this is the first time that platinum-DNA adducts have been shown to have catalytic activity. We propose two pathways for the interaction of hydrated electrons with TTTTTGTGTTT-cisplatin: (1) the hydrated electron is initially captured by a thymine base and transferred by base to base electron hopping to the guanine site, where the cisplatin moiety detaches from the oligonucleotide via dissociative electron attachment, and (2) the hydrated electron interacts directly with the platinum-guanine adduct and induces detachment of the cisplatin moiety via dissociative electron attachment. Although the precise mechanism remains to be elucidated, our results provide important insights into the radiosensitization of DNA by cisplatin. PMID:24779712
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Association of gas hydrate formation in fluid discharges with anomalous hydrochemical profiles
NASA Astrophysics Data System (ADS)
Matveeva, T.
2009-04-01
Numerous investigations worldwide have shown that active underwater fluid discharge produces specific structures on the seafloor such as submarine seepages, vents, pockmarks, and collapse depressions. Intensive fluxes of fluids, especially of those containing hydrocarbon gases, result in specific geochemical and physical conditions favorable for gas hydrate (GH) formation. GH accumulations associated with fluid discharge are usually controlled by fluid conduits such as mud volcanoes, diapirs or faults. During last decade, subaqueous GHs become the subject of the fuel in the nearest future. However, the expediency of their commercial development can be proved solely by revealing conditions and mechanisms of GH formation. Kinetic of GH growth (although it is incompletely understood) is one of the important parameters controlling their formation among with gas solubility, pressure, temperature, gas quantity and others. Original large dataset on hydrate-related interstitial fluids obtained from different fluid discharge areas at the Sea of Okhotsk, Black Sea, Gulf of Cadiz, Lake Baikal (Eastern Siberia) allow to suggest close relation of the subaqueous GH formation process to anomalous hydrochemical profiles. We have studied the chemical and isotopic composition of interstitial fluids from GH-bearing and GH-free sediments obtained at different GH accumulations. Most attention was paid to possible influence of the interstitial fluid chemistry on the kinetic of GH formation in a porous media. The influence of salts on methane solubility within hydrate stability zones was considered by Handa (1990), Zatsepina & Buffet (1998), and later by Davie et al. (2004) from a theoretical point of view. Our idea is based on the experimentally proved fact that fugacity coefficient of methane dissolved in saline gas-saturated water which is in equilibrium with hydrates, is higher than that in more fresh water though the solubility is lower. Therefore, if a gradient of water salinity exist under conditions of hydrate stability, diffusion of methane induces hydrate formation by segregation on the outside a boundary fresher/saline water. Geochemical analysis of the interstitial fluids was used to define the mechanisms of GH accumulation and spatial distribution pattern of GHs in sediments from gas seeps abundant off NE Sakhaline Island (Sea of Okhotsk) (Matveeva et al., 2005; Mazurenko et al., submitted). A model of the ascending fluid discharge along one of the seeps named CHAOS was made based on the measured chlorinity (salinity function) of the pore waters and calculated chlorinity gradients. The chloride ion distributionprofiles with depth at the CHAOS site represent alike increasing and decreasing trends both in hydrate-bearing and hydrate-free cores. The model testifies an upward water infiltration of more saline water in vicinity of coring stations recovered GHs and relatively desalinated water mostly around those hydrate-free. It was established that GH formation at the CHAOS site is focused at the locations of intensive ascending flow of water enriched by salts that is probably function of gas solubility in water in the equilibrium with hydrate supposing that the feature is responsible for the hydrate formation just at the locations of the saline water up flows (other conditions being equal). Another case study supporting direct relation of GH formation with anomalous fluids and possible GH formation just on the interface of water flows with different salinity (defining chemical potentials of the water) is fresh-water GH accumulation at the Malenkiy fluid vent in the southern basin of Lake Baikal (Matveeva et al., 2003). The GH accumulation characterizes by heterogeneity in the spatial distribution of GH within a very small vent area. The spatial distribution of the GH-bearing and gas-saturated sediments suggests that several small fluid vents exist within the Malenkiy structure. Based on coring results, the size of these vents should not exceed a few meters. Interstitial water chemistry data indicates that water discharged within the Malenkiy vent is enriched with salts, especially Ca, Cl, and SO4 ions. The ascending water delivering gas into the GH stability zone is thought to be the main GH-forming fluid. Geochemical data suggest that the GH in the subsurface sediments of Lake Baikal originated from a deep source of water with anomalous composition assumed to be derived from buried paleolakes. As a whole, the GH accumulation corresponds to the area of the Malenkiy structure and is represented by several small scale GH occurrences coincident with local fluid discharge manifestations. The data obtained may serve as useful tool for development of geological and hydrogeochemical models of separate GH accumulations forming in the fluid discharge areas. The models on may also serve as a base for the gas inventory of the GH accumulations.
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Combined effects of lithium and borate ions on the hydration of calcium sulfoaluminate cement
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cau Dit Coumes, Céline, E-mail: celine.cau-dit-coumes@cea.fr; Dhoury, Mélanie; Champenois, Jean-Baptiste
This work investigates the combined influence of borate and lithium ions on the hydration of two calcium sulfoaluminate (CSA) cements containing 0 or 10 wt% gypsum. On the one hand, borates are known to retard CSA cement hydration due to the rapid precipitation of ulexite. On the other hand, lithium ions accelerate CSA cement hydration thanks to the fast precipitation of Li-containing aluminum hydroxide. When borates and lithium are present simultaneously, these two mechanisms are superimposed. With a gypsum-free cement, a third process is additionally observed: lithium promotes the initial precipitation of a borated AFm phase which is later convertedmore » into a borated AFt phase when hydration accelerates. Lithium salts can counteract the retardation by sodium borate. However, their influence is limited once a sufficient amount of Li-containing Al(OH){sub 3} seeds is formed. For the CSA cements under investigation, the threshold lithium concentration is close to 0.03 mmol/g of cement and similar with or without borate.« less
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A Coupled THMC model of FEBEX mock-up test
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zheng, Liange; Samper, Javier
2008-09-15
FEBEX (Full-scale Engineered Barrier EXperiment) is a demonstration and research project for the engineered barrier system (EBS) of a radioactive waste repository in granite. It includes two full-scale heating and hydration tests: the in situ test performed at Grimsel (Switzerland) and a mock-up test operating at CIEMAT facilities in Madrid (Spain). The mock-up test provides valuable insight on thermal, hydrodynamic, mechanical and chemical (THMC) behavior of EBS because its hydration is controlled better than that of in situ test in which the buffer is saturated with water from the surrounding granitic rock. Here we present a coupled THMC model ofmore » the mock-up test which accounts for thermal and chemical osmosis and bentonite swelling with a state-surface approach. The THMC model reproduces measured temperature and cumulative water inflow data. It fits also relative humidity data at the outer part of the buffer, but underestimates relative humidities near the heater. Dilution due to hydration and evaporation near the heater are the main processes controlling the concentration of conservative species while surface complexation, mineral dissolution/precipitation and cation exchanges affect significantly reactive species as well. Results of sensitivity analyses to chemical processes show that pH is mostly controlled by surface complexation while dissolved cations concentrations are controlled by cation exchange reactions.« less
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First results from experiment in South China Sea using marine controlled source electromagnetic
NASA Astrophysics Data System (ADS)
Li, Yuan; Wang, Lipeng; Deng, Ming
2016-04-01
We concentrated on the use of marine controlled-source electromagnetic (CSEM) sounding with a horizontal electric dipole source towed close to the seafloor and receivers anchored on the seafloor. We applied the CSEM method in South China Sea for the first time in 2014, which not only test the application of our instrument, but also test our data processing method. Electromagnetic fields transmitted by a towed electric dipole source in deep sea were measured by a linear array of six seafloor receivers, positioned 600 meter (m) apart. Our results provided two highly resistivity layers beneath the survey line and the gas hydrate saturation profile associated with the anomalous resistivity. In the letter, we discussed some anomalous layers during the interpretation steps. The most plausible explanation of the first resistivity layer anomalies is that large amounts of gas hydrate have accumulated at 200 m depth below the seep sites, and the second layers is considerable volumes of gas hydrate have accumulated the seafloor at survey line according to the conceptual model, during the resistivity compared with other evidence like seismic and well data from the same survey. We should try other observation like heat flow, geochemical or other evidence to test the statement in the future.
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Two Mechanisms for Methane Release at the Paleocene/Eocene Boundary
NASA Astrophysics Data System (ADS)
Katz, M. E.; Cramer, B. S.; Mountain, G. S.; Mountain, G. S.; Katz, S.; Miller, K. G.; Miller, K. G.
2001-12-01
The rapid global warming of the Paleocene/Eocene thermal maximum (PETM) has been attributed to a massive methane release from marine gas hydrate reservoirs. Two mechanisms have been proposed for this methane release. The first relies on a deepwater circulation change and water temperature increase that was sufficiently large and rapid to trigger massive thermal dissociation of gas hydrate frozen beneath the seafloor (Dickens et al., 1995). The second relies on slope failure (via erosion or seismic activity) of the oversteepened continental margins of the western North Atlantic to allow methane to escape from gas reservoirs trapped between the hydrate-bearing sediments and the underlying reef front (Katz et al., in press). We evaluate thermal dissociation by modeling heat flow through the sediments to show the effect of the temperature change on the gas hydrate stability zone through time. We use Paleocene bottom water temperatures (constrained by isotope records) and assume an instantaneous water temperature increase (i.e., no time allotted for ocean circulation change and water mass mixing). This yields an end-member minimum estimate of >2350 years necessary to melt all gas hydrate at locations shallower than 1570m; gas hydrates at greater depths remain frozen. We also use this model to predict the amount of C12-enriched methane that could have contributed to the carbon isotope excursion (CIE). Using reasonable methane distributions within sediments, we conclude that thermal dissociation alone cannot account for the full magnitude of the CIE. We propose that thermal dissociation did not initiate the CIE; rather, a different mechanism injected a large amount of carbon into the atmosphere, causing global greenhouse warming that could have led to subsequent thermal dissociation. Methane remains a plausible source for this initial carbon injection; however, initial release would have resulted from mechanical disruption of sediments rather than thermal dissociation. Seismic evidence tied to borehole data shows that methane may have been released from the U.S. continental slope in areas proximal to a buried Mesozoic reef, in contrast to the broader depth range predicted for methane release via thermal dissociation.
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Bai, Dongsheng; Zhang, Diwei; Zhang, Xianren; Chen, Guangjin
2015-01-01
Gas hydrates could show an unexpected high stability at conditions out of thermodynamic equilibrium, which is called the self-preservation effect. The mechanism of the effect for methane hydrates is here investigated via molecular dynamics simulations, in which an NVT/E method is introduced to represent different levels of heat transfer resistance. Our simulations suggest a coupling between the mass transfer resistance and heat transfer resistance as the driving mechanism for self-preservation effect. We found that the hydrate is initially melted from the interface, and then a solid-like water layer with temperature-dependent structures is formed next to the hydrate interface that exhibits fractal feature, followed by an increase of mass transfer resistance for the diffusion of methane from hydrate region. Furthermore, our results indicate that heat transfer resistance is a more fundamental factor, since it facilitates the formation of the solid-like layer and hence inhibits the further dissociation of the hydrates. The self-preservation effect is found to be enhanced with the increase of pressure and particularly the decrease of temperature. Kinetic equations based on heat balance calculations is also developed to describe the self-preservation effect, which reproduces our simulation results well and provides an association between microscopic and macroscopic properties. PMID:26423519
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Bai, Dongsheng; Zhang, Diwei; Zhang, Xianren; Chen, Guangjin
2015-10-01
Gas hydrates could show an unexpected high stability at conditions out of thermodynamic equilibrium, which is called the self-preservation effect. The mechanism of the effect for methane hydrates is here investigated via molecular dynamics simulations, in which an NVT/E method is introduced to represent different levels of heat transfer resistance. Our simulations suggest a coupling between the mass transfer resistance and heat transfer resistance as the driving mechanism for self-preservation effect. We found that the hydrate is initially melted from the interface, and then a solid-like water layer with temperature-dependent structures is formed next to the hydrate interface that exhibits fractal feature, followed by an increase of mass transfer resistance for the diffusion of methane from hydrate region. Furthermore, our results indicate that heat transfer resistance is a more fundamental factor, since it facilitates the formation of the solid-like layer and hence inhibits the further dissociation of the hydrates. The self-preservation effect is found to be enhanced with the increase of pressure and particularly the decrease of temperature. Kinetic equations based on heat balance calculations is also developed to describe the self-preservation effect, which reproduces our simulation results well and provides an association between microscopic and macroscopic properties.
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Shah, D K; Khandavilli, S; Panchagnula, R
2008-09-01
Vehicles and permeation enhancers (PEs) used in transdermal drug delivery (TDD) of a drug can affect skin hydration, integrity and permeation of the solute administered. This investigation was designed to study the effect of the most commonly used vehicles and PEs on rat skin hydration, barrier function and permeation of an amphiphilic drug, imipramine hydrochloride (IMH). An array of well-established techniques were used to confirm the findings of the study. Thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy were used to determine changes in skin hydration. Alteration of the stratum corneum (SC) structure was investigated using FTIR studies. To monitor the barrier function alteration, transepidermal water loss (TEWL) measurement and permeation studies were performed. Our findings indicate that with hydration, there was an increase in the bound water content of the skin, and pseudoequilibrium of hydration (a drastic decrease in hydration rate) was achieved at around 12 h. Hydration increased the ratio between amide-I and amide-II peaks in FTIR and reduced the C-H stretching peak area. Both propylene glycol (PG) and ethanol (EtOH) dehydrated skin, with the latter showing a predominant effect. Furthermore, it was confirmed that PG and EtOH decreased the bound water content due to alteration in the protein domains and extraction of SC lipids, respectively. The effect of hydration on the SC was found to be similar to that reported for temperature. Permeation studies revealed that the dehydration caused by vehicles decreased IMH flux, whereas the flux was enhanced by PEs. The role of partition was predominant for the permeation of IMH through dehydrated skin. A synergistic effect was observed for PG and menthol in the enhancement of IMH. Further findings provided strong evidence that PG affects protein domains and EtOH extracts lipids from the bilayer. Both PG and EtOH, with or without PEs, increased TEWL. Initial TEWL was well correlated with the flux of IMH through the same skin. It was found that both PG and EtOH affect the permeation of solute and TEWL by dehydration. The experiments also proved that the initial TEWL value has a strong potential as a predictive tool for the permeation of the solute. Copyright 2008 Prous Science, S.A.U. or its licensors. All rights reserved.
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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.
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Choi, Yoon-Seok; Nesic, Srdjan; Young, David
2010-12-01
The corrosion property of carbon steel was evaluated using an autoclave under CO(2)-saturated water phase and water-saturated CO(2) phase with impurities (O(2) and SO(2)) at 80 bar CO(2) and 50 °C to simulate the condition of CO(2) transmission pipeline in the carbon capture and storage (CCS) applications. The results showed that the corrosion rate of carbon steel in CO(2)-saturated water was very high and it increased with adding O(2) in the system due to the inhibition effect of O(2) on the formation of protective FeCO(3). It is noteworthy that corrosion took place in the water-saturated CO(2) phase under supercritical condition when no free water is present. The addition of O(2) increased the corrosion rates of carbon steel in water-saturated CO(2) phase. The addition of 0.8 bar SO(2) (1%) in the gas phase dramatically increased the corrosion rate of carbon steel from 0.38 to 5.6 mm/y. This then increased to more than 7 mm/y with addition of both O(2) and SO(2). SO(2) can promote the formation of iron sulfite hydrate (FeSO(3)·3H(2)O) on the steel surface which is less protective than iron carbonate (FeCO(3)), and it is further oxidized to become FeSO(4) and FeOOH when O(2) is present with SO(2) in the CO(2)-rich phase. The corrosion rates of 13Cr steel were very low compared with carbon steel in CO(2)-saturated water environments with O(2), whereas it was as high as carbon steel in a water-saturated CO(2) phase with O(2) and SO(2).
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Kao, Ping; Parhi, Purnendu; Krishnan, Anandi; Noh, Hyeran; Haider, Waseem; Tadigadapa, Srinivas; Allara, David L.; Vogler, Erwin A.
2010-01-01
The maximum capacity of a hydrophobic adsorbent is interpreted in terms of square or hexagonal (cubic and face-centered-cubic, FCC) interfacial packing models of adsorbed blood proteins in a way that accommodates experimental measurements by the solution-depletion method and quartz-crystal-microbalance (QCM) for the human proteins serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa). A simple analysis shows that adsorbent capacity is capped by a fixed mass/volume (e.g. mg/mL) surface-region (interphase) concentration and not molar concentration. Nearly analytical agreement between the packing models and experiment suggests that, at surface saturation, above-mentioned proteins assemble within the interphase in a manner that approximates a well-ordered array. HSA saturates a hydrophobic adsorbent with the equivalent of a single square-or-hexagonally-packed layer of hydrated molecules whereas the larger proteins occupy two-or-more layers, depending on the specific protein under consideration and analytical method used to measure adsorbate mass (solution depletion or QCM). Square-or-hexagonal (cubic and FCC) packing models cannot be clearly distinguished by comparison to experimental data. QCM measurement of adsorbent capacity is shown to be significantly different than that measured by solution depletion for similar hydrophobic adsorbents. The underlying reason is traced to the fact that QCM measures contribution of both core protein, water of hydration, and interphase water whereas solution depletion measures only the contribution of core protein. It is further shown that thickness of the interphase directly measured by QCM systematically exceeds that inferred from solution-depletion measurements, presumably because the static model used to interpret solution depletion does not accurately capture the complexities of the viscoelastic interfacial environment probed by QCM. PMID:21035180
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Kao, Ping; Parhi, Purnendu; Krishnan, Anandi; Noh, Hyeran; Haider, Waseem; Tadigadapa, Srinivas; Allara, David L; Vogler, Erwin A
2011-02-01
The maximum capacity of a hydrophobic adsorbent is interpreted in terms of square or hexagonal (cubic and face-centered-cubic, FCC) interfacial packing models of adsorbed blood proteins in a way that accommodates experimental measurements by the solution-depletion method and quartz-crystal-microbalance (QCM) for the human proteins serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa). A simple analysis shows that adsorbent capacity is capped by a fixed mass/volume (e.g. mg/mL) surface-region (interphase) concentration and not molar concentration. Nearly analytical agreement between the packing models and experiment suggests that, at surface saturation, above-mentioned proteins assemble within the interphase in a manner that approximates a well-ordered array. HSA saturates a hydrophobic adsorbent with the equivalent of a single square or hexagonally-packed layer of hydrated molecules whereas the larger proteins occupy two-or-more layers, depending on the specific protein under consideration and analytical method used to measure adsorbate mass (solution depletion or QCM). Square or hexagonal (cubic and FCC) packing models cannot be clearly distinguished by comparison to experimental data. QCM measurement of adsorbent capacity is shown to be significantly different than that measured by solution depletion for similar hydrophobic adsorbents. The underlying reason is traced to the fact that QCM measures contribution of both core protein, water of hydration, and interphase water whereas solution depletion measures only the contribution of core protein. It is further shown that thickness of the interphase directly measured by QCM systematically exceeds that inferred from solution-depletion measurements, presumably because the static model used to interpret solution depletion does not accurately capture the complexities of the viscoelastic interfacial environment probed by QCM. Copyright © 2010 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Dessirier, B.; Frampton, A.; Fransson, À.; Jarsjö, J.
2016-08-01
The repository concept for geological disposal of spent nuclear fuel in Sweden and Finland is planned to be constructed in sparsely fractured crystalline bedrock and with an engineered bentonite buffer to embed the waste canisters. An important stage in such a deep repository is the postclosure phase following the deposition and the backfilling operations when the initially unsaturated buffer material gets hydrated by the groundwater delivered by the natural bedrock. We use numerical simulations to interpret observations on buffer wetting gathered during an in situ campaign, the Bentonite Rock Interaction Experiment, in which unsaturated bentonite columns were introduced into deposition holes in the floor of a 417 m deep tunnel at the Äspö Hard Rock Laboratory in Sweden. Our objectives are to assess the performance of state-of-the-art flow models in reproducing the buffer wetting process and to investigate to which extent dependable predictions of buffer wetting times and saturation patterns can be made based on information collected prior to buffer insertion. This would be important for preventing insertion into unsuitable bedrock environments. Field data and modeling results indicate the development of a de-saturated zone in the rock and show that in most cases, the presence or absence of fractures and flow heterogeneity are more important factors for correct wetting predictions than the total inflow. For instance, for an equal open-hole inflow value, homogeneous inflow yields much more rapid buffer wetting than cases where fractures are represented explicitly thus creating heterogeneous inflow distributions.
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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
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Hydration products and thermokinetic properties of cement-bentonite and cement-chalk mortars
DOE Office of Scientific and Technical Information (OSTI.GOV)
Klyusov, A.A.
1988-08-20
Bentonite and chalk are the most popular auxiliary additives to portland cement for borehole cementation. The authors studied by physicochemical analysis methods (x-ray phase, derivatographic, and scanning and electron microscopy in combination with microdiffraction) the newly formed solid-phase composition of cement-bentonite and cement-chalk mortars (binder-additive ratio 9:1) prepared from portland cement for cold boreholes and 8% calcium chloride solution at a water-mixing ratio of 0.9. The mechanism of the influence of Ca-bentonite and chalk additives on the portland cement hydration rate was ascertained from the heat evolution rate curves. It was found that the phase compositions of the hydration productsmore » are represented in the studied systems by newly formed substances typical for portland cement. It has been noted that Ca-bentonite interacts with the calcium hydroxide of hydrated cement with the formation of hexagonal and cubic calcium hydroaluminates. Unlike Ca-bentonite, chalk does not react with portland cement at normal and reduced temperatures, does not block hydrated cement particles, which, in turn, ensures all other conditions remaining equal, a higher initial rate of hydration of cement-chalk mortar.« less
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NASA Astrophysics Data System (ADS)
Talaghat, Mohammad Reza; Jokar, Seyyed Mohammad
2018-03-01
The induction time is a time interval to detect the initial hydrate formation, which is counted from the moment when the stirrer is turned on until the first detection of hydrate formation. The main objective of the present work is to predict and measure the induction time of methane hydrate formation in the presence or absence of tetrahydrofuran (THF) as promoter in the flow loop system. A laboratory flow mini-loop apparatus was set up to measure the induction time of methane hydrate formation. The induction time is predicted using developed Kashchiev and Firoozabadi model and modified model of Natarajan for a flow loop system. Furthermore, the effects of volumetric flow rate of the fluid on the induction time were investigated. The results of the models were compared with experimental data. They show that the induction time of hydrate formation in the presence of THF is very short at high pressure and high volumetric flow rate of the fluid. It decreases with increasing pressure and liquid volumetric flow rate. It is also shown that the modified Natarajan model is more accurate than the Kashchiev and Firoozabadi ones in prediction of the induction time.
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Boyd, Glen R; Ocampo-Gómez, Ana M; Li, Minghua; Husserl, Johana
2006-11-20
Packed column experiments were conducted to study effects of initial saturation of tetrachloroethene (PCE) in the range of 1.0-14% pore volume (PV) on mobilization and downward migration of the non-aqueous phase liquid (NAPL) product upon contact with aqueous isobutanol ( approximately 10 vol.%). This study focused on the consequences of swelling beyond residual saturation. Columns were packed with mixtures of neat PCE, water and glass beads and waterflooded to establish a desired homogeneous residual saturation, and then flooded with aqueous isobutanol under controlled hydraulic conditions. Results showed a critical saturation of approximately 8% PV for these packed column experimental conditions. At low initial PCE saturations (<8% PV), experimental results showed reduced risk of NAPL-product migration upon contact with aqueous isobutanol. At higher initial PCE saturations (>8% PV), results showed NAPL-product mobilization and downward migration which was attributed to interfacial tension (IFT) reduction, swelling of the NAPL-product, and reduced density modification. Packed column results were compared with good agreement to theoretical predictions of NAPL-product mobilization using the total trapping number, N(T). In addition to the packed column study, preliminary batch experiments were conducted to study the effects of PCE volumetric fraction in the range of 0.5-20% on density, viscosity, and IFT modification as a function of time following contact with aqueous isobutanol ( approximately 10 vol.%). Modified NAPL-product fluid properties approached equilibrium within approximately 2 h of contact for density and viscosity. IFT reduction occurred immediately as expected. Measured fluid properties were compared with good agreement to theoretical equilibrium predictions based on UNIQUAC. Overall, this study demonstrates the importance of initial DNAPL saturation, and the associated risk of downward NAPL-product migration, in applying alcohol flooding for remediation of DNAPL contaminated ground water sites.
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Radiation hardening of low condensation products containing amino group (in Japanese)
DOE Office of Scientific and Technical Information (OSTI.GOV)
Okamura, S.; Hayashi, K.; Kaetsu, I.
1967-11-01
An initial condensation product is prepared by condensing a monomer selected from the group of urea, thiourea, melanine, aniline and acidamide with formalin. 0ne or more of the initial condensation product is then mixed with a substance which forms an acid or base by irradiation with an ionizing radiation in the presence or absence of the initial condensation product, except for halogenated hydrocarbon. The mixture is hardened by irradiation of the ionizing radiation to form a resinous substance. Formamide, acetamide, oxalic diamide, succinic diamide, acrylamide, etc. can be used as the acidamide monomer. Phosphonitrile chloride, cyanuric chloride, chloral hydrate, trichloroaceticmore » acid, monochloroacetic acid, ammonium chloride, aluminium chloride, gaseous chlorine, sullurous acid gas, sodium sulfite, aluminium sulfate, potassium hydrogensulfate, sodium pyrophosphate, potassium pyrophosphate, potassium phosphate, ammonia, bromine, bromal, bromal hydrate, dibromoacetic acid, sulfonated benzene, sulfonated toluene, etc. can be used as the acid- or base- forming substance. To the initial condensation product may be added 0.5-20%, in certain cases 20-50%, by weight of the said substances. The ionizing radiation can be electron beams. In an example, 2% chloral hydrate was homogeneously dissolved in the initial urea-formalin condensation product having a degree of condensation of 3--5. The solution was then irradiated by gamma rays at the dose rate of 4 x 10/sup 4/ r/hour from a /sup 60/Co source with a dose 5.0 x 10/sup 6/ roentgens. A white resinous composition was obtained. (JA)« less
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Solid-support substrates for plant growth at a lunar base
NASA Technical Reports Server (NTRS)
Ming, D. W.; Galindo, C.; Henninger, D. L.
1990-01-01
Zeoponics is only in its developmental stages at the Johnson Space Center and is defined as the cultivation of plants in zeolite substrates that contain several essential plant growth cations on their exchange sites, and have minor amounts of mineral phases and/or anion-exchange resins that supply essential plant growth anions. Zeolites are hydrated aluminosilicates of alkali and alkaline earth cations with the ability to exchange most of their constituent exchange cations as well as hydrate/dehydrate without change to their structural framework. Because zeolites have extremely high cation exchange capabilities, they are very attractive media for plant growth. It is possible to partially or fully saturate plant-essential cations on zeolites. Zeoponic systems will probably have their greatest applications at planetary bases (e.g., lunar bases). Lunar raw materials will have to be located that are suited for the synthesis of zeolites and other exchange resings. Lunar 'soil' simulants have been or are being prepared for zeolite/smectite synthesis and 'soil' dissolution studies.
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NASA Astrophysics Data System (ADS)
Shevkunov, S. V.
2017-11-01
The mean force potential (MFP) of interaction between counterions Na+ and Cl- in a planar nanopore with structureless hydrophobic walls is calculated via computer simulation under the condition that the nanopore is in contact with water at an external pressure that exceeds the saturation pressure but remains insufficient to fill the nanopore with water. For a nanopore with a liquid phase, the MFP dependence on the interionic distance indicates the dissociation of an ion pair into two hydrated ions in a nanopore that is not completely filled with water. Fluctuations in the number of water molecules drawn into the interionic space decisively influence the dissociation. The attraction between counterions, averaged over thermal fluctuations, depends largely on the pore width and grows as the shielding of the ions' electric field by water molecules in a narrow pore diminishes. The contributions from energy and entropy to the free energy of hydration are analyzed.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Loring, John S.; Schaef, Herbert T.; Turcu, Romulus VF
2012-04-25
The interaction of anhydrous supercritical CO2 (scCO2) with both kaolinite and ~1W (i.e. close to but less than one layer of hydration) calcium-saturated montmorillonite was investigated under conditions relevant to geologic carbon sequestration (50 °C and 90 bar). The CO2 molecular environment was probed in situ using a combination of three novel high-pressure techniques: X-ray diffraction, magic angle spinning nuclear magnetic resonance spectroscopy and attenuated total reflection infrared spectroscopy. We report the first direct evidence that the expansion of montmorillonite under scCO2 conditions is due to CO2 migration into the interlayer. Intercalated CO2 molecules are rotationally constrained and do notmore » appear to react with waters to form bicarbonate or carbonic acid. In contrast, CO2 does not intercalate into kaolinite. The findings show that predicting the seal integrity of caprock will have complex dependence on clay mineralogy and hydration state.« less
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NASA Astrophysics Data System (ADS)
Bowles, J. A.; Patiman, A.
2017-12-01
The recorded geomagnetic field intensity is a function of magnetic mineralogy, grain size, and mineral concentration as well as material stability in nature and during laboratory experiments. Fresh, unhydrated, volcanic glasses are recognized as a nearly ideal natural material for use in paleointensity experiments because they contain the requisite single domain to pseudo-single-domain magnetic particles. Although alteration of magnetic mineralogy can be monitored during the experiments, it is unclear how mineralogy and hence magnetization might change with age as the metastable glass structure relaxes and/or the glass becomes hydrated. Bulk magnetic properties as a function of age show no clear trend, even over hundreds of millions of years. This may be due to the fact that even in fresh, unhydrated glass, there are small-scale differences in magnetic properties due to variation cooling rate or composition variations. Therefore, in order to better understand how magnetic mineralogy evolves with time and hydration, we conducted artificial aging and hydration experiments on fresh, unhydrated rhyolitic (South Deadman Creek, California, 650-yr) and basaltic (Axial Seamount, 2011) end-member glasses. Here, we present the results of artificial aging and hydration experiments. Elevated temperatures accelerate the glass relaxation process in a way that relaxation time decreases with increasing temperature. Aged samples are dry-annealed at 200, 300 and 400 °C for up to 240 days. A second set of samples are hydrated under pressure at 300°C and 450°C. In all cases, isothermal remanent magnetization (IRM) acquisition is monitored to assess changes in the coercivity spectrum and saturation IRM. Preliminary aging results show that in basaltic and rhyolitic glass there is one main peak coercivity at 150 mT and 35 mT, respectively. An increasing sIRM and decreasing peak coercivity trend is observed in basaltic glass whereas no trend is shown in the rhyolitic glass in both parameters after 60 days for all three temperatures in aging experiment. This could be caused by the coarsening of the existing magnetic grains as the glass structure relaxes during aging. We tentatively conclude that one should be cautious with using older glassy samples in absolute paleointensity experiments.
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Forecasting Ocean Acidification in the coastal waters of the Pacific Northwest
NASA Astrophysics Data System (ADS)
Siedlecki, S. A.; Alin, S. R.; Feely, R. A.; Hermann, A. J.; Bednarsek, N.; Nguyen, T.; Officer, S.; Kaplan, I.; Bond, N.; Newton, J.; Fisher, J. L.; Morgan, C.; Saenger, C.
2016-12-01
The co-occurrence of submarine landslides and hydrate-bearing sediment suggests that hydrates may play a role in landslide triggering and/or the mobility and dynamic characteristics of the submarine landslide. In turn, the removal of large sections of seafloor perturbs the hydrate stability field by removing overburden pressure and disturbing the temperature field. These potential hydrate-landslide feedbacks are not well understood. Here we combine three-dimensional seismic and petrophysical logs to characterize the deposits of submarine landslides that failed from hydrate-bearing sediments in the Orca Basin in the northern Gulf of Mexico. The Orca Basin contains a regionally mappable bottom simulating reflector, hydrate saturations within sands and muds, as well as numerous landslides. In addition, the Orca Basin features a well-known 123 km2 anoxic hypersaline brine pool that is actively being fed by outcropping salt. Lying at the bottom of the brine pool are deposits of submarine landslides. Slope instability in the Orca Basin is likely associated with near-seafloor salt tectonics. The most prominent landslide scar observable on the seafloor has a correlative deposit that now lies at the bottom of the brine pool 11.6 km away. The headwall is amphitheater-shaped with an average height of 80 meters and with only a minor amount of rubble remaining near the headwall. A total of 8.7 km3 of material was removed and deposited between the lower slopes of the basin and the base of the brine pool. Around the perimeter of the landslide headwall, two industry wells were drilled and well logs show elevated resistivity that are likely caused by gas hydrate. The slide deposits have a chaotic seismic facies with large entrained blocks and the headwall area does not retain much original material, which together suggests a relatively mobile style of landslide and therefore may have generated a wave upon impacting the brine pool. Such a slide-induced wave may have sloshed hypersaline water along the basin walls and potentially out of the confining basin. Local chemosynthetic marine communities could have been affected as they were bathed in the brine, which has been previously measured to be a factor of eight higher than normal seawater salinity.
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Salt exclusion in silane-laced epoxy coatings.
Wang, Peng; Schaefer, Dale W
2010-01-05
The corrosion protection mechanism of a one-step silane-laced epoxy coating system was investigated using neutron reflectivity. Pure epoxy and silane-laced epoxy films were examined at equilibrium with saturated NaCl water solution. The results demonstrate that the addition of silane introduces a salt-exclusion effect to epoxy coating. Specifically, the addition of silane densifies the epoxy network, which leads to exclusion of hydrated salt ions by a size effect. The effect is particularly significant at the metal-coating interface. Exclusion of ions improves the corrosion resistance, particularly for metals susceptible to pitting.
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NASA Astrophysics Data System (ADS)
Yamamoto, K.; Dallimore, S. R.; Numasawa, M.; Yasuda, M.; Fujii, T.; Fujii, K.; Wright, J.; Nixon, F.
2007-12-01
Japan Oil, Gas and Metals National Corporation (JOGMEC) and Natural Resource Canada (NRCan) have embarked on a new research program to study the production potential of gas hydrates. The program is being carried out at the Mallik gas hydrate field in the Mackenzie Delta, a location where two previous scientific investigations have been carried in 1998 and 2002. In the 2002 program that was undertaken by seven partners from five countries, 468m3 of gas flow was measured during 124 hours of thermal stimulation using hot warm fluid. Small-scale pressure drawdown tests were also carried out using Schlumberger's Modular Dynamics Tester (MDT) wireline tool, gas flow was observed and the inferred formation permeabilities suggested the possible effectiveness of the simple depressurization method. While the testing undertaken in 2002 can be cited as the first well constrained gas production from a gas hydrate deposit, the results fell short of that required to fully calibrate reservoir simulation models or indeed establish the technical viability of long term production from gas hydrates. The objectives of the current JOGMEC/NRCan/Aurora Mallik production research program are to undertake longer term production testing to further constrain the scientific unknowns and to demonstrate the technical feasibility of sustained gas hydrate production using the depressurization method. A key priority is to accurately measure water and gas production using state-of-art production technologies. The primary production test well was established during the 2007 field season with the re-entry and deepening of JAPEX/JNOC/GSC Mallik 2L-38 well, originally drilled in 1998. Production testing was carried out in April of 2007 under a relatively low drawdown pressure condition. Flow of methane gas was measured from a 12m perforated interval of gas-hydrate-saturated sands from 1093 to 1105m. The results establish the potential of the depressurization method and provide a basis for future prolonged testing planned in the near future. The authors acknowledge the Research Consortium for Methane Hydrate Resources in Japan (MH21), the Ministry of Economy, Trade and Industry (METI) and NRCan for the support and funding. The Mallik 2002 program was undertaken jointly by JNOC, NRCan, GeoForschungsZentrum Potsdam (GFZ), the United State Geological Survey (USGS), the United States Department of Energy (USDOE), the India Ministry of Petroleum and Natural Gas (MOPNG)-Gas Authority of India (GAIL), and the BP-Chevron Texaco Mackenzie Delta Joint Venture.
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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.
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Cracking and reformation of saturated hydrocarbons by ultrasound in the presence of water
NASA Technical Reports Server (NTRS)
Prudhomme, M. R. O.; Lefort, J.
1974-01-01
The exposure of saturated hydrocarbons to ultrasound (800 kHz, 6 W/sq cm) in the presence of water results in: (1) cleavage of the carbon chain, producing saturated and unsaturated hydrocarbons with a lower number of carbons than the initial hydrocarbon (cracking); and (2) recombination after cleavage, producing saturated and unsaturated hydrocarbons with a higher number of carbons than the initial hydrocarbon (reformation). The addition of argon facilitates these phenomena. The effects are attributed to a homolytic (radical) mechanism occurring within the cavitation bubbles under the effects of microsparks.
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The character and amplitude of ‘discontinuous’ bottom-simulating reflections in marine seismic data
Hillman, Jess I. T.; Cook, Ann E.; Sawyer, Derek E.; ...
2016-11-22
Bottom-simulating reflections (BSRs) identified in seismic data are well documented; and are commonly interpreted to indicate the presence of gas hydrates along continental margins, as well as to estimate regional volumes of gas hydrate. A BSR is defined as a reflection that sub-parallels the seafloor but is opposite in polarity and cross-cuts dipping sedimentary strata. BSRs form as a result of a strong negative acoustic impedance contrast. BSRs, however, are a diverse seismic phenomena that manifest in strikingly contrasting ways in different geological settings, and in different seismic data types. We investigate the characteristics of BSRs, using conventional and highmore » resolution, 2D and 3D seismic data sets in three locations: the Terrebonne and Orca Basins in the Gulf of Mexico, and Blake Ridge on the US Atlantic Margin. The acquisition geometry and frequency content of the seismic data significantly impact the resultant character of BSRs, as observed with depth and amplitude maps of the BSRs. Furthermore, our amplitude maps reinforce the concept that the BSR represents a zone, over which the transition from hydrate to free gas occurs, as opposed to the conventional model of the BSR occurring at a single interface. Our results show that a BSR can be mapped in three dimensions but it is not spatially continuous, at least not at the basin scale. Rather, a BSR manifests itself as a discontinuous, or patchy, reflection and only at local scales is it continuous. We suggest the discontinuous nature of BSRs is the result of variable saturation and distribution of free gas and hydrate, acquisition geometry and frequency content of the recorded seismic data. Lastly, the commonly accepted definition of a BSR should be broadened with careful consideration of these factors, to represent the uppermost extent of enhanced amplitude at the shallowest occurrence of free gas trapped by overlying hydrate-bearing sediments.« less
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Hydrogen speciation in hydrated layers on nuclear waste glass
DOE Office of Scientific and Technical Information (OSTI.GOV)
Aines, R.D.; Weed, H.C.; Bates, J.K.
1987-01-15
The hydration of an outer layer on nuclear waste glasses is known to occur during leaching, but the actual speciation of hydrogen (as water or hydroxyl groups) in these layers has not been determined. As part of the Nevada Nuclear Waste Storage Investigations Project, we have used infrared spectroscopy to determine hydrogen speciations in three nuclear waste glass compositions (SRL-131 & 165, and PNL 76-68), which were leached at 90{sup 0}C (all glasses) or hydrated in a vapor-saturated atmosphere at 202{sup 0}C (SRL-131 only). Hydroxyl groups were found in the surface layers of all the glasses. Molecular water was foundmore » in the surface of SRL-131 and PNL 76-68 glasses that had been leached for several months in deionized water, and in the vapor-hydrated sample. The water/hydroxyl ratio increases with increasing reaction time; molecular water makes up most of the hydrogen in the thick reaction layers on vapor-phase hydrated glass while only hydroxyl occurs in the least reacted samples. Using the known molar absorptivities of water and hydroxyl in silica-rich glass the vapor-phase layer contained 4.8 moles/liter of molecular water, and 0.6 moles water in the form hydroxyl. A 15 {mu}m layer on SRL-131 glass formed by leaching at 90{sup 0}C contained a total of 4.9 moles/liter of water, 2/3 of which was as hydroxyl. The unreacted bulk glass contains about 0.018 moles/liter water, all as hydroxyl. The amount of hydrogen added to the SRL-131 glass was about 70% of the original Na + Li content, not the 300% that would result from alkali=hydronium ion interdiffusion. If all the hydrogen is then assumed to be added as the result of alkali-H{sup +} interdiffusion, the molecular water observed may have formed from condensation of the original hydroxyl groups.« less
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The character and amplitude of 'discontinuous' bottom-simulating reflections in marine seismic data
NASA Astrophysics Data System (ADS)
Hillman, Jess I. T.; Cook, Ann E.; Sawyer, Derek E.; Küçük, H. Mert; Goldberg, David S.
2017-02-01
Bottom-simulating reflections (BSRs) identified in seismic data are well documented; and are commonly interpreted to indicate the presence of gas hydrates along continental margins, as well as to estimate regional volumes of gas hydrate. A BSR is defined as a reflection that sub-parallels the seafloor but is opposite in polarity and cross-cuts dipping sedimentary strata. BSRs form as a result of a strong negative acoustic impedance contrast. BSRs, however, are a diverse seismic phenomena that manifest in strikingly contrasting ways in different geological settings, and in different seismic data types. We investigate the characteristics of BSRs, using conventional and high resolution, 2D and 3D seismic data sets in three locations: the Terrebonne and Orca Basins in the Gulf of Mexico, and Blake Ridge on the US Atlantic Margin. The acquisition geometry and frequency content of the seismic data significantly impact the resultant character of BSRs, as observed with depth and amplitude maps of the BSRs. Furthermore, our amplitude maps reinforce the concept that the BSR represents a zone, over which the transition from hydrate to free gas occurs, as opposed to the conventional model of the BSR occurring at a single interface. Our results show that a BSR can be mapped in three dimensions but it is not spatially continuous, at least not at the basin scale. Rather, a BSR manifests itself as a discontinuous, or patchy, reflection and only at local scales is it continuous. We suggest the discontinuous nature of BSRs is the result of variable saturation and distribution of free gas and hydrate, acquisition geometry and frequency content of the recorded seismic data. The commonly accepted definition of a BSR should be broadened with careful consideration of these factors, to represent the uppermost extent of enhanced amplitude at the shallowest occurrence of free gas trapped by overlying hydrate-bearing sediments.
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NASA Astrophysics Data System (ADS)
Gehrmann, R. A. S.; Schwalenberg, K.; Hölz, S.; Zander, T.; Dettmer, J.; Bialas, J.
2016-12-01
In 2014 an interdisciplinary survey was conducted as part of the German SUGAR project in the Western Black Sea targeting gas hydrate occurrences in the Danube Delta. Marine controlled source electromagnetic (CSEM) data were acquired with an inline seafloor-towed array (BGR), and a two-polarization horizontal ocean-bottom source and receiver configuration (GEOMAR). The CSEM data are co-located with high-resolution 2-D and 3-D seismic reflection data (GEOMAR). We present results from 2-D regularized inversion (MARE2DEM by Kerry Key), which provides a smooth model of the electrical resistivity distribution beneath the source and multiple receivers. The 2-D approach includes seafloor topography and structural constraints from seismic data. We estimate uncertainties from the regularized inversion and compare them to 1-D Bayesian inversion results. The probabilistic inversion for a layered subsurface treats the parameter values and the number of layers as unknown by applying reversible-jump Markov-chain Monte Carlo sampling. A non-diagonal data covariance matrix obtained from residual error analysis accounts for correlated errors. The resulting resistivity models show generally high resistivity values between 3 and 10 Ωm on average which can be partly attributed to depleted pore water salinities due to sea-level low stands in the past, and locally up to 30 Ωm which is likely caused by gas hydrates. At the base of the gas hydrate stability zone resistivities rise up to more than 100 Ωm which could be due to gas hydrate as well as a layer of free gas underneath. However, the deeper parts also show the largest model parameter uncertainties. Archie's Law is used to derive estimates of the gas hydrate saturation, which vary between 30 and 80% within the anomalous layers considering salinity and porosity profiles from a distant DSDP bore hole.
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Haines, Seth S.; Hart, Patrick E.; Collett, Timothy S.; Shedd, William; Frye, Matthew; Weimer, Paul; Boswell, Ray
2017-01-01
The Pliocene and Pleistocene sediments at lease block Green Canyon 955 (GC955) in the Gulf of Mexico include sand-rich strata with high saturations of gas hydrate; these gas hydrate accumulations and the associated geology have been characterized over the past decade using conventional industry three-dimensional (3D) seismic data and dedicated logging-while-drilling (LWD) borehole data. To improve structural and stratigraphic characterization and to address questions of gas flow and reservoir properties, in 2013 the U.S. Geological Survey acquired high-resolution two-dimensional (2D) seismic data at GC955. Combined analysis of all available data improves our understanding of the geological evolution of the study area, which includes basin-scale migration of the Mississippi River sediment influx as well as local-scale shifting of sedimentary channels at GC955 in response to salt-driven uplift, structural deformation associated with the salt uplift, and upward gas migration from deeper sediments that charges the main gas hydrate reservoir and shallower strata. The 2D data confirm that the sand-rich reservoir is composed principally of sediments deposited in a proximal levee setting and that episodes of channel scour, interspersed with levee deposition, have resulted in an assemblage of many individual proximal levee deposit “pods” each with horizontal extent up to several hundred meters. Joint analysis of the 2D and 3D data reveals new detail of a complex fault network that controls the fluid-flow system; large east-west trending normal faults allow fluid flow through the reservoir-sealing fine-grained unit, and smaller north-south oriented faults provide focused fluid-flow pathways (chimneys) through the shallower sediments. This system has enabled the flow of gas from the main reservoir to the seafloor throughout the recent history at GC955, and its intricacies help explain the distributed occurrences of gas hydrate in the intervening strata.
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The character and amplitude of ‘discontinuous’ bottom-simulating reflections in marine seismic data
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hillman, Jess I. T.; Cook, Ann E.; Sawyer, Derek E.
Bottom-simulating reflections (BSRs) identified in seismic data are well documented; and are commonly interpreted to indicate the presence of gas hydrates along continental margins, as well as to estimate regional volumes of gas hydrate. A BSR is defined as a reflection that sub-parallels the seafloor but is opposite in polarity and cross-cuts dipping sedimentary strata. BSRs form as a result of a strong negative acoustic impedance contrast. BSRs, however, are a diverse seismic phenomena that manifest in strikingly contrasting ways in different geological settings, and in different seismic data types. We investigate the characteristics of BSRs, using conventional and highmore » resolution, 2D and 3D seismic data sets in three locations: the Terrebonne and Orca Basins in the Gulf of Mexico, and Blake Ridge on the US Atlantic Margin. The acquisition geometry and frequency content of the seismic data significantly impact the resultant character of BSRs, as observed with depth and amplitude maps of the BSRs. Furthermore, our amplitude maps reinforce the concept that the BSR represents a zone, over which the transition from hydrate to free gas occurs, as opposed to the conventional model of the BSR occurring at a single interface. Our results show that a BSR can be mapped in three dimensions but it is not spatially continuous, at least not at the basin scale. Rather, a BSR manifests itself as a discontinuous, or patchy, reflection and only at local scales is it continuous. We suggest the discontinuous nature of BSRs is the result of variable saturation and distribution of free gas and hydrate, acquisition geometry and frequency content of the recorded seismic data. Lastly, the commonly accepted definition of a BSR should be broadened with careful consideration of these factors, to represent the uppermost extent of enhanced amplitude at the shallowest occurrence of free gas trapped by overlying hydrate-bearing sediments.« less
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Simulation of water-table aquifers using specified saturated thickness
Sheets, Rodney A.; Hill, Mary C.; Haitjema, Henk M.; Provost, Alden M.; Masterson, John P.
2014-01-01
Simulating groundwater flow in a water-table (unconfined) aquifer can be difficult because the saturated thickness available for flow depends on model-calculated hydraulic heads. It is often possible to realize substantial time savings and still obtain accurate head and flow solutions by specifying an approximate saturated thickness a priori, thus linearizing this aspect of the model. This specified-thickness approximation often relies on the use of the “confined” option in numerical models, which has led to confusion and criticism of the method. This article reviews the theoretical basis for the specified-thickness approximation, derives an error analysis for relatively ideal problems, and illustrates the utility of the approximation with a complex test problem. In the transient version of our complex test problem, the specified-thickness approximation produced maximum errors in computed drawdown of about 4% of initial aquifer saturated thickness even when maximum drawdowns were nearly 20% of initial saturated thickness. In the final steady-state version, the approximation produced maximum errors in computed drawdown of about 20% of initial aquifer saturated thickness (mean errors of about 5%) when maximum drawdowns were about 35% of initial saturated thickness. In early phases of model development, such as during initial model calibration efforts, the specified-thickness approximation can be a very effective tool to facilitate convergence. The reduced execution time and increased stability obtained through the approximation can be especially useful when many model runs are required, such as during inverse model calibration, sensitivity and uncertainty analyses, multimodel analysis, and development of optimal resource management scenarios.
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Naval Research Laboratory Arctic Initiatives
2011-06-01
Campaign Code 7420 Arctic Modeling Code 7320/7500/7600 In-situ NRL, CRREL NRL boreholes Strategy Remote Sensing Synergism −Collect in-situ...Navy and Marine Corps Corporate Laboratory An array of BMFCs being prepared for deployment. Each BMFC consists of a weighted anode laid flat onto...Gas CH4 E C D CO2 BGHS Free Methane Gas Hydrates HCO3- HCO3- Seismic and geochemical data to predict deep sediment hydrates Estimate spatial
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NASA Astrophysics Data System (ADS)
Loring, J.; Thompson, C.; Ilton, E. S.; McGrail, B. P.; Schaef, T.
2014-12-01
Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2 -enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of a Na-saturated montmorillonite (Na-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane and mixtures of methane and carbon dioxide were investigated usingCH4 IR spectroscopic titrations andCH4 XRD. The goals were to (1) determine if the hydration/expansion behavior of the clay in supercritical methane is different than in supercritical CO2, (2) determine if methane intercalates the clay, and (3) probe the effects of increasing CO2 concentrations. IR spectra were collected as Na-SWy-2 was titrated with water under several fluid exposures: pure methane, 25, 50, and 75 mole% CO2 in methane, and pure CO2. ComplementaryCH4 XRD experiments were conducted in the same fluids at discrete dissolved water concentrations to measure the d001 values of the clay and thus its volume change on hydration and CH4 and/or CO2 intercalation. In pure methane, no direct evidence of CH4 intercalation was detected in CH bending or stretching regions of the IR spectra. Similarly, in situ XRD indicated the montmorillonite structure was stable in the presence of CH4 and no measurable changes to the basal spacing were observed. However, under low water conditions where the montmorillonite structure was partially expanded (~sub 1W), the IR data indicated a rapid intercalation of CO2 into the interlayer, even with fluid mixtures containing the lowest concentrations of CO2. Likewise,CH4 XRD showed indirect evidence of CO2 intercalation from an increase in the basal spacing from 11.8 to 12.3 under identical conditions. These findings demonstrate that water and CO2 intercalation processes could lead to permeability changes that directly impact methane transmissivity in shales.
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NASA Astrophysics Data System (ADS)
Ghaedi, Hosein; Ayoub, Muhammad; Bhat, A. H.; Mahmood, Syed Mohammad; Akbari, Saeed; Murshid, Ghulam
2016-11-01
Hydration is an alternative method for CO2 capture. In doing so, some researchers use porous media on an experimental scale. This paper tries to gather the researches on the formation of CO2 hydrate in different types of porous media such as silica sand, quartz sand, Toyoura, pumice, and fire hardened red clay. This review has attempted to examine the effects of salt and particle sizes as two major factors on the induction time, water to hydrate conversion, gas uptake (or gas consumption), and the rate of CO2 hydrate formation. By performing a critical assessment of previous research works, it was observed that the figure for the gas uptake (or gas consumption) and water to hydrate conversion in porous media was decreased by increasing the particle size provided that the pore size was constant. Although, salt can play a role in hydrate formation as the thermodynamic inhibitor, the results show that salt can be regarded as the kinetic growth inhibitor and kinetic promoter. Because of the fact that the gas uptake in seawater is lower than pure water at the end of experiment, the salt can act as a kinetic growth inhibitor. However, since gas uptake (after the nucleation period and for a short period) and the initial rate of hydrate formation in saline water were more than that of pure water, salt can play a promoter role in the kinetic reaction, too. Besides these, in the case of pure water and within a certain particle size, the amount of the hydrate formation rate has been seen to be greater in smaller particles (provided that the pore size is constant), however this has not been observed for seawater.
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Sirotkin, Vladimir A; Kuchierskaya, Alexandra A
2017-10-01
We investigated water/organic solvent sorption and residual enzyme activity to simultaneously monitor preferential solvation/hydration of protein macromolecules in the entire range of water content at 25°C. We applied this approach to estimate protein destabilization/stabilization due to the preferential interactions of bovine pancreatic α-chymotrypsin with water-acetone (moderate-strength H-bond acceptor) and water-DMSO (strong H-bond acceptor) mixtures. There are three concentration regimes for the dried α-chymotrypsin. α-Chymotrypsin is preferentially hydrated at high water content. The residual enzyme activity values are close to 100%. At intermediate water content, the dehydrated α-chymotrypsin has a higher affinity for acetone/DMSO than for water. Residual enzyme activity is minimal in this concentration range. The acetone/DMSO molecules are preferentially excluded from the protein surface at the lowest water content, resulting in preferential hydration. The residual catalytic activity in the water-poor acetone is ∼80%, compared with that observed after incubation in pure water. This effect is very small for the water-poor DMSO. Two different schemes are operative for the hydrated enzyme. At high and intermediate water content, α-chymotrypsin exhibits preferential hydration. However, at intermediate water content, in contrast to the dried enzyme, the initially hydrated α-chymotrypsin possesses increased preferential hydration parameters. At low water content, no residual enzyme activity was observed. Preferential binding of DMSO/acetone to α-chymotrypsin was detected. Our data clearly demonstrate that the hydrogen bond accepting ability of organic solvents and the protein hydration level constitute key factors in determining the stability of protein-water-organic solvent systems. © 2017 Wiley Periodicals, Inc.
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May, Eric F; Lim, Vincent W; Metaxas, Peter J; Du, Jianwei; Stanwix, Paul L; Rowland, Darren; Johns, Michael L; Haandrikman, Gert; Crosby, Daniel; Aman, Zachary M
2018-03-13
Gas hydrate formation is a stochastic phenomenon of considerable significance for any risk-based approach to flow assurance in the oil and gas industry. In principle, well-established results from nucleation theory offer the prospect of predictive models for hydrate formation probability in industrial production systems. In practice, however, heuristics are relied on when estimating formation risk for a given flowline subcooling or when quantifying kinetic hydrate inhibitor (KHI) performance. Here, we present statistically significant measurements of formation probability distributions for natural gas hydrate systems under shear, which are quantitatively compared with theoretical predictions. Distributions with over 100 points were generated using low-mass, Peltier-cooled pressure cells, cycled in temperature between 40 and -5 °C at up to 2 K·min -1 and analyzed with robust algorithms that automatically identify hydrate formation and initial growth rates from dynamic pressure data. The application of shear had a significant influence on the measured distributions: at 700 rpm mass-transfer limitations were minimal, as demonstrated by the kinetic growth rates observed. The formation probability distributions measured at this shear rate had mean subcoolings consistent with theoretical predictions and steel-hydrate-water contact angles of 14-26°. However, the experimental distributions were substantially wider than predicted, suggesting that phenomena acting on macroscopic length scales are responsible for much of the observed stochastic formation. Performance tests of a KHI provided new insights into how such chemicals can reduce the risk of hydrate blockage in flowlines. Our data demonstrate that the KHI not only reduces the probability of formation (by both shifting and sharpening the distribution) but also reduces hydrate growth rates by a factor of 2.
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Stephen, Marie Christy Sharafine; Mathew, John; Varghese, Ajoy Mathew; Kurien, Mary; Mathew, George Ani
2015-12-01
To evaluate the efficacy and safety of intranasal midazolam and chloral hydrate syrup for procedural sedation in children. Prospective randomized placebo-controlled trial (double blind, double dummy). Tertiary care hospital over 18 months. Eighty-two children, 1 to 6 years old, undergoing auditory brainstem response testing were randomized to receive either intranasal midazolam with oral placebo or chloral hydrate syrup with placebo nasal spray. Intranasal midazolam was delivered at 0.5 mg/kg (100 mcg per spray) and oral syrup at 50 mg/kg. Children not sedated at 30 minutes had a second dose at half the initial dose. The primary outcomes measured were safety and efficacy. Secondary outcomes were time to onset of sedation, parental separation, nature of parental separation, parental satisfaction, audiologist's satisfaction, time to recovery, and number of attempts. Forty-one children were in each group, and no major adverse events were noted. The chloral hydrate group showed earlier onset of sedation (66%) compared with the intranasal midazolam group (33%). Significant difference in time to recovery was noted in the chloral hydrate group (78 minutes) versus the intranasal midazolam group (108 minutes). The parents' and audiologist's satisfaction was higher for chloral hydrate (95% and 75%) than for intranasal midazolam (49% and 29%, respectively). Overall, sedation was 95% with chloral hydrate versus 51% with intranasal midazolam. Both drugs maintained sedation. Intranasal midazolam and chloral hydrate are both safe and efficacious for pediatric procedural sedation. Chloral hydrate was superior to intranasal midazolam, with an earlier time to onset of sedation, a faster recovery, better satisfaction among parents and the audiologist, and successful sedation. © American Academy of Otolaryngology—Head and Neck Surgery Foundation 2015.
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Hirai, Hisako; Takahara, Naoya; Kawamura, Taro; Yamamoto, Yoshitaka; Yagi, Takehiko
2008-12-14
High-pressure experiments of ethane hydrate and methane-ethane mixed hydrates with five compositions were performed using a diamond anvil cell in a pressure range of 0.1-2.8 GPa at room temperature. X-ray diffractometry and Raman spectroscopy showed structural changes as follows. The initial structure, structure I (sI), of ethane hydrate was retained up to 2.1 GPa without any structural change. For the mixed hydrates, sI was widely distributed throughout the region examined except for the methane-rich and lower pressure regions. For the ethane-rich and intermediate composition regions (73 mol % ethane sample and 53% sample), sI was maintained up to 2.1 GPa. With increasing methane component (34% and 30% samples), sI existed at pressures from 0.1 to about 1.0 GPa. Hexagonal structure (sH) appeared in addition to sI at 1.3 GPa for the 34% sample and at 1.1 GPa for the 30% sample. By further increasing the methane component (22% sample), structure II (sII) existed solely up to 0.3 GPa. From 0.3 to 0.6 GPa, sII and sI coexisted, and from 0.6 to 1.0 GPa only sI existed. At 1.2 GPa sH appeared, and sH and sI coexisted up to 2.1 GPa. Above 2.1 GPa, ethane hydrate and all of the mixed hydrates decomposed into ice VI and ethane fluid or methane-ethane fluid, respectively. The Raman study revealed that occupation of the small cages by ethane molecules occurred above 0.1 GPa in ethane hydrate and continued up to decomposition at 2.1 GPa, although it is thought that ethane molecules are contained only in the large cage.
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Opening-mode cracking in asphalt pavements : crack initiation and saturation.
DOT National Transportation Integrated Search
2009-12-01
This paper investigates the crack initiation and saturation for opening-mode cracking. Using elastic governing equations : and a weak form stress boundary condition, we derive an explicit solution of elastic fields in the surface course and : obtain ...
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NASA Astrophysics Data System (ADS)
Ebrahimi, Ali N.; Or, Dani
2014-09-01
The dispersal rates of self-propelled microorganisms affect their spatial interactions and the ecological functioning of microbial communities. Microbial dispersal rates affect risk of contamination of water resources by soil-borne pathogens, the inoculation of plant roots, or the rates of spoilage of food products. In contrast with the wealth of information on microbial dispersal in water replete systems, very little is known about their dispersal rates in unsaturated porous media. The fragmented aqueous phase occupying complex soil pore spaces suppress motility and limits dispersal ranges in unsaturated soil. The primary objective of this study was to systematically evaluate key factors that shape microbial dispersal in model unsaturated porous media to quantify effects of saturation, pore space geometry, and chemotaxis on characteristics of principles that govern motile microbial dispersion in unsaturated soil. We constructed a novel 3-D angular pore network model (PNM) to mimic aqueous pathways in soil for different hydration conditions; within the PNM, we employed an individual-based model that considers physiological and biophysical properties of motile and chemotactic bacteria. The effects of hydration conditions on first passage times in different pore networks were studied showing that fragmentation of aquatic habitats under dry conditions sharply suppresses nutrient transport and microbial dispersal rates in good agreement with limited experimental data. Chemotactically biased mean travel speed of microbial cells across 9 mm saturated PNM was ˜3 mm/h decreasing exponentially to 0.45 mm/h for the PNM at matric potential of -15 kPa (for -35 kPa, dispersal practically ceases and the mean travel time to traverse the 9 mm PNM exceeds 1 year). Results indicate that chemotaxis enhances dispersal rates by orders of magnitude relative to random (diffusive) motions. Model predictions considering microbial cell sizes relative to available liquid pathways sizes were in good agreement with experimental results for unsaturated soils. The new modeling platform enables quantitative consideration of key biophysical factors (e.g., pore space heterogeneities and hydration conditions) governing microbial interactions in 3-D soil pore spaces.
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Experimental Work Conducted on MgO Inundated Hydration in WIPP-Relevant Brines
NASA Astrophysics Data System (ADS)
Deng, H.; Xiong, Y.; Nemer, M. B.; Johnsen, S.
2009-12-01
Magnesium oxide (MgO) is being emplaced in the Waste Isolation Pilot Plant (WIPP) as an engineered barrier to mitigate the effect of microbial CO2 generation on actinide mobility in a postclosure repository environment. MgO will sequester CO2 and consume water in brine or water vapor in the gaseous phase. Martin Marietta (MM) MgO is currently being emplaced in the WIPP. A fractional-factorial experiment has been performed to study the inundated-hydration of MM MgO as a function of its particle size, solid-to-liquid ratio, and brine type. MgO hydration experiments have been carried out with three MgO particle sizes and two solid-to-liquid ratios in three WIPP-related brines: ERDA-6, GWB and simplified GWB. ERDA-6 is a synthetic NaCl-rich brine typical of a Castile brine reservoir below the repository. GWB is a synthetic MgCl2- and NaCl-rich brine representative of intergranular brines from the Salado Formation at or near the stratigraphic horizon of the repository. Simplified GWB contains amounts of Mg, Na, and Cl similar to those in GWB without other minor constituents. The hydration products include brucite (Mg(OH)2) and phase 5 (Mg3(OH)5Cl4H2O). In addition to phase 5, MgO hydration in GWB or simplified GWB produces brucite, whereas MgO hydrated in ERDA-6 only produces brucite. The MgO particle size has had a significant effect on the formation of hydration products: small MgO particles have hydrated before the large particles. MgO has hydrated faster in simplified GWB than in the other two brines. In ERDA-6, the solid-to-liquid ratio has affected the brine pH due to the presence of CaO (~1 wt %) as an impurity in MM MgO. GWB has sufficient dissolved Mg to buffer pH despite small amounts of CaO. Both our results and thermodynamic modeling indicate that phase-5 is the stable Mg-OH-Cl phase in Mg-Na-Cl-dominated brines with ionic strengths and chemical compositions similar to that of GWB. In contrast, phase-3 (Mg2(OH)3Cl4H2O) is the stable phase in the MgCl2-saturated Q-brine, a high-ionic-strength (up to 15 m) brine from Asse, Germany. We used EQ3/6 to simulate MgO hydration and carbonation in a closed system containing brine and CO2 at atmospheric concentration by titrating periclase into the system. (EQ3/6 is a geochemical software package for speciation, solubility calculations and reaction path modeling.) EQ3/6 predicted Mg and Cl concentrations and pH similar to the experimentally observed values. EQ3/6 also predicted hydration products similar to thsoe observed experimentally. * This research is funded by WIPP programs administered by the U.S. Department of Energy. ** Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.
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Deb, S K; Swinton, P A; Dolan, E
2016-01-01
Saturation diving is an occupation that involves prolonged exposure to a confined, hyperoxic, hyperbaric environment. The unique and extreme environment is thought to result in disruption to physiological and metabolic homeostasis, which may impact human health and performance. Appropriate nutritional intake has the potential to alleviate and/or support many of these physiological and metabolic concerns, whilst enhancing health and performance in saturation divers. Therefore, the purpose of this review is to identify the physiological and practical challenges of saturation diving and consequently provide evidence-based nutritional recommendations for saturation divers to promote health and performance within this challenging environment. Saturation diving has a high-energy demand, with an energy intake of between 44 and 52 kcal/kg body mass per day recommended, dependent on intensity and duration of underwater activity. The macronutrient composition of dietary intake is in accordance with the current Institute of Medicine guidelines at 45-65 % and 20-35 % of total energy intake for carbohydrate and fat intake, respectively. A minimum daily protein intake of 1.3 g/kg body mass is recommended to facilitate body composition maintenance. Macronutrient intake between individuals should, however, be dictated by personal preference to support the attainment of an energy balance. A varied diet high in fruit and vegetables is highly recommended for the provision of sufficient micronutrients to support physiological processes, such as vitamin B12 and folate intake to facilitate red blood cell production. Antioxidants, such as vitamin C and E, are also recommended to reduce oxidised molecules, e.g. free radicals, whilst selenium and zinc intake may be beneficial to reinforce endogenous antioxidant reserves. In addition, tailored hydration and carbohydrate fueling strategies for underwater work are also advised.
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Hydrophobic hydration and the anomalous partial molar volumes in ethanol-water mixtures
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tan, Ming-Liang; Te, Jerez; Cendagorta, Joseph R.
2015-02-14
The anomalous behavior in the partial molar volumes of ethanol-water mixtures at low concentrations of ethanol is studied using molecular dynamics simulations. Previous work indicates that the striking minimum in the partial molar volume of ethanol V{sub E} as a function of ethanol mole fraction X{sub E} is determined mainly by water-water interactions. These results were based on simulations that used one water model for the solute-water interactions but two different water models for the water-water interactions. This is confirmed here by using two more water models for the water-water interactions. Furthermore, the previous work indicates that the initial decreasemore » is caused by association of the hydration shells of the hydrocarbon tails, and the minimum occurs at the concentration where all of the hydration shells are touching each other. Thus, the characteristics of the hydration of the tail that cause the decrease and the features of the water models that reproduce this type of hydration are also examined here. The results show that a single-site multipole water model with a charge distribution that mimics the large quadrupole and the p-orbital type electron density out of the molecular plane has “brittle” hydration with hydrogen bonds that break as the tails touch, which reproduces the deep minimum. However, water models with more typical site representations with partial charges lead to flexible hydration that tends to stay intact, which produces a shallow minimum. Thus, brittle hydration may play an essential role in hydrophobic association in water.« less
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Tian, Haoting; Guo, Yong; Pan, Bo; Gu, Cheng; Li, Hui; Boyd, Stephen A
2015-07-07
A new photoreduction pathway for nitro-aromatic compounds (NACs) and the underlying degradation mechanism are described. 1,3-Dinitrobenzene was reduced to 3-nitroaniline by the widely distributed aromatic molecule indole; the reaction is facilitated by montmorillonite clay mineral under both simulated and natural sunlight irradiation. The novel chemical reaction is strongly affected by the type of exchangeable cation present on montmorillonite. The photoreduction reaction is initiated by the adsorption of 1,3-dinitrobenzene and indole in clay interlayers. Under light irradiation, the excited indole molecule generates a hydrated electron and the indole radical cation. The structural negative charge of montmorillonite plausibly stabilizes the radical cation hence preventing charge recombination. This promotes the release of reactive hydrated electrons for further reductive reactions. Similar results were observed for the photoreduction of nitrobenzene. In situ irradiation time-resolved electron paramagnetic resonance and Fourier transform infrared spectroscopies provided direct evidence for the generation of hydrated electrons and the indole radical cations, which supported the proposed degradation mechanism. In the photoreduction process, the role of clay mineral is to both enhance the generation of hydrated electrons and to provide a constrained reaction environment in the galley regions, which increases the probability of contact between NACs and hydrated electrons.
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Chen, Quanyuan; Zhang, Lina; Ke, Yujuan; Hills, Colin; Kang, Yanming
2009-02-01
Portland cement (PC) and blended cements containing pulverized fuel ash (PFA) or granulated blast-furnace slag (GGBS) were used to solidify/stabilize an electroplating sludge in this work. The acid neutralization capacity (ANC) of the hydrated pastes increased in the order of PC > PC/GGBS > PC/PFA. The GGBS or PFA replacement (80 wt%) reduced the ANC of the hydrated pastes by 30-50%. The ANC of the blended cement-solidified electroplating sludge (cement/sludge 1:2) was 20-30% higher than that of the hydrated blended cement pastes. Upon carbonation, there was little difference in the ANC of the three cement pastes, but the presence of electroplating sludge (cement/sludge 1:2) increased the ANC by 20%. Blended cements were more effective binders for immobilization of Ni, Cr and Cu, compared with PC, whereas Zn was encapsulated more effectively in the latter. Accelerated carbonation improved the immobilization of Cr, Cu and Zn, but not Ni. The geochemical code PHREEQC, with the edited database from EQ3/6 and HATCHES, was used to calculate the saturation index and solubility of likely heavy metal precipitates in cement-based solidification/stabilization systems. The release of heavy metals could be related to the disruption of cement matrices and the remarkable variation of solubility of heavy metal precipitates at different pH values.
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Lee, Myung W.
2007-01-01
The amplitude of a bottom simulating reflection (BSR), which occurs near the phase boundary between gas hydrate-bearing sediments and underlying gas-filled sediments, strongly depends on the frequency content of a seismic signal, as well as the impedance contrast across the phase boundary. A strong-amplitude BSR, detectable in a conventional seismic profile, is a good indicator of the presence of free gas beneath the phase boundary. However, the BSR as observed in low-frequency multichannel seismic data is generally difficult to identify in high-frequency, single-channel seismic data. To investigate the frequency dependence of BSR amplitudes, single-channel seismic data acquired with an air gun source at Blake Ridge, which is located off the shore of South Carolina, were analyzed in the frequency range of 10-240 Hz. The frequency-dependent impedance contrast caused by the velocity dispersion in partially gas saturated sediments is important to accurately analyze BSR amplitude. Analysis indicates that seismic attenuation of gas hydrate-bearing sediments, velocity dispersion, and a transitional base all contribute to the frequency-dependent BSR amplitude variation in the frequency range of 10-500 Hz. When velocity dispersion is incorporated into the BSR amplitude analysis, the frequency-dependent BSR amplitude at Blake Ridge can be explained with gas hydrate-bearing sediments having a quality factor of about 250 and a transitional base with a thickness of about 1 meter.
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2011-01-01
Background Dengue fever is one of the most common tropical diseases worldwide. Early detection of the disease, followed by intravenous fluid therapy in patients with dengue hemorrhagic fever (DHF) or with warning signs of dengue has a major impact on the prognosis. The purpose of this study is to describe the care provided in a hydration tent, including early detection, treatment, and serial follow-up of patients with dengue fever. Findings The analysis included all patients treated in the hydration tent from April 8 to May 9, 2008. The tent was set up inside the premises of the 2nd Military Firemen Group, located in Meier, a neighborhood in Rio de Janeiro, Brazil. The case form data were stored in a computerized database for subsequent assessment. Patients were referred to the tent from primary care units and from secondary city and state hospitals. The routine procedure consisted of an initial screening including vital signs (temperature, blood pressure, heart rate, and respiratory rate), tourniquet test and blood sampling for complete blood count. Over a 31-day period, 3,393 case recordings were seen at the hydration tent. The mean was 109 patients per day. A total of 2,102 initial visits and 1,291 return visits were conducted. Of the patients who returned to the hydration tent for reevaluation, 850 returned once, 230 returned twice, 114 returned three times, and 97 returned four times or more. Overall, 93 (5.3%) patients with DHF seen at the tent were transferred to a tertiary hospital. There were no deaths among these patients. Discussion As the epidemics were already widespread and there were no technical conditions for routine serology, all cases of suspected dengue fever were treated as such. Implementing hydration tents decrease the number of dengue fever hospitalizations. PMID:21902823
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Tracking Dissolved Methane Concentrations near Active Seeps and Gas Hydrates: Sea of Japan.
NASA Astrophysics Data System (ADS)
Snyder, G. T.; Aoki, S.; Matsumoto, R.; Tomaru, H.; Owari, S.; Nakajima, R.; Doolittle, D. F.; Brant, B.
2015-12-01
A number of regions in the Sea of Japan are known for active gas venting and for gas hydrate exposures on the sea floor. In this investigation we employed several gas sensors mounted on a ROV in order to determine the concentrations of dissolved methane in the water near these sites. Methane concentrations were determined during two-second intervals throughout each ROV deployment during the cruise. The methane sensor deployments were coupled with seawater sampling using Niskin bottles. Dissolved gas concentrations were later measured using gas chromatography in order to compare with the sensor results taken at the same time. The observed maximum dissolved methane concentrations were much lower than saturation values, even when the ROV manipulators were in contact with gas hydrate. Nonetheless, dissolved concentrations did reach several thousands of nmol/L near gas hydrate exposures and gas bubbles, more than two orders of magnitude over the instrumental detection limits. Most of the sensors tested were able to detect dissolved methane concentrations as low as 10 nmol/L which permitted detection when the ROV approached methane plume sites, even from several tens of meters above the sea floor. Despite the low detection limits, the methane sensors showed variable response times when returning to low-background seawater (~5nM). For some of the sensors, the response time necessary to return to background values occurred in a matter of minutes, while for others it took several hours. Response time, as well as detection limit, should be an important consideration when selecting methane sensors for ROV or AUV investigations. This research was made possible, in part, through funding provided by the Japanese Ministry of Economy, Trade and Industry (METI).
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Dynamical properties of the hydration shell of fully deuterated myoglobin
DOE Office of Scientific and Technical Information (OSTI.GOV)
Achterhold, Klaus; Parak, Fritz G.; Ostermann, Andreas
2011-10-15
Freeze-dried perdeuterated sperm whale myoglobin was kept in a water-saturated atmosphere in order to obtain a hydration degree of 335 {sup 1}H{sub 2}O molecules per one myoglobin molecule. Incoherent neutron scattering was performed at the neutron spectrometer TOFTOF at the FRM II in an angular range of q from 0.6 to 1.8 A{sup -1} and a temperature range from 4 to 297 K. We used neutrons with a wavelength of {lambda}{alpha}E 6 A and an energy resolution of about 65 {mu}eV corresponding to motions faster than 10 ps. At temperatures above 225 K, broad lines appear in the spectra causedmore » by quasielastic scattering. For an explanation of these lines, we assumed that there are only two types of protons, those that are part of the hydration water (72%) and those that belong to the protein (28%). The protons of the hydration water were analyzed with the diffusion model of Singwi and Sjoelander [Phys. Rev. 119, 863 (1960)]. In this model, a water molecule stays for a time {tau}{sub 0} in a bound state performing oscillatory motions. Thereafter, the molecule performs free diffusion for the time {tau}{sub 1} in a nonbound state followed again by the oscillatory motions for {tau}{sub 0} and so forth. We used the general formulation with no simplifications as {tau}{sub 0}>>{tau}{sub 1} or {tau}{sub 1}>>{tau}{sub 0}. At room temperature, we obtained {tau}{sub 0} {alpha}E 104 ps and {tau}{sub 1} {alpha}E 37 ps. For the protein bound hydrogen, the dynamics is described by a Brownian oscillator where the protons perform overdamped motions in limited space.« less
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Davis, J.A.; Fuller, C.C.; Cook, A.D.
1987-01-01
The rate of Cd2+ sorption by calcite was determined as a function of pH and Mg2+ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO3. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca2+ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd2+ sorption decrease with increasing pH or with increasing Mg2+. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer. A model is presented which is consistent with the rates of Cd2+ sorption and Ca2+ isotopic exchange. In the model, the first step in Cd2+ sorption involves a fast adsorption reaction that is followed by diffusion of Cd2+ into a surface layer of hydrated CaCO3 that overlies crystalline calcite. Desorption of Cd2+ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO3, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution. ?? 1987.
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NASA Astrophysics Data System (ADS)
Dzidek, Brygida; Bochereau, Séréna; Johnson, Simon A.; Hayward, Vincent; Adams, Michael J.
2017-10-01
The process by which human fingers gives rise to stable contacts with smooth, hard objects is surprisingly slow. Using high-resolution imaging, we found that, when pressed against glass, the actual contact made by finger pad ridges evolved over time following a first-order kinetics relationship. This evolution was the result of a two-stage coalescence process of microscopic junctions made between the keratin of the stratum corneum of the skin and the glass surface. This process was driven by the secretion of moisture from the sweat glands, since increased hydration in stratum corneum causes it to become softer. Saturation was typically reached within 20 s of loading the contact, regardless of the initial moisture state of the finger and of the normal force applied. Hence, the gross contact area, frequently used as a benchmark quantity in grip and perceptual studies, is a poor reflection of the actual contact mechanics that take place between human fingers and smooth, impermeable surfaces. In contrast, the formation of a steady-state contact area is almost instantaneous if the counter surface is soft relative to keratin in a dry state. It is for this reason that elastomers are commonly used to coat grip surfaces.
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Removal of phosphate from greenhouse wastewater using hydrated lime.
Dunets, C Siobhan; Zheng, Youbin
2014-01-01
Phosphate (P) contamination in nutrient-laden wastewater is currently a major topic of discussion in the North American greenhouse industry. Precipitation of P as calcium phosphate minerals using hydrated lime could provide a simple, inexpensive method for retrieval. A combination of batch experiments and chemical equilibrium modelling was used to confirm the viability of this P removal method and determine lime addition rates and pH requirements for greenhouse wastewater of varying nutrient compositions. Lime: P ratio (molar ratio of CaMg(OH)₄: PO₄‒P) provided a consistent parameter for estimating lime addition requirements regardless of initial P concentration, with a ratio of 1.5 providing around 99% removal of dissolved P. Optimal P removal occurred when lime addition increased the pH from 8.6 to 9.0, suggesting that pH monitoring during the P removal process could provide a simple method for ensuring consistent adherence to P removal standards. A Visual MINTEQ model, validated using experimental data, provided a means of predicting lime addition and pH requirements as influenced by changes in other parameters of the lime-wastewater system (e.g. calcium concentration, temperature, and initial wastewater pH). Hydrated lime addition did not contribute to the removal of macronutrient elements such as nitrate and ammonium, but did decrease the concentration of some micronutrients. This study provides basic guidance for greenhouse operators to use hydrated lime for phosphate removal from greenhouse wastewater.
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A Smoking Gun for Methane Hydrate Release During the Paleocene-Eocene Thermal Maximum
NASA Astrophysics Data System (ADS)
Frieling, J.; Peterse, F.; Lunt, D. J.; Bohaty, S. M.; S Sinninghe Damsté, J.; Reichart, G. J.; Sluijs, A.
2016-12-01
The Paleocene-Eocene Thermal Maximum (PETM; 56 Ma) was a period of rapid 4-5ºC global warming and a global negative carbon isotope excursion (CIE) of 3-4.5‰, signaling the input of at least 1500 Gt of δ13C-depleted carbon into the ocean-atmosphere system. Methane from submarine hydrates has long been proposed as a carbon source, but direct and indirect evidence is lacking. We generated a new high-resolution TEX86 and δ13C record from Ocean Drilling Program Site 959 in the eastern tropical Atlantic and find that initial warming preceded the PETM CIE by 10 kyr. Moreover, time-shifted cross-correlations on these new and published temperature-δ13C data imply that substantial (2-3 °C) warming lead 13C-depleted carbon injection by an average of 2-3 kyr globally. Finally, a data compilation shows that global burial fluxes of biogenic Ba approximately doubled across all depths of the ocean studied, which on PETM time scales can only be explained by significant Ba addition to the oceans. Submarine hydrates are Ba-rich and require warming to dissociate. The simplest explanation for the temperature lead and Ba addition to the ocean is that methane hydrate dissociated as a response to initial warming and acted as a positive carbon cycle feedback during the PETM.
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NASA Astrophysics Data System (ADS)
Haeckel, M.; Bialas, J.; Wallmann, K. J.
2009-12-01
Gas hydrates occur in nature at all active and passive continental margins as well as in permafrost regions, and vast amounts of natural gas are bound in those deposits. Geologists estimate that twice as much carbon is bound in gas hydrates than in any other fossil fuel reservoir, such as gas, oil and coal. Hence, natural gas hydrates represent a huge potential energy resource that, in addition, could be utilized in a CO2-neutral and therefore environmentally friendly manner. However, the utilization of this natural treasure is not as easy as the conventional production of oil or natural gas and calls for new and innovative techniques. In the framework of the large-scale collaborative research project SUGAR (Submarine Deposits of Gas Hydrates - Exploration, Production and Transportation), we aim to produce gas from methane hydrates and to sequester carbon dioxide from power plants and other industrial sources as CO2 hydrates in the same host sediments. Thus, the SUGAR project addresses two of the most pressing and challenging topics of our time: development of alternative energy strategies and greenhouse gas mitigation techniques. The SUGAR project is funded by two federal German ministries and the German industry for an initial period of three years. In the framework of this project new technologies starting from gas hydrate exploration techniques over drilling technologies and innovative gas production methods to CO2 storage in gas hydrates and gas transportation technologies will be developed and tested. Beside the performance of experiments, numerical simulation studies will generate data regarding the methane production and CO2 sequestration in the natural environment. Reservoir modelling with respect to gas hydrate formation and development of migration pathways complete the project. This contribution will give detailed information about the planned project parts and first results with focus on the production methods.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Rack, Frank; Storms, Michael; Schroeder, Derryl
The primary accomplishments of the JOI Cooperative Agreement with DOE/NETL in this quarter were (1) the preliminary postcruise evaluation of the tools and measurement systems that were used during ODP Leg 204 to study hydrate deposits on Hydrate Ridge, offshore Oregon from July through September 2002; and (2) the preliminary study of the hydrate-bearing core samples preserved in pressure vessels and in liquid nitrogen cryofreezers, which are now stored at the ODP Gulf Coast Repository in College Station, TX. During ODP Leg 204, several newly modified downhole tools were deployed to better characterize the subsurface lithologies and environments hosting microbialmore » populations and gas hydrates. A preliminary review of the use of these tools is provided herein. The DVTP, DVTP-P, APC-methane, and APC-Temperature tools (ODP memory tools) were used extensively and successfully during ODP Leg 204 aboard the D/V JOIDES Resolution. These systems provided a strong operational capability for characterizing the in situ properties of methane hydrates in subsurface environments on Hydrate Ridge during ODP Leg 204. Pressure was also measured during a trial run of the Fugro piezoprobe, which operates on similar principles as the DVTP-P. The final report describing the deployments of the Fugro Piezoprobe is provided in Appendix A of this report. A preliminary analysis and comparison between the piezoprobe and DVTP-P tools is provided in Appendix B of this report. Finally, a series of additional holes were cored at the crest of Hydrate Ridge (Site 1249) specifically geared toward the rapid recovery and preservation of hydrate samples as part of a hydrate geriatric study partially funded by the Department of Energy (DOE). In addition, the preliminary results from gamma density non-invasive imaging of the cores preserved in pressure vessels are provided in Appendix C of this report. An initial visual inspection of the samples stored in liquid nitrogen is provided in Appendix D of this report.« less
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Feng, Gang; Liu, Cheng-Wen; Zeng, Zhen; Hou, Gao-Lei; Xu, Hong-Guang; Zheng, Wei-Jun
2017-06-14
To understand the initial hydration processes of MgCl 2 , we measured photoelectron spectra of MgCl 2 (H 2 O) n - (n = 0-6) and conducted ab initio calculations on MgCl 2 (H 2 O) n - and their neutral counterparts up to n = 7. A dramatic drop in the vertical detachment energy (VDE) was observed upon addition of the first water molecule to bare MgCl 2 - . This large variation in VDE can be associated with the charge-transfer-to-solvent (CTTS) effect occurring in the MgCl 2 (H 2 O) n - clusters, as hydration induces transfer of the excess electron of MgCl 2 - to the water molecules. Investigation of the separation of Cl - -Mg 2+ ion pair shows that, in MgCl 2 (H 2 O) n - anions, breaking of the first Mg-Cl bond occurs at n = 4, while breaking of the second Mg-Cl bond takes place at n = 6. For neutral MgCl 2 (H 2 O) n clusters, breaking of the first Mg-Cl bond starts at n = 7.
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Effects of silicone gel sheet on the stratum corneum hydration.
Suetak, T; Sasai, S; Zhen, Y X; Tagami, H
2000-09-01
Various groups have reported the efficacy of treatment with topical silicone gel sheet (SGS) for keloids and hypertrophic scars. Because its hydrating effect on the stratum corneum (SC) has been suggested as a mechanism underlying its therapeutic effectiveness, we evaluated it by comparing it with simple plastic film occlusion. With biophysical instruments we assessed the water content of the skin surface as well as its water evaporation on the flexor aspects of bilateral forearms of 10 healthy volunteers for 30min after removal of dressings of SGS or a plastic film that were applied either for 1 day or for 7 days. Occlusion with SGS or plastic film induced hydration of the skin surface, which was followed by an initial quick and later slow process of dehydration when the skin was exposed to the ambient atmosphere. The magnitude of the increase in hydration induced by SGS was always smaller than that of the plastic film occlusion and, unlike the latter treatment, hydration became less with repetition of SGS treatment. On day 7, the SC hydration quickly reduced to the level of non-treated control skin after removal of the dressings. An in vivo test demonstrated that the water-holding capacity of the SC normalised after 7 days of SGS treatment. SGS probably produces a favourable condition for the skin by protecting it from various environmental stimuli, while keeping the SC in an adequately but not over-hydrated condition.
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Biological variability of transferrin saturation and unsaturated iron binding capacity
Adams, PC; Reboussin, DM; Press, RD; Barton, JC; Acton, RT; Moses, GC; Leiendecker-Foster, C; McLaren, GD; Dawkins, FW; Gordeuk, VR; Lovato, L; Eckfeldt, JH
2007-01-01
Background Transferrin saturation is widely considered the preferred screening test for hemochromatosis. Unsaturated iron binding capacity has similar performance at lower cost. However, the within-person biological variability of both these tests may limit their ability at commonly used cut points to detect HFE C282Y homozygous patients. Methods The Hemochromatosis and Iron Overload Screening (HEIRS) Study screened 101,168 primary care participants for iron overload using tansferrin saturation, unsaturated iron binding capacity, ferritin and HFE C282Y and H63D genotyping. Transferrin saturation and unsaturated iron binding capacity were performed at initial screening and again when selected participants and controls returned for a clinical examination several months later. A missed case was defined as a C282Y homozygote who had transferrin saturation below cut point (45 % women, 50 % men) or unsaturated iron binding capacity above cut point (150 μmol/L women, 125 μmol/L men) at either the initial screening or clinical examination, or both, regardless of serum ferritin. Results There were 209 C282Y previously undiagnosed homozygotes with transferrin saturation and unsaturated iron binding capacity testing done at initial screening and clinical examination. Sixty-eight C282Y homozygotes (33%) would have been missed at these transferrin saturation cut points (19 men, 49 women, median SF 170 μg/L, first and third quartiles 50 and 474 μg/L), and 58 homozygotes (28 %) would have been missed at the unsaturated iron binding capacity cut points (20 men, 38 women, median SF 168 μg/L, quartiles 38 and 454 μg/L). There was no advantage to using fasting samples. Conclusions The within-person biological variability of transferrin saturation and unsaturated iron binding capacity limit their usefulness as an initial screening test for expressing C282Y homozygotes. PMID:17976429
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Francis, Jill J; Johnston, Marie; Robertson, Clare; Glidewell, Liz; Entwistle, Vikki; Eccles, Martin P; Grimshaw, Jeremy M
2010-12-01
In interview studies, sample size is often justified by interviewing participants until reaching 'data saturation'. However, there is no agreed method of establishing this. We propose principles for deciding saturation in theory-based interview studies (where conceptual categories are pre-established by existing theory). First, specify a minimum sample size for initial analysis (initial analysis sample). Second, specify how many more interviews will be conducted without new ideas emerging (stopping criterion). We demonstrate these principles in two studies, based on the theory of planned behaviour, designed to identify three belief categories (Behavioural, Normative and Control), using an initial analysis sample of 10 and stopping criterion of 3. Study 1 (retrospective analysis of existing data) identified 84 shared beliefs of 14 general medical practitioners about managing patients with sore throat without prescribing antibiotics. The criterion for saturation was achieved for Normative beliefs but not for other beliefs or studywise saturation. In Study 2 (prospective analysis), 17 relatives of people with Paget's disease of the bone reported 44 shared beliefs about taking genetic testing. Studywise data saturation was achieved at interview 17. We propose specification of these principles for reporting data saturation in theory-based interview studies. The principles may be adaptable for other types of studies.
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Dabinett, J A; Reid, K; James, N
2001-09-01
The purpose of the present study was to develop a hydration strategy for use by female English field hockey players at the 1998 Commonwealth Games in Malaysia. An additional aim was to initiate the process of acclimation. Fifteen elite players, mean age (+/-SEM) 24.1 +/- 1.19 years, height 1.67 +/- 0.01 m, and body mass 62.8 +/- 1.76 kg, took part in a 5-day training camp immediately prior to departure for the Games. In order to develop the hydration strategy, training took place under similar environmental conditions to those to be experienced in Malaysia (i.e., 32 degrees C, 80% humidity). Acclimation training consisted of 30-50 min of either continuous, low intensity cycling or high intensity intermittent cycling, which more closely replicated the pattern of activity in field hockey. Body mass measures taken each morning, and pre and post training, together with urine color measures, were used to assess hydration status. Pre-loading with up to 1 L of a 3% carbohydrate-electrolyte solution or water immediately prior to acclimation training, as well as regular drinks throughout, ensured that players avoided significant dehydration, with percent body mass changes ranging from -0.34% to +4.24% post training. Furthermore, the protocol used was sufficient to initiate the process of acclimation as demonstrated by a significant reduction in exercising heart rate and core temperature at all time points by days 4 and 5. In conclusion, although labor intensive and time consuming, the camp was successful in developing a hydration strategy that players were able to utilize once at the Games.
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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
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Chiou, Cary T.; Rutherford, David W.
1997-01-01
The effects of exchanged cation and layer charge on the sorption of water and ethylene glycol monoethyl ether (EGME) vapors on montmorillonite have been studied on SAz-1 and SWy-1 source clays, each exchanged respectively with Ca, Na, K, Cs and tetramethylammonium (TMA) cations. The corresponding lattice expansions were also determined, and the corresponding N2 adsorption data were provided for comparison. For clays exchanged with cations of low hydrating powers (such as K, Cs and TMA), water shows a notably lower uptake than does N2 at low relative pressures (P/P0). By contrast, EGME shows higher uptakes than N2 on all exchanged clays at all P/P0. The anomaly for water is attributed to its relatively low attraction for siloxane surfaces of montmorillonite because of its high cohesive energy density. In addition to solvating cations and expanding interlayers, water and EGME vapors condense into small clay pores and interlayer voids created by interlayer expansion. The initial (dry) interlayer separation varies more significantly with cation type than with layer charge; the water-saturated interlayer separation varies more with cation type than the EGME-saturated interlayer separation. Because of the differences in surface adsorption and interlayer expansion for water and EGME, no general correspondence is found between the isotherms of water and EGME on exchanged clays, nor is a simple relation observed between the overall uptake of either vapor and the cation solvating power. The excess interlayer capacities of water and of EGME that result from lattice expansion of the exchanged clays are estimated by correcting for amounts of vapor adsorption on planar clay surfaces and of vapor condensation into intrinsic clay pores. The resulting data follow more closely the relative solvating powers of the exchanged cations.
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Alkyl phospholipid antihypertensive agents in method of lowering blood pressure
Snyder, Fred L.; Blank, Merle L.; Muirhead, Ernest E.; Leach, deceased, Byron E.; Byers, Lawrence W.
1988-01-01
The composition of this invention is 1-O-alkyl-2-acetoyl-sn-glycero-3-phosphocholine, having the ionic structural formula; ##STR1## wherein R is saturated alkyl having 9-21 carbon atoms, or salts or hydrates of the composition. Preferably R has 13-19 carbon atoms and most preferably R has 15 carbon atoms. The composition of this invention is useful for reducing hypertension in warm-blooded animals, including humans, when administered either orally or by injection or innoculation, e.g., intravenous injection. The composition can be prepared from naturally occurring lipids or synthetically from commercially available material.
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NASA Astrophysics Data System (ADS)
Loring, J.
2015-12-01
Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2-enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of Na-, Cs-, and NH4+-saturated montmorillonite (Na-, Cs-, and NH4-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane, carbon dioxide, and CO2/CH4 mixtures (3 and 25 mole% CO2) were investigated using in situ IR spectroscopic titrations, in situ XRD, in situ MAS-NMR, and ab initio electronic structure calculations. The overarching goal was to better understand the hydration/expansion behavior of Na-SWy-2 in CO2/CH4 fluid mixtures by comparison to Cs-, and NH4+-saturated clays. Specific aims were to (1) determine if CH4 intercalates the clays, (2) probe the effects of increasing dissolved CO2 and H2O concentrations, and (3) understand the role of cation solvation by H2O and/or CO2. In pure CH4, no evidence of CH4 intercalation was detected by IR for any of the clays. Similarly, no measurable changes to the basal spacing were observed by XRD in the presence of pure CH4. However, when dry Cs- and NH4-SWy-2 were exposed to dry fluids containing CO2, IR showed maximum CO2 penetrated the interlayer, XRD indicated the clays expanded, and NMR showed evidence for cation solvation by CO2, in line with theoretical predictions. IR titration of these clays with water showed sorbed H2O concentrations decreased with increasing dissolved CO2, suggesting competition for interlayer residency by CO2 and H2O. For Na-SWy-2, on the other hand, CO2 intercalated the clay and was at a maximum only after a minimum sorbed H2O was achieved. Further increases in sorbed H2O led to displacement of intercalated CO2. These findings demonstrate that complicated H2O and CO2 intercalation processes could lead to permeability changes that directly impact methane transmissivity in shales.
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Nechaeva, O V; Tikhomirova, E I; Zayarsky, D A; Bespalova, N V; Glinskaya, E V; Shurshalova, N F; Al Bayati, B M; Babailova, A I
2017-04-01
The dynamics of microbial biofilm formation by standard strain and by clinical strains of uropathogenic coliform bacteria was investigated in vitro and the effect of sublethal concentrations of the polymer compound polyazolidinammonium modified with iodine hydrate ions on the initial stages of biofilm formation was assessed. Treatment of immunological plate wells with the polymeric compound prevented film formation, especially in case of clinical E. coli strain carrying FimH virulence gene.
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Wang, Xiujuan; Lee, Myung W.; Collett, Timothy S.; Yang, Shengxiong; Guo, Yiqun; Wu, Shiguo
2014-01-01
Downhole wireline log (DWL) data was acquired from eight drill sites during China's first gas hydrate drilling expedition (GMGS-1) in 2007. Initial analyses of the acquired well log data suggested that there were no significant gas hydrate occurrences at Site SH4. However, the re-examination of the DWL data from Site SH4 indicated that there are two intervals of high resistivity, which could be indicative of gas hydrate. One interval of high resistivity at depth of 171–175 m below seafloor (mbsf) is associated with a high compressional- wave (P-wave) velocities and low gamma ray log values, which suggests the presence of gas hydrate in a potentially sand-rich (low clay content) sedimentary section. The second high resistivity interval at depth of 175–180 mbsf is associated with low P-wave velocities and low gamma values, which suggests the presence of free gas in a potentially sand-rich (low clay content) sedimentary section. Because the occurrence of free gas is much shallower than the expected from the regional depth of the bottom simulating reflector (BSR), the free gas could be from the dissociation of gas hydrate during drilling or there may be a local anomaly in the depth to the base of the gas hydrate stability zone. In order to determine whether the low P-wave velocity with high resistivity is caused by in-situ free gas or dissociated free gas from the gas hydrate, the surface seismic data were also used in this analysis. The log analysis incorporating the surface seismic data through the construction of synthetic seismograms using various models indicated the presence of free gas directly in contact with an overlying gas hydrate-bearing section. The occurrence of the anomalous base of gas hydrate stability at Site SH4 could be caused by a local heat flow conditions. This paper documents the first observation of gas hydrate in what is believed to be a sand-rich sediment in Shenhu area of the South China Sea.
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NASA Astrophysics Data System (ADS)
Mihalache, Constance
Assessing the potential for instability in non-saturated geomaterials is of critical importance for the prevention of disastrous failures that occur through these materials, from natural hazards such as rainfall-induced flow slides, to underwater sediment collapse due to methane hydrate dissociation, to the failure of key infrastructure components. In particular, the gaseous and liquid phases present within the pores of a geomaterial play a vital role in its overall behavior, and consequently must be considered in stability analyses. In this work, analytical techniques are presented to evaluate material stability for the different saturation states that occur during a wetting process, where soils progress from unsaturated conditions in the funicular regime, to quasi-saturated conditions in the insular regime, to complete saturation. Each of these different saturation states involves different interactions between the pore fluids and the solid skeleton hosting them. For example, while unsaturated soil behavior is characterized by the capillary effects from the interface between the gaseous and liquid phases, the dominant effect of isolated bubbles within the quasi-saturated regime is to increase the compressibility of the interstitial fluid mixture. By considering the different characteristics of these saturation states, energy-based work input expressions are developed and then used to derive criteria for loss of controllability of the material response. These criteria are then used to assess the stability of geomaterials under various loading configurations. Then, to unite the funicular and insular saturation regimes, the same methodology is adapted to the derivation of comprehensive three-phase criteria for non-saturated soils. An alternative interpretation of such constitutive singularities is also derived, with reference to the ill-posedness of the mass balance equations that control the transient flow of the fluid constituents of a deformable multiphase porous medium. Lastly, the concepts considered throughout the study are applied to the solution of boundary-value problems, using a finite element approach. Overall, it is shown that depending on the considered saturation regime, different stability criteria need to be applied for the accurate interpretation of material behavior. These techniques provide a mechanistic interpretation for a range of processes, such as the nature of so-called "wetting-collapse" events, the variability of the instability line for flow failures acting through gassy sediments, and the onset of runaway failures at the transition between funicular and insular states.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Humphrey, Gary
The objective of this project (and report) is to produce a guide to developing scientific, operational, and logistical plans for a future methane hydrate-focused offshore pressure coring program. This report focuses primarily on a potential coring program in the Walker Ridge 313 and Green Canyon 955 blocks where previous investigations were undertaken as part of the 2009 Department of Energy JIP Leg II expedition, however, the approach to designing a pressure coring program that was utilized for this project may also serve as a useful model for planning pressure coring programs for hydrates in other areas. The initial portion ofmore » the report provides a brief overview of prior investigations related to gas hydrates in general and at the Walker Ridge 313 and Green Canyon 955 blocks in particular. The main content of the report provides guidance for various criteria that will come into play when designing a pressure coring program.« less
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Initial Estimates of Optical Constants of Mars Candidate Materials
NASA Technical Reports Server (NTRS)
Rousch, Ted L.; Brown, Adrian Jon; Bishop, Janice L.; Blake, David F.; Bristow, Thomas F.
2013-01-01
Data obtained at visible and near-infrared wavelengths by OMEGA on Mars Express and CRISM on MRO provide definitive evidence for the presence of phyllosilicates and other hydrated phases on Mars. A diverse range of both Fe/Mg-OH and Al- OH-bearing phyllosilicates were identified including the smectites, nontronite, saponite, and montmorillonite. To constrain the abundances of these phyllosilicates, spectral analyses of mixtures are needed. We report on our effort to enable the quantitative evaluation of the abundance of hydrated-hydroxylated silicates when they are contained in mixtures. We include two component mixtures of hydrated/ hydroxylated silicates with each other and with two analogs for other Martian materials; pyroxene (enstatite) and palagonitic soil (an alteration product of basaltic glass, hereafter referred to as palagonite). For the hydrated-hydroxylated silicates we include saponite and montmorillonite (Mg- and Al-rich smectites). We prepared three size separates of each end-member for study: 20-45, 63-90, and 125-150 micron.
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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.
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A simple method for environmental cell depressurization for use with an electron microscope.
Ogawa, Naoki; Mizokawa, Ryo; Saito, Minoru; Ishikawa, Akira
2017-12-01
With the aid of the environmental cell (EC) in electron microscopy, hydrated specimens have been observed at high resolutions that optical microscopy cannot attain. Due to the ultra-high vacuum conditions of the inner column of the electron microscope, the EC requires sealing films that are sufficiently thin to allow electron transmission and that are sufficiently tough to withstand the pressure difference between the inside and outside of the EC. However, most hydrated specimens can be observed at low vacuum because the saturated vapor pressure of water is known to be 0.02 atm at room temperature. These concepts have been used in the differential pumping system, but it is complicated and relatively expensive. In this work, we propose a simple method for depressurization of the EC using a 'balloon structure' and demonstrate the theoretical benefits and practical improvement for specimen observations in low-vacuum conditions. © The Author 2017. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.
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GULF OF MEXICO SEAFLOOR STABILITY AND GAS HYDRATE MONITORING STATION PROJECT
DOE Office of Scientific and Technical Information (OSTI.GOV)
J. Robert Woolsey; Thomas M. McGee; Robin C. Buchannon
The gas hydrates research Consortium (HRC), established and administered at the University if Mississippi's Center for Marine Research and Environmental Technology (CMRET) has been active on many fronts in FY 03. Extension of the original contract through March 2004, has allowed completion of many projects that were incomplete at the end of the original project period due, primarily, to severe weather and difficulties in rescheduling test cruises. The primary objective of the Consortium, to design and emplace a remote sea floor station for the monitoring of gas hydrates in the Gulf of Mexico by the year 2005 remains intact. However,more » the possibility of levering HRC research off of the Joint Industries Program (JIP) became a possibility that has demanded reevaluation of some of the fundamental assumptions of the station format. These provisions are discussed in Appendix A. Landmark achievements of FY03 include: (1) Continuation of Consortium development with new researchers and additional areas of research contribution being incorporated into the project. During this period, NOAA's National Undersea Research Program's (NURP) National Institute for Undersea Science and Technology (NIUST) became a Consortium funding partner, joining DOE and Minerals Management Service (MMS); (2) Very successful annual and semiannual meetings in Oxford Mississippi in February and September, 2003; (3) Collection of piston cores from MC798 in support of the effort to evaluate the site for possible monitoring station installation; (4) Completion of the site evaluation effort including reports of all localities in the northern Gulf of Mexico where hydrates have been documented or are strongly suspected to exist on the sea floor or in the shallow subsurface; (5) Collection and preliminary evaluation of vent gases and core samples of hydrate from sites in Green Canyon and Mississippi Canyon, northern Gulf of Mexico; (6) Monitoring of gas activity on the sea floor, acoustically and thermally; (7) Design, construction, and successful deployment of an in situ pore-water sampling device; (8) Improvements to the original Raman spectrometer (methane sensor); (9) Laboratory demonstration of the impact of bacterially-produced surfactants' rates of hydrate formation; (10) Construction and sea floor emplacement and testing--with both watergun and ship noise sources--of the prototypal vertical line array (VLA); (11) Initiation of studies of spatial controls on hydrates; (12) Compilation and analyses of seismic data, including mapping of surface anomalies; (13) Additional field verification (bottom samples recovered), in support of the site selection effort; (14) Collection and preliminary analyses of gas hydrates from new sites that exhibit variant structures; (15) Initial shear wave tests carried out in shallow water; (16) Isolation of microbes for potential medicinal products development; (17) Preliminary modeling of occurrences of gas hydrates.« less
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Thermal structure of the TTL and its relation to stratospheric-tropospheric exchange of water.
NASA Astrophysics Data System (ADS)
de La Torre Juárez, M.; Ao, C. O.; Schr\\O der, T. M.; Hermann, R.
2004-12-01
The annual cycle of the TTL fine scale thermal structure is described as captured by GPS radio occultation and the pressure levels of the ECMWF weather analysis. This annual cycle is compared to the annual cycle in water concentrations at the upper troposphere/lower stratosphere measured by HALOE. It is found that the saturation mixing ratios at the Cold Point Tropopause temperatures are consistent and sligthly below HALOE values with some temporal lag. This suggests that if dehydration mechanisms other than those associated with slow vertical asscent are working effectively, they must be counterbalanced by other hydration mechanisms. A comparison between saturation mixing ratios at the temperatures captured by GPS radio occultation and HALOE concentrations of water vapor show an annual cycle dominated by supersaturation in the boreal winter months, when the upward mass fluxes are larger, and subsaturation in the summer. The longitudinal dependence of these cycles is discussed and so is its possible implication for the seasonality of statospheric-tropospheric exchange of water.
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Kinetics of CH4 and CO2 hydrate dissociation and gas bubble evolution via MD simulation.
Uddin, M; Coombe, D
2014-03-20
Molecular dynamics simulations of gas hydrate dissociation comparing the behavior of CH4 and CO2 hydrates are presented. These simulations were based on a structurally correct theoretical gas hydrate crystal, coexisting with water. The MD system was first initialized and stabilized via a thorough energy minimization, constant volume-temperature ensemble and constant volume-energy ensemble simulations before proceeding to constant pressure-temperature simulations for targeted dissociation pressure and temperature responses. Gas bubble evolution mechanisms are demonstrated as well as key investigative properties such as system volume, density, energy, mean square displacements of the guest molecules, radial distribution functions, H2O order parameter, and statistics of hydrogen bonds. These simulations have established the essential similarities between CH4 and CO2 hydrate dissociation. The limiting behaviors at lower temperature (no dissociation) and higher temperature (complete melting and formation of a gas bubble) have been illustrated for both hydrates. Due to the shift in the known hydrate stability curves between guest molecules caused by the choice of water model as noted by other authors, the intermediate behavior (e.g., 260 K) showed distinct differences however. Also, because of the more hydrogen-bonding capability of CO2 in water, as reflected in its molecular parameters, higher solubility of dissociated CO2 in water was observed with a consequence of a smaller size of gas bubble formation. Additionally, a novel method for analyzing hydrate dissociation based on H-bond breakage has been proposed and used to quantify the dissociation behaviors of both CH4 and CO2 hydrates. Activation energies Ea values from our MD studies were obtained and evaluated against several other published laboratory and MD values. Intrinsic rate constants were estimated and upscaled. A kinetic reaction model consistent with macroscale fitted kinetic models has been proposed to indicate the macroscopic consequences of this analysis.
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Rutqvist, J.; Moridis, G.J.; Grover, T.; Collett, T.
2009-01-01
In this simulation study, we analyzed the geomechanical response during depressurization production from two known hydrate-bearing permafrost deposits: the Mallik (Northwest Territories, Canada) deposit and Mount Elbert (Alaska, USA) deposit. Gas was produced from these deposits at constant pressure using horizontal wells placed at the top of a hydrate layer (HL), located at a depth of about 900??m at the Mallik site and 600??m at the Mount Elbert site. The simulation results show that general thermodynamic and geomechanical responses are similar for the two sites, but with substantially higher production and more intensive geomechanical responses at the deeper Mallik deposit. The depressurization-induced dissociation begins at the well bore and then spreads laterally, mainly along the top of the HL. The depressurization results in an increased shear stress within the body of the receding hydrate and causes a vertical compaction of the reservoir. However, its effects are partially mitigated by the relatively stiff permafrost overburden, and compaction of the HL is limited to less than 0.4%. The increased shear stress may lead to shear failure in the hydrate-free zone bounded by the HL overburden and the downward-receding upper dissociation interface. This zone undergoes complete hydrate dissociation, and the cohesive strength of the sediment is low. We determined that the likelihood of shear failure depends on the initial stress state as well as on the geomechanical properties of the reservoir. The Poisson's ratio of the hydrate-bearing formation is a particularly important parameter that determines whether the evolution of the reservoir stresses will increase or decrease the likelihood of shear failure.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Halpern, A.M.; Ruggles, C.J.; Zhang, X.K.
Fluorescence spectra and decay curves of dilute solutions (<3 x 10/sup -4/ M) of triethylamine (TEA), tri-n-propylamine (TPA), and 1,4-diazabicyclo(2.2.2)octane (DABCO) in H/sub 2/O- and D/sub 2/O-saturated n-hexane reveal the presence of a complex formed between the electronically excited amine and water. The decay curves, measured between 273 and 323 K (and at 280 and 360 nm; 300 and 400 nm for DABCO), conform to the standard monomer-excimer photokinetic scheme and are analyzed accordingly. These results indicate that the binding energy of the excited TEA-H/sub 2/O complex (B*) is ca. 7.8 kcal/mol, which is larger than that of the ground-statemore » TEA hydrate. B* for the TPA and DABCO-H/sub 2/O complexes is estimated to be ca. 10 and 8.8 kcal/mol, respectively. Stationary-state measurements are consistent with these assignments. The activation energy for the diffusion of water in n-hexane (assumed to be monomeric) appears to be very small (<1 kcal/mol). The decay constants of the three complexes studied are ca. 3.4 x 10/sup 7/ s/sup -1/ for amine-H/sub 2/O and 2.9 x 10/sup 7/ s/sup -1/ for the amine-D/sub 2/O systems. Intrinsic fluorescence quantum efficiencies of the amine-H/sub 2/O complexes are 0.17, 0.23, and 0.28 for TEA, TPA, and DABCO, respectively, at 303 K. A Foerster cycle analysis of the dry and H/sub 2/O-saturated fluorescence spectra of TEA, when taking the ground-state hydrate into account indicates that the repulsion energy of the post-fluorescence (TEA-H/sub 2/O) complex is ca. 10 kcal/mol.« less
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Electronic transport in disordered chains with saturable nonlinearity
NASA Astrophysics Data System (ADS)
dos Santos, J. L. L.; Nguyen, Ba Phi; de Moura, F. A. B. F.
2015-10-01
In this work we study numerically the dynamics of an initially localized wave packet in one-dimensional disordered chains with saturable nonlinearity. By using the generalized discrete nonlinear Schrödinger equation, we calculate two different physical quantities as a function of time, which are the participation number and the mean square displacement from the excitation site. From detailed numerical analysis, we find that the saturable nonlinearity can promote a sub-diffusive spreading of the wave packet even in the presence of diagonal disorder for a long time. In addition, we also investigate the effect of the saturated nonlinearity for initial times of the electronic evolution thus showing the possibility of mobile breather-like modes.
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NASA Astrophysics Data System (ADS)
Choukroun, M.; Barmatz, M. B.; Castillo, J. C.; Sotin, C.
2008-12-01
Surface features potentially associated with cryovolcanism have been identified on Titan, and the processes taking place beneath the surface are likely associated with the dissociation of clathrate hydrates and the release of methane. On Enceladus, the South Pole plume discovered by the Cassini-Huygens mission contains a large proportion of volatiles, in amounts consistent with models of clathrate hydrates dissociation at depth (Kieffer et al., Science 314, 1764-1766, 2006). The stability of clathrate hydrates is relatively well constrained in pure and mixed gas systems (e.g., Sloan, Clathrate hydrates of natural gases, Marcel Dekker, New York, 1998). Recent measurements of clathrate destabilization in presence of ammonia, a likely component of Titan's interior, led to the development of a new model of cryovolcanism (Choukroun et al., Lunar Planet. Sci. Conf., #1837, Houston, 2008). Internal dynamics relies on ice convection at depth on Titan and Enceladus (e.g., Tobie et al., Icarus 175, 496-502, 2005), and on relatively large tidal stresses on Enceladus. Clathrates are expected to destabilize when subject to stress (Durham et al., J. Geophys. Res. 108 (B4), 2182, 2003). Therefore, addressing the mechanical properties of clathrate hydrates in these environments is a necessary step toward better understanding cryovolcanic processes. We have developed a new apparatus for growing clathrate hydrates samples with controlled geometry, composition, and grain size. This system consists of a high-pressure autoclave and a cooling system and supports gas pressures up to 500 bars, and temperatures within the range -50 - 150 °C. We have started the production of clathrate hydrates of CH4, CO2, and N2 with this system, with the purpose to test their mechanical properties using an Instron compression system (Castillo-Rogez et al., submitted to J. Geophys. Res.; Castillo-Rogez et al., this meeting). We will present initial measurements on the creep response and on the viscoelastic response of clathrate hydrates as a function of frequency. These measurements will provide new information on the behavior of clathrate hydrates during dynamic motions within icy satellites.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Jaiswal, Priyank
The goal of this project was to determine structural and stratigraphic controls on hydrate occurrence and distribution in Green Canyon (GC) 955 and Walker Ridge (WR) 313 blocks using seismic and well data. Gas hydrate was discovered in these blocks in coarse- and fine-grained sediments during the 2009 Joint Industrial project (JIP) Leg 11 drilling expedition. Although the immediate interest of the exploration community is exclusively hydrate which is present in coarse–grained sediments, factors that control hydrate and free gas distribution in the two blocks and whether coarse and fine-grained hydrate-bearing units are related in any manner, formed the coremore » of this research. The project spanned from 10/01/2012 to 07/31/2016. In the project, in both the leased blocks, the interval spanning the gas hydrate stability zone (GHSZ) was characterized using a joint analysis of sparse Ocean Bottom Seismic (OBS) and dense, surface–towed multichannel seismic (MCS) data. The project team had the luxury of calibrating their results with two well logs. Advance processing methods such as depth migration and full-waveform inversion (FWI) were used for seismic data analysis. Hydrate quantification was achieved through interpretation of the FWI velocity field using appropriate rock physics models at both blocks. The seismic modeling/inversion methodology (common to both GC955 and WR313 blocks) was as follows. First, the MCS data were depth migrated using a P-wave velocity (VP) model constructed using inversion of reflection arrival times of a few (four in both cases) key horizons carefully picked in the OBS data to farthest possible offsets. Then, the resolution of the traveltime VP model was improved to wavelength scale by inverting OBS gathers up to the highest frequency possible (21.75 Hz for GC955 and 17.5 for WR313) using FWI. Finally, the hydrate saturation (or the volume fraction) was estimated at the well location assuming one of the other hydrate morphology (filling the primary or the secondary porosity) was extrapolated out from the wells using the FWI VP as a guide. General outcomes were as follows. First and foremost, an imaging methodology using sparse seismic data, which is easily replicable at other sites with similar datasets, has been demonstrated. The end product of this methodology at both the leased blocks is quantitative estimates of hydrate distribution. Second, at both locations there is strong evidence that the base of the GHSZ, which does not appear as a clear Bottom Simulating Reflection (BSR), manifests in the VP perturbations created by FWI, suggesting that FWI is sensitive to subtle compositional changes in shallow sediments and establishes it as a valuable tool for investigations of hydrate-bearing basins. Third, through joint interpretation of the depth migrated image and the FWI VP model, how structure and stratigraphy jointly determine hydrate and free gas distribution in both blocks could be clearly visualized. The joint interpretation also suggests that the coarse and fine grained hydrate-bearing sediments at both leased are connected. Site specific results, in addition to general results, are as follows. At GC955 the overlying fine-grained hydrate-bearing unit could have been sourced from the underlying hydrate coarse-grained channel-levee complex through a chimney feature. The channel-levee system at GC955 is compartmentalized by faults, of which only a few may be impermeable. Although compartmentalized, the channel-levee system in the GC955 as a whole might be in communication except selected zones. At WR313 the overlying fine-grained fracture-filled hydrate unit appears to be sourced from below the GHSZ. The reason that only a particular fine-grained unit has hydrate, despite having lower porosity that the bounding units, could be the presence of secondary porosity (such as those formed from clay dewatering under compaction). In conclusion, the project was a pioneering effort in in joint analysis of OBS and MCS datasets for advancing the knowledge about a hydrate and free–gas system dynamics using advanced processing methods such as FWI and depth migration. Results obtained in this project can greatly advance the tools and techniques used for delineating specific hydrate prospects. Results obtained in this project can also be seamlessly incorporated into other DOE funded project on modeling the potential productivity and commercial viability of hydrate from sand-dominated reservoirs. The OBS and MCS data in this project were acquired in 2012 (after the JIP II drilling) by the USGS and therefore the results are a posteriori. Nonetheless, the seismic inversion workflow established through this project can be used to generate various what-if quantification scenarios even in absence of logs and serve as a valuable tool for guiding drilling operations. Results from this project can augment other DOE sponsored projects on determining the commercial viability of methane production from the Gulf of Mexico.« less
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Craig, Laura; Stillings, Lisa; Decker, David L.
2017-01-01
Adsorption using activated alumina is a simple method for removing fluoride from drinking water, but to be cost effective the adsorption capacity must be high and effective long-term. The intent of this study was to assess changes in its adsorption capacity under varied conditions. This was determined by evaluating the physico-chemical properties, surface charge, and fluoride (F−) adsorption capacity and rate of activated alumina under conditions such as hydration period, particle size, and slow vs. fast titrations. X-ray diffraction and scanning electron microscopy analyses show that the mineralogy of activated alumina transformed to boehmite, then bayerite with hydration period and a corresponding reduction in adsorption capacity was expected; while surface area analyses show no notable changes with hydration period or particle size. The pH dependent surface charge was three times higher using slow potentiometric titrations as compared to fast titrations (due largely to diffusion into pore space), with the surface acidity generally unaffected by hydration period. Results from batch adsorption experiments similarly show no change in fluoride adsorption capacity with hydration period. There was also no notable difference in fluoride adsorption capacity between the particle size ranges of 0.5–1.0 mm and 0.125–0.250 mm, or with hydration period. However, adsorption rate increased dramatically with the finer particle sizes: at an initial F− concentration of 0.53 mmol L−1 (10 mg L−1), 90% was adsorbed in the 0.125–0.250 mm range after 1 h, while the 0.5–1.0 mm range required 24 h to achieve 90% adsorption. Also, the pseudo-second-order adsorption rate constants for the finer vs. larger particle sizes were 3.7 and 0.5 g per mmol F− per min respectively (24 h); and the initial intraparticle diffusion rate of the former was 2.6 times faster than the latter. The results show that adsorption capacity of activated alumina remains consistent and high under the conditions evaluated in this study, but in order to increase adsorption rate, a relatively fine particle size is recommended.
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Kwon, Yang-Hee; Kang, Sung-Hoon; Hong, Sung-Gul; Moon, Juhyuk
2017-02-24
Without using strong alkaline solution or ordinary Portland cement, a new structural binder consisting of fly ash and hydrated lime was hardened through an intensified pozzolanic reaction. The main experimental variables are the addition of silica fume and initial thermal treatment (60 °C for 3 days). A series of experiments consisting of mechanical testing (compressive and flexural strength, modulus of elasticity), X-ray diffraction, and measurements of the heat of hydration, pore structure, and shrinkage were conducted. These tests show that this new fly ash-based mortar has a compressive strength of 15 MPa at 91 days without any silica fume addition or initial thermal treatment. The strength increased to over 50 MPa based on the acceleration of the intensified pozzolanic reaction from the silica fume addition and initial thermal treatment. This is explained by a significant synergistic effect induced by the silica fume. It intensifies the pozzolanic reaction under thermal treatment and provides a space filling effect. This improved material performance can open a new pathway to utilize the industrial by-product of fly ash in cementless construction materials.
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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.
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Revisiting the horizontal redistribution of water in soils: Experiments and numerical modeling.
Zhuang, L; Hassanizadeh, S M; Kleingeld, P J; van Genuchten, M Th
2017-09-01
A series of experiments and related numerical simulations were carried out to study one-dimensional water redistribution processes in an unsaturated soil. A long horizontal Plexiglas box was packed as homogenously as possible with sand. The sandbox was divided into two sections using a very thin metal plate, with one section initially fully saturated and the other section only partially saturated. Initial saturation in the dry section was set to 0.2, 0.4, or 0.6 in three different experiments. Redistribution between the wet and dry sections started as soon as the metal plate was removed. Changes in water saturation at various locations along the sandbox were measured as a function of time using a dual-energy gamma system. Also, air and water pressures were measured using two different kinds of tensiometers at various locations as a function of time. The saturation discontinuity was found to persist during the entire experiments, while observed water pressures were found to become continuous immediately after the experiments started. Two models, the standard Richards equation and an interfacial area model, were used to simulate the experiments. Both models showed some deviations between the simulated water pressures and the measured data at early times during redistribution. The standard model could only simulate the observed saturation distributions reasonably well for the experiment with the lowest initial water saturation in the dry section. The interfacial area model could reproduce observed saturation distributions of all three experiments, albeit by fitting one of the parameters in the surface area production term.
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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.
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Comparison on Promotion Effect of Various Types of Surfactants on HCFC-141b Hydrate Induction Time
NASA Astrophysics Data System (ADS)
Li, Juan; Sun, Zhigao; Liu, Chenggang; Zhu, Minggui
2018-03-01
Cold storage in air conditioning based on refrigerant hydrate is a new-type energy saving technology to reduce initial investment and running cost of air conditioning equipments and improve system stability. Refrigerant hydrate is generated under critical temperature and pressure condition, while surfactant is an effective medium to promote its phase equilibrium. In this paper, in order to research such promotion effect, different type of surfactants with unique mechanism, SDS, Tween80 and Span80, n-BA were selected to compare the respective impact on HCFC141b hydrate induction time based on temperature curve. Experimental results showed that no obvious change had been discovered when no surfactant was added into pure water system, which coincided with phase equilibrium diagram of HCFC141b. All the four kinds of surfactants had realized promotion effect to various degrees. For each hydration system, a large gap existed between the longest and the shortest induction time in 6 groups of parallel experiments, meaning relatively poor system stability. Under the combined effect of Tween80 (2wt%), Span80 (0.1wt%) and n-BA (0.1wt%), average and the shortest induction time was 20.9min and 17.5min respectively, corresponding to the best promotion effect.
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NASA Astrophysics Data System (ADS)
Matsumoto, R.; Kakuwa, Y.; Snyder, G. T.; Tanahashi, M.; Yanagimoto, Y.; Morita, S.
2016-12-01
The initial scientific research that was carried out between 2004 and 2013 has provided us with invaluable evidence that gas hydrates occur widely on and below the sea floor down to approximately 30 mbsf within gas chimney structures in Japan Sea (Matsumoto, 2005; 2009). In 2013, METI (Ministry of Economy, Trade and Industry) launched a 3-year exploration project to assess the resource potential of shallow gas hydrates in Japan Sea. During the course of the project, Meiji University and AIST conducted: sea-going geophysical surveys with AUV, and high resolution 3D seismic and CSEM. These were followed by LWD and coring down to BSR depths, and coupled with a number of analyses and experiments. Regional mapping by MBES and SBP has confirmed 1742 gas chimneys in an area of 64,000km2 along the eastern margin of Japan Sea and around Hokkaido. Multiple LWD operations have revealed anomalous profiles such as extremely low natural gamma ray, high velocity Vp, and high resistivity Ro down to BSR depths, providing a strong indication that thick and massive gas hydrates exist throughout gas chimneys above the BSR. In several cases, conventional coring using 6-m long core liners recovered nearly 6 m long massive gas hydrates in several horizons adjacent to the anomalous LWD sites.The PCTB pressure coring system (Geotek Ltd) successfully cored 2-m long intervals of undisturbed, pressurized hydrate-bearing cores, providing valuable information about the in-situ occurrence and textural relations of hydrate and surrounding sediments. Full dissociation and slow degassing experiments of pressurized cores were conducted using onboard PCATS (Pressure core analysis and transfer system) to measure the amount of gases from hydrates. The mean volume fraction of gas hydrates in well-developed gas chimney structures is estimated to be 30 to 86 vol.% based on coupled PCATS and chloride anomaly profiles. Such an unusually high accumulation of gas hydrates in gas chimneys is assumed to have been caused by high TOC accumulation in rifted basins, followed by enhanced thermal maturation by high heat flow of young Japan Sea and, the subsequent migration of deep seated thermogenic gases as a consequence of the tectonic inversion some million years ago. This study was conducted under the commission from AIST as a part of the methane hydrate project of METI.
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NASA Astrophysics Data System (ADS)
Hamilton, T. S.; Enkin, R. J.; Esteban, L.
2007-05-01
Bulk magnetic properties provide a sensitive measure of sedimentary diagenesis related to the stability and growth of gas hydrates. The deposit at Mallik (Mackenzie Delta, Canadian Arctic) occurs in unconsolidated Tertiary sands, but is absent in interstratified silt layers. A detailed sampling of the JAPEX/JNOC/GSC Mallik 5L-38 core tested the use of magnetic properties for detecting diagenetic changes related to the hydrate. Petrographic studies reveal that the sands are well sorted and clean, with quartz > chert >> muscovite and little fines content. Excepting a few rare bands of indurated dolomite in the midst of the gas hydrate zone, there is little or no cementation in the sands. Detrital magnetite is the dominant magnetic mineral, comprising up to a few percent of the sand grain population. In contrast, the muddier layers have a somewhat different detrital grain composition, richer in lithic (sedimentary and metamorphic) grains, feldspar, and clays. They are extensively diagenetically altered (to as much as 30- 40%) and cemented with carbonates, clays, chlorite and the iron sulphide greigite (the dominant magnetic mineral). The greigite is recognized by its isotropic creamy-white reflectance, cubic to prismatic habit, and characteristic tarnish to faintly bluish bireflectant mackinawite. Habits range from disseminated cubes and colliform masses to inflationary massive sulphide veins and clots. Rare detrital grains of magnetite were observed among the silt grains, but never in a reaction relationship or overgrown. Instead the greigite has nucleated separately, in tensional fractures and granular masses up to 4 mm across. In this particular sediment sequence, being so quartz and chert rich, there is insufficient local source for the introduced cements (calcite, dolomite, greigite, clays, jarosite), so ions must have been introduced by fluid flow. Magnetic studies reveal a bi-modal character related to the lithology (sands versus silts) and their magnetic mineralogy. Silt samples are significantly stronger than sand samples in saturation magnetization and magnetic susceptibility. The silt samples have single-domain to pseudo-single domain coercivity ratios whereas the gas hydrate bearing sands have a more multi-domain nature. Sands with current gas hydrate concentrations > 80% have less magnetic material and single domain characteristics. The source of the greigite, carbonates, and other diagenetic minerals was apparently concentrated solutes excluded from formation waters by the freezing and formation of the water dominated gas hydrate. The hydrates served as a cementing agent for the unconsolidated sediments, allowing them to fracture. Some layers have been so inflated by the introduction carbonate and sulfide cements that they resemble hydrothermal tufa and skarns with floating sand grains. In the silts, the magnetic properties reflect the mixture of primary detrital magnetite and diagenetic greigite in various grain sizes and concentrations. At Mallik, the magnetic properties are sensitive to the diagenetic mineralogy and redox state associated with the transport of methane and pore fluids and the creation of gas hydrates. Hypersaline brines, produced by solute exclusion from pore waters, fractured and inflated less permeable sediments and forced rapid disequilibrium growth of greigite without dissolving primary detrital magnetite grains.
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NASA Astrophysics Data System (ADS)
Hsu, S. Y.; Chen, H.; Huang, Q. Z.; Lee, T. Y.; Chiu, Y.; Chang, L. C.; Lamorski, K.; Sławiński, C.; Tsao, C. W.
2017-12-01
The interplay between resident ("old") fluid already in the vadose zone and infiltrating ("new") fluid was examined with micromodel experiments. The geometric patterns of the micromodels are based on a pore doublet and a 2D pore geometry of a sand-packing soil scanned by Micro X-Ray CT. We studied the old and new fluid interaction during imbibition process subject to different evaporation times (different the initial old fluid saturations). The results found that, in the pore-doublet micromodel experiment, the old fluid was mixed and displaced by the new fluid, and an increase in the initial old fluid saturation led to a decrease in the amount of old fluid displaced by the new fluid. On the other hand, the most of the old fluid in the micromodel of 2D sand-packing pore geometry was displaced by and mixed with the new fluid. However, a small amount of the initial old fluid that occupied pore throats remained untouched by the new fluid due to the air blockage. The amount of untouched old fluid increased as the initial old fluid saturation decreased. Our finding reveals the effect of pore geometry and inital old fluid distribution on the interaction between resident and infiltrating fluids.
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Application of reusable PZT sensors for monitoring initial hydration of concrete
NASA Astrophysics Data System (ADS)
Sabet Divsholi, Bahador; Yang, Yaowen
2009-03-01
To increase the efficiency of in-situ casting or precast of concrete, determining the optimal time of demolding is very important for concrete suppliers. In the first few hours after mixing, the fresh concrete gradually achieves solid properties with reasonable compressive strength. Due to different type and amount of cementitious materials, concrete additives (e.g. retarders) and curing temperature, different rates of hardening are expected. In addition, some other factors like the quality of the cementitious materials further increase the uncertainty in determining appropriate time for demolding of concrete. Electro-mechanical impedance (EMI) based lead zirconate titanate (PZT) sensors have been used for damage detection and structural identification for various engineering structures. In this work, a reusable PZT sensor for monitoring initial hydration of concrete is developed, where a piece of PZT is bonded to a piece of metal with two bolts tightened inside of the holes drilled in the metal. An impedance analyzer is used to acquire the signature of this reusable sensor. During the concrete casting, the bolts and the bottom surface of the metal is set to penetrate part of the fresh concrete. At different stages of the first 48 hours after casting, the PZT signatures are acquired. A statistical analysis technique is employed to associate the change in concrete strength with the changes in the PZT admittance signatures. The results show that the developed sensor is able to effectively monitor the initial hydration of concrete, and can be detached from the concrete for future use.
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The impact of flow focusing on gas hydrate accumulations in overpressured marine sediments
DOE Office of Scientific and Technical Information (OSTI.GOV)
Nole, Michael; Daigle, Hugh; Cook, Ann
This study demonstrates the potential for flow focusing due to overpressuring in marine sedimentary environments to act as a significant methane transport mechanism from which methane hydrate can precipitate in large quantities in dipping sandstone bodies. Traditionally, gas hydrate accumulations in nature are discussed as resulting from either short-range diffusive methane migration or from long-range advective fluid transport sourced from depth. However, 3D simulations performed in this study demonstrate that a third migration mechanism, short-range advective transport, can provide a significant methane source that is unencumbered by limitations of the other two end-member mechanisms. Short-range advective sourcing is advantageous overmore » diffusion because it can convey greater amounts of methane to sands over shorter timespans, yet it is not necessarily limited by down-dip pore blocking in sands as is typical of updip advection from a deep source. These results are novel because they integrate pore size impacts on spatial solubility gradients, grid block properties that evolve through time, and methane sourcing through microbial methanogenesis into a holistic characterization of environments exposed to multiple methane hydrate sourcing mechanisms. We show that flow focusing toward sand bodies transports large quantities of methane, the magnitude of which are determined by the sand-clay solubility contrast, and generates larger quantities of hydrate in sands than a solely diffusive system; after depositing methane as hydrate, fluid exiting a sand body is depleted in methane and leaves a hydrate free region in its wake above the sand. Additionally, we demonstrate that in overpressured environments, hydrate growth is initially diffusively dominated before transitioning to an advection-dominated regime. The timescale and depth at which this transition takes place depends primarily on the rate of microbial metabolism and the sedimentation rate but only depends loosely on the degree of overpressuring.« less
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Magnetic Diagenesis in the Gas Hydrate System
NASA Astrophysics Data System (ADS)
Enkin, R. J.; Hamilton, T. S.; Esteban, L.
2009-05-01
Natural gas hydrate is a methane-bearing form of ice which occurs in permafrost and continental slope settings. Geochemical processes associated with gas hydrate formation lead to the growth of iron sulphides which have a geophysically measurable magnetic signature. Detailed magnetic investigation and complementary petrological observations were undertaken on unconsolidated sediments from three gas hydrate (GH) settings: permafrost in fluvial-deltaic silts and sands in the Western Canadian Arctic (Japex et al. Mallik 5L-38 in 2002); diamictons and hemipelagics in the Cascadia accretionary wedge west of Vancouver Island (IODP Exp.311 in 2006); and marine sands and hemipelagics from the Bay of Bengal (NGHP Exp.01 in 2007). These magnetic measurements provide stratigraphic profiles which reveal fine scale variations in lithology, magnetic grain size, and paleo-pore fluid geochemistry. The highest magnetic susceptibility values are observed in strata which preserve high initial concentrations of detrital magnetite, such as glacial deposits. The lowest values of magnetic susceptibility are observed where iron has been reduced to paramagnetic pyrite, formed in settings with high methane and sulphate flux such as at methane vents. Enhanced values of magnetic susceptibility characterize the introduction of the ferrimagnetic iron sulphide minerals greigite and smythite. These magnetic minerals are mostly found immediately adjacent to the sedimentary horizons which host the gas hydrate and their textures and compositions indicate rapid disequilibrium crystallization. The observed diagenesis result from the unique physical and geochemical properties of the environment where gas hydrates form: methane is available to fuel microbiological activity and the freezing which accompanied GH crystallization quickly removed pure water, froze the sediments into an impermeable solid and expelled more concentrated brines into the adjacent less permeable strata to the point of inducing fracture formation. Magnetic surveying techniques can help delineate anomalies related to gas hydrate deposits, and magnetic logging of wells and core samples provide information on the original lithology and diagenesis caused by gas hydrate formation.