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Sample records for hydrate dissociation mechanisms

  1. Experimental Study on Mechanism of Depressurizing Dissociation of Methane Hydrate under Saturated Pore Fluid

    Institute of Scientific and Technical Information of China (English)

    Sun Youhong; Su Kai; Guo Wei; Li Bing; Jia Rui

    2016-01-01

    Sediment-hosted hydrate reservoir often contains saturated pore lfuid, which changes the heat transfer and mass transfer characteristics of the hydrate reservoir. The exploitation of hydrate under saturated pore lfuid using depressurization is simulated experimentally to investigate the inlfuence of particle size of porous media, dissociation temperature, pressure drop and injected lfuid type on gas production behavior. Homogeneous methane hydrate was ifrstly formed in frozen quartz sand. With the formed hydrate sample, hydrate dissociation experiments by depressurization were conducted. The test results showed that the gas production rate of hydrate under saturated pore lfuid was substantially inlfuenced by the particle size, the pressure drop and the injected lfuid type, while it was inlfuenced little by the dissociation temperature. The hydrate dissociates faster under larger pressure drop and in the presence of smaller porous media within the experimental region. The dissociation rate increases with an increasing lfuid salinity in the initial stage, while it decreases in the later stage. The increase of gas diffusion resistance resulted from ionic hydration atmosphere in saturated chloride solution impeded the dissociation of hydrate. It can be solved by increasing the pressure drop and decreasing the lfuid salinity in the process of gas recovery from hydrate reservoir.

  2. A molecular dynamic study on the dissociation mechanism of SI methane hydrate in inorganic salt aqueous solutions.

    Science.gov (United States)

    Xu, Jiafang; Chen, Zhe; Liu, Jinxiang; Sun, Zening; Wang, Xiaopu; Zhang, Jun

    2017-08-01

    Gas hydrate is not only a potential energy resource, but also almost the biggest challenge in oil/gas flow assurance. Inorganic salts such as NaCl, KCl and CaCl2 are widely used as the thermodynamic inhibitor to reduce the risk caused by hydrate formation. However, the inhibition mechanism is still unclear. Therefore, molecular dynamic (MD) simulation was performed to study the dissociation of structure I (SI) methane hydrate in existence of inorganic salt aqueous solution on a micro-scale. The simulation results showed that, the dissociation became stagnant due to the presence of liquid film formed by the decomposed water molecules, and more inorganic ions could shorten the stagnation-time. The diffusion coefficients of ions and water molecules were the largest in KCl system. The structures of ion/H2O and H2O/H2O were the most compact in hydrate/NaCl system. The ionic ability to decompose hydrate cells followed the sequence of: Ca(2+)>2K(+)>2Cl(-)>2Na(+). Copyright © 2017 Elsevier Inc. All rights reserved.

  3. Gas hydrate dissociation structures in submarine slopes

    Energy Technology Data Exchange (ETDEWEB)

    Gidley, I.; Grozic, J.L.H. [Calgary Univ., AB (Canada). Dept. of Civil Engineering

    2008-07-01

    Studies have suggested that gas hydrates may play a role in submarine slope failures. However, the mechanics surrounding such failures are poorly understood. This paper discussed experimental tests conducted on a small-scale physical model of submarine soils with hydrate inclusions. The laboratory tests investigated the effects of slope angle and depth of burial of the hydrate on gas escape structures and slope stability. Laponite was used to model the soils due to its ability to swell and produce a clear, colorless thixotropic gel when dispersed in water. An R-11 refrigerant was used to form hydrate layers and nodules. The aim of the experiment was to investigate the path of the fluid escape structures and the development of a subsequent slip plane caused by the dissociation of the R-11 hydrates. Slope angles of 5, 10, and 15 degrees were examined. Slopes were examined using high-resolution, high-speed imaging techniques. Hydrate placement and slope inclinations were varied in order to obtain stability data. Results of the study showed that slope angle influenced the direction of travel of the escaping gas, and that the depth of burial affected sensitivity to slope angle. Theoretical models developed from the experimental data have accurately mapped deformations and stress states during testing. Further research is being conducted to investigate the influence of the size, shape, and placement of the hydrates. 30 refs., 15 figs.

  4. Experimental Dissociation of Methane Hydrates Through Depressurization

    Science.gov (United States)

    Borgfeldt, T.; Flemings, P. B.; Meyer, D.; You, K.

    2015-12-01

    We dissociated methane hydrates by stepwise depressurization. The initial hydrates were formed by injecting gas into a cylindrical sample of brine-saturated, coarse-grained sand at hydrate-stable conditions with the intention of reaching three-phase equilibrium. The sample was initially at 1°C with a pore pressure of 1775 psi and a salinity of 7 wt. % NaBr. The depressurization setup consisted of one pump filled with tap water attached to the confining fluid port and a second pump attached to the inlet port where the methane was injected. Depressurization was conducted over sixteen hours at a constant temperature of 1°C. The pore pressure was stepwise reduced from 1775 psi to atmospheric pressure by pulling known volumes of gas from the sample. After each extraction, we recorded the instantaneous and equilibrium pore pressure. 0.503 moles of methane were removed from the sample. The pore pressure decreased smoothly and nonlinearly with the cumulative gas withdrawn from the sample. We interpret that hydrate began to dissociate immediately with depressurization, and it continued to dissociate when the pressure decreased below the three-phase pressure for 1°C and 0 wt. % salinity. Two breaks in slope in the pressure vs. mass extracted data are bounded by smooth, nonlinear curves with differing slopes on either side. We attribute the breaks to dissociation of three zones of hydrate concentration. We created a box model to simulate the experimental behavior. For a 10% initial gas saturation (estimated from the hydrate formation experiment and based on mass conservation), an initial hydrate saturation of 55% is required to match the total methane extracted from the sample. Future experiments will be conducted over a longer timespan while monitoring hydrate dissociation with CT imaging throughout the process.

  5. Stability evaluation of hydrate-bearing sediments during thermally-driven hydrate dissociation

    Science.gov (United States)

    Kwon, T.; Cho, G.; Santamarina, J.; Kim, H.; Lee, J.

    2009-12-01

    Hydrate-bearing sediments may destabilize spontaneously as part of geological processes, unavoidably during petroleum drilling/production operations, or intentionally as part of gas extraction from the hydrate itself. In all cases, high pore fluid pressure generation is anticipated during hydrate dissociation. This study examined how thermal changes destabilize gas hydrate-bearing sediments. First, an analytical formulation was derived for predicting fluid pressure evolution in hydrate-bearing sediments subjected to thermal stimulation without mass transfer. The formulation captures the self-preservation behavior, calculates the hydrate and free gas quantities during dissociation, considering effective stress-controlled sediment compressibility and gas solubility in aqueous phase. Pore fluid pressure generation is proportional to the initial hydrate fraction and the sediment bulk stiffness; is inversely proportional to the initial gas fraction and gas solubility; and is limited by changes in effective stress that cause the failure of the sediment. Second, the analytical formulation for hydrate dissociation was incorporated as a user-defined function into a verified finite difference code (FLAC2D). The underlying physical processes of hydrate-bearing sediments, including hydrate dissociation, self-preservation, pore pressure evolution, gas dissolution, and sediment volume expansion, were coupled with the thermal conduction, pore fluid flow, and mechanical response of sediments. We conducted the simulations for a duration of 20 years, assuming a constant-temperature wellbore transferred heat to the surrounding hydrate-bearing sediments, resulting in dissociation of methane hydrate in the well vicinity. The model predicted dissociation-induced excess pore fluid pressures which resulted in a large volume expansion and plastic deformation of the sediments. Furthermore, when the critical stress was reached, localized shear failure of the sediment around the borehole was

  6. Controls on Gas Hydrate Formation and Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Miriam Kastner; Ian MacDonald

    2006-03-03

    The main objectives of the project were to monitor, characterize, and quantify in situ the rates of formation and dissociation of methane hydrates at and near the seafloor in the northern Gulf of Mexico, with a focus on the Bush Hill seafloor hydrate mound; to record the linkages between physical and chemical parameters of the deposits over the course of one year, by emphasizing the response of the hydrate mound to temperature and chemical perturbations; and to document the seafloor and water column environmental impacts of hydrate formation and dissociation. For these, monitoring the dynamics of gas hydrate formation and dissociation was required. The objectives were achieved by an integrated field and laboratory scientific study, particularly by monitoring in situ formation and dissociation of the outcropping gas hydrate mound and of the associated gas-rich sediments. In addition to monitoring with the MOSQUITOs, fluid flow rates and temperature, continuously sampling in situ pore fluids for the chemistry, and imaging the hydrate mound, pore fluids from cores, peepers and gas hydrate samples from the mound were as well sampled and analyzed for chemical and isotopic compositions. In order to determine the impact of gas hydrate dissociation and/or methane venting across the seafloor on the ocean and atmosphere, the overlying seawater was sampled and thoroughly analyzed chemically and for methane C isotope ratios. At Bush hill the pore fluid chemistry varies significantly over short distances as well as within some of the specific sites monitored for 440 days, and gas venting is primarily focused. The pore fluid chemistry in the tub-warm and mussel shell fields clearly documented active gas hydrate and authigenic carbonate formation during the monitoring period. The advecting fluid is depleted in sulfate, Ca Mg, and Sr and is rich in methane; at the main vent sites the fluid is methane supersaturated, thus bubble plumes form. The subsurface hydrology exhibits both

  7. Stability Analysis of Methane Hydrate-Bearing Soils Considering Dissociation

    Directory of Open Access Journals (Sweden)

    Hiromasa Iwai

    2015-06-01

    Full Text Available It is well known that the methane hydrate dissociation process may lead to unstable behavior such as large ground deformations, uncontrollable gas production, etc. A linear instability analysis was performed in order to investigate which variables have a significant effect on the onset of the instability behavior of methane hydrate-bearing soils subjected to dissociation. In the analysis a simplified viscoplastic constitutive equation is used for the soil sediment. The stability analysis shows that the onset of instability of the material system mainly depends on the strain hardening-softening parameter, the degree of strain, and the permeability for water and gas. Then, we conducted a numerical analysis of gas hydrate-bearing soil considering hydrate dissociation in order to investigate the effect of the parameters on the system. The simulation method used in the present study can describe the chemo-thermo-mechanically coupled behaviors such as phase changes from hydrates to water and gas, temperature changes and ground deformation. From the numerical results, we found that basically the larger the permeability for water and gas is, the more stable the simulation results are. These results are consistent with those obtained from the linear stability analysis.

  8. The role of water in gas hydrate dissociation

    Science.gov (United States)

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

    2004-01-01

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

  9. Thermal dissociation behavior and dissociation enthalpies of methane-carbon dioxide mixed hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, T.H.; Kneafsey, T.J.; Rees, E.V.L.

    2011-02-15

    Replacement of methane with carbon dioxide in hydrate has been proposed as a strategy for geologic sequestration of carbon dioxide (CO{sub 2}) and/or production of methane (CH{sub 4}) from natural hydrate deposits. This replacement strategy requires a better understanding of the thermodynamic characteristics of binary mixtures of CH{sub 4} and CO{sub 2} hydrate (CH{sub 4}-CO{sub 2} mixed hydrates), as well as thermophysical property changes during gas exchange. This study explores the thermal dissociation behavior and dissociation enthalpies of CH{sub 4}-CO{sub 2} mixed hydrates. We prepared CH{sub 4}-CO{sub 2} mixed hydrate samples from two different, well-defined gas mixtures. During thermal dissociation of a CH{sub 4}-CO{sub 2} mixed hydrate sample, gas samples from the head space were periodically collected and analyzed using gas chromatography. The changes in CH{sub 4}-CO{sub 2} compositions in both the vapor phase and hydrate phase during dissociation were estimated based on the gas chromatography measurements. It was found that the CO{sub 2} concentration in the vapor phase became richer during dissociation because the initial hydrate composition contained relatively more CO{sub 2} than the vapor phase. The composition change in the vapor phase during hydrate dissociation affected the dissociation pressure and temperature; the richer CO{sub 2} in the vapor phase led to a lower dissociation pressure. Furthermore, the increase in CO{sub 2} concentration in the vapor phase enriched the hydrate in CO{sub 2}. The dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate was computed by fitting the Clausius-Clapeyron equation to the pressure-temperature (PT) trace of a dissociation test. It was observed that the dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate lays between the limiting values of pure CH{sub 4} hydrate and CO{sub 2} hydrate, increasing with the CO{sub 2} fraction in the hydrate phase.

  10. Methane hydrate formation and dissociation in synthetic seawater

    Institute of Scientific and Technical Information of China (English)

    Vikash Kumar Saw; Iqbal Ahmad; Ajay Mandal; G.Udayabhanu; Sukumar Laik

    2012-01-01

    The formation and dissociation of methane gas hydrate at an interface between synthetic seawater (SSW) and methane gas have been experimentally investigated in the present work.The amount of gas consumed during hydrate formation has been calculated using the real gas equation.Induction time for the formation of hydrate is found to depend on the degree of subcooling.All the experiments were conducted in quiescent system with initial cell pressure of 11.14 MPa.Salinity effects on the onset pressure and temperature of hydrate formation are also observed.The dissociation enthalpies of methane hydrate in synthetic seawater were determined by Clausius-Clapeyron equation based on the measured phase equilibrium data.The dissociation data have been analyzed by existing models and compared with the reported data.

  11. Study of Formation Mechanisms of Gas Hydrate

    Science.gov (United States)

    Yang, Jia-Sheng; Wu, Cheng-Yueh; Hsieh, Bieng-Zih

    2015-04-01

    Gas hydrates, which had been found in subsurface geological environments of deep-sea sediments and permafrost regions, are solid crystalline compounds of gas molecules and water. The estimated energy resources of hydrates are at least twice of that of the conventional fossil fuel in the world. Gas hydrates have a great opportunity to become a dominating future energy. In the past years, many laboratory experiments had been conducted to study chemical and thermodynamic characteristics of gas hydrates in order to investigate the formation and dissociation mechanisms of hydrates. However, it is difficult to observe the formation and dissociation of hydrates in a porous media from a physical experiment directly. The purpose of this study was to model the dynamic formation mechanisms of gas hydrate in porous media by reservoir simulation. Two models were designed for this study: 1) a closed-system static model with separated gas and water zones; this model was a hydrate equilibrium model to investigate the behavior of the formation of hydrates near the initial gas-water contact; and 2) an open-system dynamic model with a continuous bottom-up gas flow; this model simulated the behavior of gas migration and studied the formation of hydrates from flowed gas and static formation water in porous media. A phase behavior module was developed in this study for reservoir simulator to model the pressure-volume-temperature (PVT) behavior of hydrates. The thermodynamic equilibriums and chemical reactions were coupled with the phase behavior module to have functions modelling the formation and dissociation of hydrates from/to water and gas. The simulation models used in this study were validated from the code-comparison project proposed by the NETL. According to the modelling results of the closed-system static model, we found that predominated location for the formation of hydrates was below the gas-water contact (or at the top of water zone). The maximum hydrate saturation

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

    Science.gov (United States)

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

    2013-01-01

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

  13. Kinetics of CH4 and CO2 hydrate dissociation and gas bubble evolution via MD simulation.

    Science.gov (United States)

    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

  14. Numerical studies of hydrate dissociation and gas production behavior in porous media during depressurization process

    Institute of Scientific and Technical Information of China (English)

    Xuke Ruan; Mingjun Yang; Yongchen Song; Haifeng Liang; Yanghui Li

    2012-01-01

    In this study,a numerical model is developed to investigate the hydrate dissociation and gas production in porous media by depressurization.A series of simulation runs are conducted to study the impacts of permeability characteristics,including permeability reduction exponent,absolute permeability,hydrate accumulation habits and hydrate saturation,sand average grain size and irreducible water saturation.The effects of the distribution of hydrate in porous media are examined by adapting conceptual models of hydrate accumulation habits into simulations to govern the evolution of permeability with hydrate decomposition,which is also compared with the conventional reservoir permeability model,i.e.Corey model.The simulations show that the hydrate dissociation rate increases with the decrease of permeability reduction exponent,hydrate saturation and the sand average grain size.Compared with the conceptual models of hydrate accumulation habits,our simulations indicate that Corey model overpredicts the gas production and the performance of hydrate coating models is superior to that of hydrate filling models in gas production,which behavior does follow by the order of capillary coating>pore coating>pore filling>capillary filling.From the analysis of t1/2,some interesting results are suggested as follows:(1) there is a "switch" value (the "switch" absolute permeability) for laboratory-scale hydrate dissociation in porous media,the absolute permeability has almost no influence on the gas production behavior when the permeability exceeds the "switch" value.In this study,the "switch" value of absolute permeability can be estimated to be between 10 and 50 md.(2) An optimum value of initial effective water saturation Sw,e exists where hydrate dissociation rate reaches the maximum and the optimum value largely coincides with the value of irreducible water saturation Swr,e.For the case of Sw,e<Swr,e,or Sw,e>Swr,e,there are different control mechanisms dominating the

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

    Science.gov (United States)

    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

  16. Mechanism of gypsum hydration

    Directory of Open Access Journals (Sweden)

    Pacheco, G.

    1991-06-01

    Full Text Available There is an hypothesis that the mechanism o f gypsum hydration and dehydration is performed through two simultaneous phenomena. In this study we try to clear up this phenomenon using chlorides as accelerators or a mixture of ethanol-methanol as retarders to carry out the gypsum setting. Natural Mexican gypsum samples and a hemihydrate prepared in the laboratory are used. The following analytical techniques are used: MO, DRX, DTA, TG and DTG. In agreement with the obtained results, it can be concluded: that colloid formation depends on the action of accelerators or retarders and the crystals are a consequence of the quantity of hemihydrate formed.

    En el mecanismo de hidratación y deshidratación del yeso existe la hipótesis de que éste se efectúa por dos fenómenos simultáneos. Este estudio intenta esclarecer estos fenómenos, empleando: cloruros como aceleradores o mezcla etanol-metanol como retardadores para efectuar el fraguado del yeso. Se emplean muestras de yeso de origen natural mexicano y hemihydrate preparado en laboratorio; se utilizan técnicas analíticas: MO, DRX, DTA, TG y DTG. De acuerdo a los resultados obtenidos se puede deducir: que la formación del coloide depende de la acción de los agentes aceleradores o retardadores y que los cristales son consecuencia de la cantidad de hemihidrato formado.

  17. Salinity-buffered methane hydrate formation and dissociation in gas-rich systems

    Science.gov (United States)

    You, Kehua; Kneafsey, Timothy J.; Flemings, Peter B.; Polito, Peter; Bryant, Steven L.

    2015-02-01

    Methane hydrate formation and dissociation are buffered by salinity in a closed system. During hydrate formation, salt excluded from hydrate increases salinity, drives the system to three-phase (gas, water, and hydrate phases) equilibrium, and limits further hydrate formation and dissociation. We developed a zero-dimensional local thermodynamic equilibrium-based model to explain this concept. We demonstrated this concept by forming and melting methane hydrate from a partially brine-saturated sand sample in a controlled laboratory experiment by holding pressure constant (6.94 MPa) and changing temperature stepwise. The modeled methane gas consumptions and hydrate saturations agreed well with the experimental measurements after hydrate nucleation. Hydrate dissociation occurred synchronously with temperature increase. The exception to this behavior is that substantial subcooling (6.4°C in this study) was observed for hydrate nucleation. X-ray computed tomography scanning images showed that core-scale hydrate distribution was heterogeneous. This implied core-scale water and salt transport induced by hydrate formation. Bulk resistivity increased sharply with initial hydrate formation and then decreased as the hydrate ripened. This study reproduced the salinity-buffered hydrate behavior interpreted for natural gas-rich hydrate systems by allowing methane gas to freely enter/leave the sample in response to volume changes associated with hydrate formation and dissociation. It provides insights into observations made at the core scale and log scale of salinity elevation to three-phase equilibrium in natural hydrate systems.

  18. Simulation of gas hydrate dissociation caused by repeated tectonic uplift events

    Science.gov (United States)

    Goto, Shusaku; Matsubayashi, Osamu; Nagakubo, Sadao

    2016-05-01

    Gas hydrate dissociation by tectonic uplift is often used to explain geologic and geophysical phenomena, such as hydrate accumulation probably caused by hydrate recycling and the occurrence of double bottom-simulating reflectors in tectonically active areas. However, little is known of gas hydrate dissociation resulting from tectonic uplift. This study investigates gas hydrate dissociation in marine sediments caused by repeated tectonic uplift events using a numerical model incorporating the latent heat of gas hydrate dissociation. The simulations showed that tectonic uplift causes upward movement of some depth interval of hydrate-bearing sediment immediately above the base of gas hydrate stability (BGHS) to the gas hydrate instability zone because the sediment initially maintains its temperature: in that interval, gas hydrate dissociates while absorbing heat; consequently, the temperature of the interval decreases to that of the hydrate stability boundary at that depth. Until the next uplift event, endothermic gas hydrate dissociation proceeds at the BGHS using heat mainly supplied from the sediment around the BGHS, lowering the temperature of that sediment. The cumulative effects of these two endothermic gas hydrate dissociations caused by repeated uplift events lower the sediment temperature around the BGHS, suggesting that in a marine area in which sediment with a highly concentrated hydrate-bearing layer just above the BGHS has been frequently uplifted, the endothermic gas hydrate dissociation produces a gradual decrease in thermal gradient from the seafloor to the BGHS. Sensitivity analysis for model parameters showed that water depth, amount of uplift, gas hydrate saturation, and basal heat flow strongly influence the gas hydrate dissociation rate and sediment temperature around the BGHS.

  19. A constitutive mechanical model for gas hydrate bearing sediments incorporating inelastic mechanisms

    KAUST Repository

    Sánchez, Marcelo

    2016-11-30

    Gas hydrate bearing sediments (HBS) are natural soils formed in permafrost and sub-marine settings where the temperature and pressure conditions are such that gas hydrates are stable. If these conditions shift from the hydrate stability zone, hydrates dissociate and move from the solid to the gas phase. Hydrate dissociation is accompanied by significant changes in sediment structure and strongly affects its mechanical behavior (e.g., sediment stiffenss, strength and dilatancy). The mechanical behavior of HBS is very complex and its modeling poses great challenges. This paper presents a new geomechanical model for hydrate bearing sediments. The model incorporates the concept of partition stress, plus a number of inelastic mechanisms proposed to capture the complex behavior of this type of soil. This constitutive model is especially well suited to simulate the behavior of HBS upon dissociation. The model was applied and validated against experimental data from triaxial and oedometric tests conducted on manufactured and natural specimens involving different hydrate saturation, hydrate morphology, and confinement conditions. Particular attention was paid to model the HBS behavior during hydrate dissociation under loading. The model performance was highly satisfactory in all the cases studied. It managed to properly capture the main features of HBS mechanical behavior and it also assisted to interpret the behavior of this type of sediment under different loading and hydrate conditions.

  20. Formation and Dissociation of Methane Hydrates from Seawater in Consolidated Sand: Mimicking Methane Hydrate Dynamics beneath the Seafloor

    Directory of Open Access Journals (Sweden)

    Prasad B. Kerkar

    2013-11-01

    Full Text Available Methane hydrate formation and dissociation kinetics were investigated in seawater-saturated consolidated Ottawa sand-pack under sub-seafloor conditions to study the influence of effective pressure on formation and dissociation kinetics. To simulate a sub-seafloor environment, the pore-pressure was varied relative to confining pressure in successive experiments. Hydrate formation was achieved by methane charging followed by sediment cooling. The formation of hydrates was delayed with increasing degree of consolidation. Hydrate dissociation by step-wise depressurization was instantaneous, emanating preferentially from the interior of the sand-pack. Pressure drops during dissociation and in situ temperature controlled the degree of endothermic cooling within sediments. In a closed system, the post-depressurization dissociation was succeeded by thermally induced dissociation and pressure-temperature conditions followed theoretical methane-seawater equilibrium conditions and exhibited excess pore pressure governed by the pore diameter. These post-depressurization equilibrium values for the methane hydrates in seawater saturated consolidated sand-pack were used to estimate the enthalpy of dissociation of 55.83 ± 1.41 kJ/mol. These values were found to be lower than those reported in earlier literature for bulk hydrates from seawater (58.84 kJ/mol and pure water (62.61 kJ/mol due to excess pore pressure generated within confined sediment system under investigation. However, these observations could be significant in the case of hydrate dissociation in a subseafloor environment where dissociation due to depressurization could result in an instantaneous methane release followed by slow thermally induced dissociation. The excess pore pressure generated during hydrate dissociation could be higher within fine-grained sediments with faults and barriers present in subseafloor settings which could cause shifting in geological layers.

  1. Monitoring hydrate formation and dissociation in sandstone and bulk with magnetic resonance imaging.

    Science.gov (United States)

    Baldwin, B A; Moradi-Araghi, A; Stevens, J C

    2003-11-01

    Magnetic resonance imaging (MRI) has been shown to be a very effective tool for monitoring the formation and dissociation of hydrates because of the large intensity contrast between the images of the liquid components and the solid hydrate. Tetrahydrofuran/water hydrate was used because the two liquid components are miscible and form hydrate at ambient pressure. These properties made this feasibility study proceed much faster than using methane/water, which requires high pressure to form the hydrate. The formation and dissociation was monitored first in a THF/water-saturated Berea sandstone plug and second in the bulk. In both cases it appeared that nucleation was needed to begin the formation process, i.e., the presence of surfaces in the sandstone and shaking of the bulk solution. Dissociation appeared to be dominated by the rate of thermal energy transfer. The dissociation temperature of hydrate formed in the sandstone plug was not significantly different from the dissociation temperature in bulk.

  2. In situ High-pressure NMR Observations on the Formation and Dissociation of Methane Hydrate

    Institute of Scientific and Technical Information of China (English)

    Ai Bing CHEN; Wei Ping ZHANG; Xi Jie LAN; Heng ZHENG; Xiu Mei LIU; Xiu Wen HAN; Xin He BAO

    2006-01-01

    A home-made static NMR cell with pressure up to 10 MPa was employed to observe the formation and dissociation processes of methane hydrate by in situ 1H and 13C NMR spectroscopies. Methane hydrate can be formed or decomposed in the temperature range of -5 to-13℃ at pressures between 4.0 and 7.0 MPa. The higher methane pressure, the formation or dissociation temperature of methane hydrate was higher. In situ 1H NMR experiments indicated that the critical size of the hydrate clusters is crucial for the formation of methane hydrate.

  3. Methane Hydrate Formation and Dissociation in the Presence of Silica Sand and Bentonite Clay

    Directory of Open Access Journals (Sweden)

    Kumar Saw V.

    2015-11-01

    Full Text Available The formation and dissociation of methane hydrates in a porous media containing silica sand of different sizes and bentonite clay were studied in the presence of synthetic seawater with 3.55 wt% salinity. The phase equilibrium of methane hydrate under different experimental conditions was investigated. The effects of the particle size of silica sand as well as a mixture of bentonite clay and silica sand on methane hydrate formation and its dissociation were studied. The kinetics of hydrate formation was studied under different subcooling conditions to observe its effects on the induction time of hydrate formation. The amount of methane gas encapsulated in hydrate was computed using a real gas equation. The Clausius-Clapeyron equation is used to estimate the enthalpy of hydrate dissociation with measured phase equilibrium data.

  4. Transient seafloor venting on continental slopes from warming-induced methane hydrate dissociation

    Science.gov (United States)

    Darnell, K. N.; Flemings, P. B.

    2015-12-01

    Methane held in frozen hydrate cages within marine sediment comprises one of the largest carbon reservoirs on the planet. Recent submarine observations of widespread methane seepage may record hydrate dissociation due to oceanic warming, which consequently may further amplify climate change. Here we simulate the effect of seafloor warming on marine hydrate deposits using a multiphase flow model. We show that hydrate dissociation, gas migration, and subsequent hydrate formation cangenerate temporary methane venting into the ocean through the hydrate stability zone. Methane seeps venting through the hydrate stability zone on the eastern Atlantic margin may record this process due to warming begun thousands of years ago. Our results contrast with the traditional view that venting occurs only updip of the hydrate stability zone.

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

    Science.gov (United States)

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

    2003-01-01

    Structure I (sI) carbon dioxide (CO2) hydrate exhibits markedly different dissociation behavior from sI methane (CH4) hydrate in experiments in which equilibrated samples at 0.1 MPa are heated isobarically at 13 K/h from 210 K through the H2O melting point (273.15 K). The CO2 hydrate samples release only about 3% of their gas content up to temperatures of 240 K, which is 22 K above the hydrate phase boundary. Up to 20% is released by 270 K, and the remaining CO2 is released at 271.0 plusmn; 0.5 K, where the sample temperature is buffered until hydrate dissociation ceases. This reproducible buffering temperature for the dissociation reaction CO2??nH2O = CO2(g) + nH2O(1 to s) is measurably distinct from the pure H2O melting point at 273.15 K, which is reached as gas evolution ceases. In contrast, when si CH4 hydrate is heated at the same rate at 0.1 MPa, >95% of the gas is released within 25 K of the equilibrium temperature (193 K at 0.1 MPa). In conjunction with the dissociation study, a method for efficient and reproducible synthesis of pure polycrystalline CO2 hydrate with suitable characteristics for material properties testing was developed, and the material was characterized. CO2 hydrate was synthesized from CO2 liquid and H2O solid and liquid reactants at pressures between 5 and 25 MPa and temperatures between 250 and 281 K. Scanning electron microscopy (SEM) examination indicates that the samples consist of dense crystalline hydrate and 50-300 ??m diameter pores that are lined with euhedral cubic hydrate crystals. Deuterated hydrate samples made by this same procedure were analyzed by neutron diffraction at temperatures between 4 and 215 K; results confirm that complete conversion of water to hydrate has occurred and that the measured unit cell parameter and thermal expansion are consistent with previously reported values. On the basis of measured weight gain after synthesis and gas yields from the dissociation experiments, approximately all cages in the

  6. Heat Transfer Analysis of Methane Hydrate Sediment Dissociation in a Closed Reactor by a Thermal Method

    Directory of Open Access Journals (Sweden)

    Mingjun Yang

    2012-05-01

    Full Text Available The heat transfer analysis of hydrate-bearing sediment involved phase changes is one of the key requirements of gas hydrate exploitation techniques. In this paper, experiments were conducted to examine the heat transfer performance during hydrate formation and dissociation by a thermal method using a 5L volume reactor. This study simulated porous media by using glass beads of uniform size. Sixteen platinum resistance thermometers were placed in different position in the reactor to monitor the temperature differences of the hydrate in porous media. The influence of production temperature on the production time was also investigated. Experimental results show that there is a delay when hydrate decomposed in the radial direction and there are three stages in the dissociation period which is influenced by the rate of hydrate dissociation and the heat flow of the reactor. A significant temperature difference along the radial direction of the reactor was obtained when the hydrate dissociates and this phenomenon could be enhanced by raising the production temperature. In addition, hydrate dissociates homogeneously and the temperature difference is much smaller than the other conditions when the production temperature is around the 10 °C. With the increase of the production temperature, the maximum of ΔToi grows until the temperature reaches 40 °C. The period of ΔToi have a close relation with the total time of hydrate dissociation. Especially, the period of ΔToi with production temperature of 10 °C is twice as much as that at other temperatures. Under these experimental conditions, the heat is mainly transferred by conduction from the dissociated zone to the dissociating zone and the production temperature has little effect on the convection of the water in the porous media.

  7. Basin scale assessment of gas hydrate dissociation in response to climate change

    Energy Technology Data Exchange (ETDEWEB)

    Reagan, M.; Moridis, G.; Elliott, S.; Maltrud, M.; Cameron-Smith, P.

    2011-07-01

    Paleooceanographic evidence has been used to postulate that methane from oceanic hydrates may have had a significant role in regulating climate. However, the behavior of contemporary oceanic methane hydrate deposits subjected to rapid temperature changes, like those now occurring in the arctic and those predicted under future climate change scenarios, has only recently been investigated. Field investigations have discovered substantial methane gas plumes exiting the seafloor along the Arctic Ocean margin, and the plumes appear at depths corresponding to the upper limit of a receding gas hydrate stability zone. It has been suggested that these plumes may be the first visible signs of the dissociation of shallow hydrate deposits due to ongoing climate change in the arctic. We simulate the release of methane from oceanic deposits, including the effects of fully-coupled heat transfer, fluid flow, hydrate dissociation, and other thermodynamic processes, for systems representative of segments of the Arctic Ocean margins. The modeling encompasses a range of shallow hydrate deposits from the landward limit of the hydrate stability zone down to water depths beyond the expected range of century-scale temperature changes. We impose temperature changes corresponding to predicted rates of climate change-related ocean warming and examine the possibility of hydrate dissociation and the release of methane. The assessment is performed at local-, regional-, and basin-scales. The simulation results are consistent with the hypothesis that dissociating shallow hydrates alone can result in significant methane fluxes at the seafloor. However, the methane release is likely to be confined to a narrow region of high dissociation susceptibility, defined by depth and temperature, and that any release will be continuous and controlled, rather than explosive. This modeling also establishes the first realistic bounds for methane release along the arctic continental shelf for potential hydrate

  8. Methane Hydrate Formation and Dissociation in the Presence of Silica Sand and Bentonite Clay

    National Research Council Canada - National Science Library

    Kumar Saw, V; Udayabhanu, G; Mandal, A; Laik, S

    2015-01-01

      The formation and dissociation of methane hydrates in a porous media containing silica sand of different sizes and bentonite clay were studied in the presence of synthetic seawater with 3.55 wt% salinity...

  9. Hydrates plugs dissociation in pipelines; Dissociation des bouchons d'hydrates de gaz dans les conduites petrolieres sous-marines

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Hong, D.

    2005-03-15

    Natural gas hydrates plugs cause problems during drilling, well operations, production, transportation and processing of oil and gas. Especially, it is a very serious problem in off-shore oil transportation where low temperature and high pressure become more and more favourable to gas hydrate formation as the new production wells are more and more deeper. Up to now, although many studies have been developed concerning the possibility of preventing pipe plugging, there is limited information in open literature on hydrate plugs dissociation and all models in literature are numerically complicated. In this study, hydrate plugs are formed from water in n-dodecane mixture with addition of a dispersant E102B in two different experimental apparatus in order to obtain hydrates plugs with different sizes (diameter of 7, 10.75 and 12 cm). Then, the plugs are dissociated by the method of two-sided depressurization. In this paper, we propose a numerical model which describes the dissociation of gas hydrate plugs in pipelines. The numerical model, which is constructed for cylindrical coordinates and for two-sided pressurization, is based on enthalpy method. We present also an approximate analytical model which has an average error 2.7 % in comparison with the numerical model. The excellent agreement between our experimental results, literature data and the two models shows that the models give a good prediction independently of the pipeline diameter, plug porosity and gas. The simplicity of the analytical model will make it easier in industrial applications. (author)

  10. Hydrate Formation/Dissociation in (Natural Gas + Water + Diesel Oil Emulsion Systems

    Directory of Open Access Journals (Sweden)

    Chang-Yu Sun

    2013-02-01

    Full Text Available Hydrate formation/dissociation of natural gas in (diesel oil + water emulsion systems containing 3 wt% anti-agglomerant were performed for five water cuts: 5, 10, 15, 20, and 25 vol%. The natural gas solubilities in the emulsion systems were also examined. The experimental results showed that the solubility of natural gas in emulsion systems increases almost linearly with the increase of pressure, and decreases with the increase of water cut. There exists an initial slow hydrate formation stage for systems with lower water cut, while rapid hydrate formation takes place and the process of the gas-liquid dissolution equilibrium at higher water cut does not appear in the pressure curve. The gas consumption amount due to hydrate formation at high water cut is significantly higher than that at low water cut. Fractional distillation for natural gas components also exists during the hydrate formation process. The experiments on hydrate dissociation showed that the dissociation rate and the amount of dissociated gas increase with the increase of water cut. The variations of temperature in the process of natural gas hydrate formation and dissociation in emulsion systems were also examined.

  11. The influence of porosity and structural parameters on different kinds of gas hydrate dissociation.

    Science.gov (United States)

    Misyura, S Y

    2016-07-22

    Methane hydrate dissociation at negative temperatures was studied experimentally for different artificial and natural samples, differing by macro- and micro-structural parameters. Four characteristic dissociation types are discussed in the paper. The internal kinetics of artificial granule gas hydrates and clathrate hydrates in coal is dependent on the porosity, defectiveness and gas filtration rate. The density of pores distribution in the crust of formed ice decreases by the several orders of magnitude and this change significantly the rate of decay. Existing models for describing dissociation at negative temperatures do not take into account the structural parameters of samples. The dissociation is regulated by internal physical processes that must be considered in the simulation. Non-isothermal dissociation with constant external heat flux was simulated numerically. The dissociation is simulated with consideration of heat and mass transfer, kinetics of phase transformation and gas filtering through a porous medium of granules for the negative temperatures. It is shown that the gas hydrate dissociation in the presence of mainly microporous structures is fundamentally different from the disintegration of gas hydrates containing meso and macropores.

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

    Science.gov (United States)

    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.

  13. Contribution of oceanic gas hydrate dissociation to the formation of Arctic Ocean methane plumes

    Energy Technology Data Exchange (ETDEWEB)

    Reagan, M.; Moridis, G.; Elliott, S.; Maltrud, M.

    2011-06-01

    Vast quantities of methane are trapped in oceanic hydrate deposits, and there is concern that a rise in the ocean temperature will induce dissociation of these hydrate accumulations, potentially releasing large amounts of carbon into the atmosphere. Because methane is a powerful greenhouse gas, such a release could have dramatic climatic consequences. The recent discovery of active methane gas venting along the landward limit of the gas hydrate stability zone (GHSZ) on the shallow continental slope (150 m - 400 m) west of Svalbard suggests that this process may already have begun, but the source of the methane has not yet been determined. This study performs 2-D simulations of hydrate dissociation in conditions representative of the Arctic Ocean margin to assess whether such hydrates could contribute to the observed gas release. The results show that shallow, low-saturation hydrate deposits, if subjected to recently observed or future predicted temperature changes at the seafloor, can release quantities of methane at the magnitudes similar to what has been observed, and that the releases will be localized near the landward limit of the GHSZ. Both gradual and rapid warming is simulated, along with a parametric sensitivity analysis, and localized gas release is observed for most of the cases. These results resemble the recently published observations and strongly suggest that hydrate dissociation and methane release as a result of climate change may be a real phenomenon, that it could occur on decadal timescales, and that it already may be occurring.

  14. Thermal regulation of methane hydrate dissociation: Implications for gas production models

    Science.gov (United States)

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

    2005-01-01

    Thermal self-regulation of methane hydrate dissociation at pressure, temperature conditions along phase boundaries, illustrated by experiment in this report, is a significant effect with potential relevance to gas production from gas hydrate. In surroundings maintained at temperatures above the ice melting point, the temperature in the vicinity of dissociating methane hydrate will decrease because heat flow is insufficient to balance the heat absorbed by the endothermic reaction: CH4??nH2O (s) = CH4 (g) + nH2O (l). Temperature decreases until either all of the hydrate dissociates or a phase boundary is reached. At pressures above the quadruple point, the temperature-limiting phase boundary is that of the dissociation reaction itself. At lower pressures, the minimum temperature is limited by the H2O solid/liquid boundary. This change in the temperature-limiting phase boundary constrains the pressure, temperature conditions of the quadruple point for the CH4-H2O system to 2.55 ?? 0.02 MPa and 272.85 ?? 0.03 K. At pressures below the quadruple point, hydrate dissociation proceeds as the liquid H2O produced by dissociation freezes. In the laboratory experiments, dissociation is not impeded by the formation of ice byproduct per se; instead rates are proportional to the heat flow from the surroundings. This is in contrast to the extremely slow dissociation rates observed when surrounding temperatures are below the H2O solid/liquid boundary, where no liquid water is present. This "anomalous" or "self" preservation behavior, most pronounced near 268 K, cannot be accessed when surrounding temperatures are above the H2O solid/liquid boundary. ?? 2005 American Chemical Society.

  15. 沉积物中水合物形成机理及分解动力学研究进展%ADVANCES IN FORMATION MECHANISM AND DISSOCIATION KINETICS OF GAS HYDRATE IN SEDIMENTS

    Institute of Scientific and Technical Information of China (English)

    李清平; 张旭辉; 鲁晓兵

    2011-01-01

    The study on the formation of gas hydrate in sediments is mainly summarized.Firstly, the formation mechanism and advances in bulk gas hydrate study, including nucleation mechanism, armor effect and memory effect etc., are briefly described.Secondly, the difficulty and advances in the formation of gas hydrate with low-solubility gases, such as methane, and the effects of chief factors, such as pore size, on the formation of gas hydrate in sediments are summarized.Thirdly, the major mathematical models on the kinetics of gas hydrate formation are presented.Finally, several issues to be further studied are highlighted.%对沉积物中水合物形成机理的研究进展作了述评.简述了纯水含物生成的机理及研究进展,包括成核机理、铠甲效应、记忆效戍等现象和机理;阐述了低可溶气体如甲烷生成水合物的难点,以及主要因素如孔隙尺寸对沉积物中水合物生成的影响研究进展;简要介绍了目前关于水合物形成和分解动力学的代表性数学模型;并对今后的研究方向进行了阐述.

  16. Gas hydrate dissociation prolongs acidification of the Anthropocene oceans

    OpenAIRE

    Boudreau, B.P.; Luo, Yiming; Filip J R Meysman; J. J. Middelburg; G. R. Dickens

    2015-01-01

    Anthropogenic warming of the oceans can release methane (CH4) currently stored in sediments as gas hydrates. This CH4 will be oxidized to CO2, thus increasing the acidification of the oceans. We employ a biogeochemical model of the multimillennial carbon cycle to determine the evolution of the oceanic dissolved carbonate system over the next 13 kyr in response to CO2 from gas hydrates, combined with a reasonable scenario for long-term anthropogenic CO2 emissions. Hydrate-derived CO2 will appr...

  17. Methane Hydrate Dissociation by Depressurization in a Mount Elbert Sandstone Sample: Experimental Observations and Numerical Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Kneafsey, T.; Moridis, G.J.

    2011-01-15

    A preserved sample of hydrate-bearing sandstone from the Mount Elbert Test Well was dissociated by depressurization while monitoring the internal temperature of the sample in two locations and the density changes at high spatial resolution using x-ray CT scanning. The sample contained two distinct regions having different porosity and grain size distributions. The hydrate dissociation occurred initially throughout the sample as a result of depressing the pressure below the stability pressure. This initial stage reduced the temperature to the equilibrium point, which was maintained above the ice point. After that, dissociation occurred from the outside in as a result of heat transfer from the controlled temperature bath surrounding the pressure vessel. Numerical modeling of the test using TOUGH+HYDRATE yielded a gas production curve that closely matches the experimentally measured curve.

  18. Dissociation behavior of methane--ethane mixed gas hydrate coexisting structures I and II.

    Science.gov (United States)

    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.

  19. Phase equilibrium and dissociation enthalpy for semi-clathrate hydrate of CO2+TBAB

    OpenAIRE

    2008-01-01

    The present work investigates equilibrium conditions and dissociation enthalpy of hydrates formed from CO2-TBAB(tetra-n-butylammonium bromide)-water mixtures. Differential Thermal Analysis (DTA) was used for Hydrate-Liquid-Vapour (H-L-V) equilibrium condition determination in a TBAB concentration range from 4.43 to 9.01 wt% and in a CO2 pressure range from 0.3 to 2.5 MPa. The results showed that the presence of TBAB allowed decreasing the formation pressure of CO2 hydrate by approximately ...

  20. Dissociation and specific heats of gas hydrates under submarine and sublacustrine environments

    Energy Technology Data Exchange (ETDEWEB)

    Nakagawa, R.; Hachikubo, A.; Shoji, H. [Kitami Inst. of Technology, Kitami (Japan)

    2008-07-01

    Studies have shown that natural gas hydrates located near a mud volcano in Lake Baikal contain high concentrations of ethane. Gas hydrates absorb and release large amounts of latent heat during their formation and dissociation processes. In this study, the specific heat of synthetic methane and ethane hydrates were measured under high pressure using a heat-flow calorimeter. The aim of the study was to develop an improved understanding of the thermal environment of gas hydrate-bearing sediments in submarine and sublacustrine environments. Ice was placed in 2 sampling cells and pressurized with methane and ethane at 5 MPa and 2 MPa. After the gas hydrates formed, the samples were then heated from 263 K to 288 K. An analysis of data obtained from the experiment showed that large negative heat flow peaks corresponding with methane gas hydrate dissociation occurred in temperature ranges of 279 to 282 K at a pressure of 5 MPa, and at temperatures of 283-286 K at 2 MPa for the ethane gas hydrate. Future experiments with the calorimeter will be conducted at higher pressure ranges. 15 refs., 3 figs.

  1. Fundamentals of Natural Gas and Species Flows from Hydrate Dissociation - Applications to Safety and Sea Floor Instability

    Energy Technology Data Exchange (ETDEWEB)

    Ahmadi, Goodarz

    2006-09-30

    Semi-analytical computational models for natural gas flow in hydrate reservoirs were developed and the effects of variations in porosity and permeability on pressure and temperature profiles and the movement of a dissociation front were studied. Experimental data for variations of gas pressure and temperature during propane hydrate formation and dissociation for crushed ice and mixture of crushed ice and glass beads under laboratory environment were obtained. A thermodynamically consistent model for multiphase liquid-gas flows trough porous media was developed. Numerical models for hydrate dissociation process in one dimensional and axisymmetric reservoir were performed. The computational model solved the general governing equations without the need for linearization. A detail module for multidimensional analysis of hydrate dissociation which make use of the FLUENT code was developed. The new model accounts for gas and liquid water flow and uses the Kim-Boshnoi model for hydrate dissociation.

  2. Gas hydrate dissociation prolongs acidification of the Anthropocene oceans

    NARCIS (Netherlands)

    Boudreau, B.P.; Luo, Y.; Meysman, F.J.R.; Middelburg, J

    2015-01-01

    Anthropogenic warming of the oceans can release methane (CH4) currently stored in sediments as gas hydrates. This CH4 will be oxidized to CO2, thus increasing the acidification of the oceans. We employ a biogeochemical model of the multimillennial carbon cycle to determine the evolution of the ocean

  3. Modeling pure methane hydrate dissociation using a numerical simulator from a novel combination of X-ray computed tomography and macroscopic data

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, A.; Moridis, G.J.; Kneafsey, T.J.; Sloan, Jr., E.D.

    2009-08-15

    The numerical simulator TOUGH+HYDRATE (T+H) was used to predict the transient pure methane hydrate (no sediment) dissociation data. X-ray computed tomography (CT) was used to visualize the methane hydrate formation and dissociation processes. A methane hydrate sample was formed from granular ice in a cylindrical vessel, and slow depressurization combined with thermal stimulation was applied to dissociate the hydrate sample. CT images showed that the water produced from the hydrate dissociation accumulated at the bottom of the vessel and increased the hydrate dissociation rate there. CT images were obtained during hydrate dissociation to confirm the radial dissociation of the hydrate sample. This radial dissociation process has implications for dissociation of hydrates in pipelines, suggesting lower dissociation times than for longitudinal dissociation. These observations were also confirmed by the numerical simulator predictions, which were in good agreement with the measured thermal data during hydrate dissociation. System pressure and sample temperature measured at the sample center followed the CH{sub 4} hydrate L{sub w}+H+V equilibrium line during hydrate dissociation. The predicted cumulative methane gas production was within 5% of the measured data. Thus, this study validated our simulation approach and assumptions, which include stationary pure methane hydrate-skeleton, equilibrium hydrate-dissociation and heat- and mass-transfer in predicting hydrate dissociation in the absence of sediments. It should be noted that the application of T+H for the pure methane hydrate system (no sediment) is outside the general applicability limits of T+H.

  4. Characterisation of gas hydrates formation and dissociation using high pressure DSC

    Energy Technology Data Exchange (ETDEWEB)

    Le Parlouer, P. [Thermal Consulting, Caluire (France); Etherington, G. [Setaram Inc., Pennsauken, NJ (United States)

    2008-07-01

    This paper provided details of an innovative methodology that used a high pressure micro-scale differential scanning calorimetry (DSC) method to characterize the thermodynamic properties and kinetics of gas hydrate formation. The calorimeter was based on a symmetrical heat flux design that used a Peltier cooling and heating principle. No refrigerating fluids were required. The method described phase transitions in relation to time, temperature and pressure. The DSC method was designed for use with gas hydrates trapped in marine sediments; hydrate formation in drilling muds and annulars during offshore oil and gas extraction; the storage and transportation of natural gas; and gas hydrate formation and dissociation for cold storage and transportation. Tests demonstrated that the DSC accurately predicted the formation of gas hydrates under high pressure conditions. Experimental studies were conducted to investigate salt solutions under methane pressure; and hydrate dissociation in a sodium chloride (NaC1) and ethyleneglycol solution. Data obtained comparing the method with classical PVT techniques showed that the MicroDSC technique was less time-consuming and required smaller sample volumes. It was concluded that the method is suitable for use with various types of fluids. 13 refs., 7 figs.

  5. Clathrate formation and dissociation in vapor/water/ice/hydrate systems in SBA-15, sol-gel and CPG porous media, as probed by NMR relaxation, novel protocol NMR cryoporometry, neutron scattering and ab initio quantum-mechanical molecular dynamics simulation.

    Science.gov (United States)

    Webber, J Beau W; Anderson, Ross; Strange, John H; Tohidi, Bahman

    2007-05-01

    The Gibbs-Thomson effect modifies the pressure and temperature at which clathrates occur, hence altering the depth at which they occur in the seabed. Nuclear magnetic resonance (NMR) measurements as a function of temperature are being conducted for water/ice/hydrate systems in a range of pore geometries, including templated SBA-15 silicas, controlled pore glasses and sol-gel silicas. Rotator-phase plastic ice is shown to be present in confined geometry, and bulk tetrahydrofuran hydrate is also shown to probably have a rotator phase. A novel NMR cryoporometry protocol, which probes both melting and freezing events while avoiding the usual problem of supercooling for the freezing event, has been developed. This enables a detailed probing of the system for a given pore size and geometry and the exploration of differences between hydrate formation and dissociation processes inside pores. These process differences have an important effect on the environment, as they impact on the ability of a marine hydrate system to re-form once warmed above a critical temperature. Ab initio quantum-mechanical molecular dynamics calculations are also being employed to probe the dynamics of liquids in pores at nanometric dimensions.

  6. Dissociation behavior of Methane Hydrate presumed by NMR log analysis

    Science.gov (United States)

    Kotera, T.

    2015-12-01

    This study has been conducted with the aim of comprehending dissociation behavior of MH. The production test was operated in the Daini-Atsumi knoll in the eastern Nankai Trough, Japan. We corresponded the NMR log data acquired from the three wells, which drilled before the test (AT1-MC) and after the test (AT1-LWD1 and AT1-LWD2). NMR log measures T2 relaxation time, and calculates porosity and permeability. We especially focused on the T2 distribution. It is assumed that MH occupied larger pore space in the sandy sediment because the T2 distribution in the MH bearing layer has no peak in the longer time zone at the AT1-MC. However, T2 peak appeared over 33ms zone at the AT1-LWD1 and AT1-LWD2. This phenomenon is observed in the thin MH bearing layers rather than thick one. On the other hand, nothing T2 peak appeared over the 33ms zone in the thick MH bearing layer, but T2 distribution shifts to longer relaxation time in the short time interval. Hence, it is assumed that the MH was dissociated from the contact faces with the grain. In terms of the thermal conductivity, near the grain-grain contact faces are more dissociable than the MH-grain contact; however both of dissociation zones are essentially MH-grain contact faces. Nothing or few MH was observed in the muddy layer at the coring campaign near these wells. Abovementioned, NMR logging detected various changes on the T2 distribution. It seems to indicate the dissociation of MH. And these data gets into alignment with other log data and monitoring data, which are resistivity and temperature measurement. However, as this logging data acquired from each location, there is possibility that the initial condition was originally distinct. This research was conducted as a part of the MH21 research, and the authors would like to express their sincere appreciation to MH21 and the Ministry of Economy, Trade and Industry for providing the permission to disclose this research.

  7. Formulating formation mechanism of natural gas hydrates.

    Science.gov (United States)

    Palodkar, Avinash V; Jana, Amiya K

    2017-07-25

    A large amount of energy, perhaps twice the total amount of all other hydrocarbon reserves combined, is trapped within gas hydrate deposits. Despite emerging as a potential energy source for the world over the next several hundred years and one of the key factors in causing future climate change, gas hydrate is poorly known in terms of its formation mechanism. To address this issue, a mathematical formulation is proposed in the form of a model to represent the physical insight into the process of hydrate growth that occurs on the surface and in the irregular nanometer-sized pores of the distributed porous particles. To evaluate the versatility of this rigorous model, the experimental data is used for methane (CH4) and carbon dioxide (CO2) hydrates grown in different porous media with a wide range of considerations.

  8. A study of hydrate formation and dissociation from high water cut emulsions and the impact on emulsion inversion

    Energy Technology Data Exchange (ETDEWEB)

    Greaves, D.P.; Boxall, J.A.; Mulligan, J.; Dendy Sloan, E.; Koh, C.A. [Colorado School of Mines, Golden, CO (United States). Dept. of Chemical Engineering, Center for Hydrate Research

    2008-07-01

    The challenges facing the petroleum industry regarding clathrate hydrate formation were discussed, with particular reference to the costly and dangerous pipeline blocking plugs that form upon hydrate accumulation and agglomeration. Although a variety of inhibitors are used to prevent hydrate plug formation, they are not designed for high water content production. As oil and gas are produced from less profitable or older wells, there is a greater probability of higher water cuts. Therefore, this study focused on methane hydrate formation and dissociation from these high water content (greater than 60 per cent volume) emulsions of water-in-oil (W/O) and oil-in-water (O/W). At high water cuts, the system can quickly agglomerate with hydrate formation, while dissociation can lead to a significant change in the emulsion type. Although inhibition can be costly at high water cuts, it must be considered because of the risk of immediate agglomeration and plug formation with hydrates. In this study, the hydrate formation and dissociation from W/O emulsions destabilized the emulsion, with the final emulsion formulation favouring a water continuous state following re-emulsification. After dissociation, the W/O emulsion formed a multiple o/W/O emulsion or inverted at even higher water cuts, forming an O/W emulsion with 68 per cent water volume. In contrast, hydrate formation and dissociation from O/W emulsions with more than 71 per cent water volume stablized the O/W emulsion. 24 refs., 13 figs.

  9. Numerical study on the deformation of soil stratum and vertical wells with gas hydrate dissociation

    Science.gov (United States)

    Chen, Xudong; Zhang, Xuhui; Lu, Xiaobing; Wei, Wei; Shi, Yaohong

    2016-07-01

    Gas hydrate (GH) dissociates owing to thermal injection or pressure reduction from the well in gas/oil or GH exploitation. GH dissociation leads to, for example, decreases in soil strength, engineering failures such as wellbore instabilities, and marine landslides. The FLAC3D software was used to analyze the deformation of the soil stratum and vertical wells with GH dissociation. The effects of Young's modulus, internal friction angle, cohesion of the GH layer after dissociation, and the thickness of the GH layer on the deformation of soils were studied. It is shown that the maximum displacement in the whole soil stratum occurs at the interface between the GH layer and the overlayer. The deformation of the soil stratum and wells increases with decreases in the modulus, internal friction angle, and cohesion after GH dissociation. The increase in thickness of the GH layer enlarges the deformation of the soil stratum and wells with GH dissociation. The hydrostatic pressure increases the settlement of the soil stratum, while constraining horizontal displacement. The interaction between two wells becomes significant when the affected zone around each well exceeds half the length of the GH dissociation zone.

  10. Numerical study on the deformation of soil stratum and vertical wells with gas hydrate dissociation

    Institute of Scientific and Technical Information of China (English)

    Xudong Chen; Xuhui Zhang; Xiaobing Lu; Wei Wei; Yaohong Shi

    2016-01-01

    Gas hydrate (GH) dissociates owing to thermal injection or pressure reduction from the well in gas/oil or GH exploitation. GH dissociation leads to, for exam-ple, decreases in soil strength, engineering failures such as wellbore instabilities, and marine landslides. The FLAC3D software was used to analyze the deformation of the soil stratum and vertical wells with GH dissociation. The effects of Young’s modulus, internal friction angle, cohesion of the GH layer after dissociation, and the thickness of the GH layer on the deformation of soils were studied. It is shown that the maximum displacement in the whole soil stratum occurs at the interface between the GH layer and the over-layer. The deformation of the soil stratum and wells increases with decreases in the modulus, internal friction angle, and cohesion after GH dissociation. The increase in thickness of the GH layer enlarges the deformation of the soil stratum and wells with GH dissociation. The hydrostatic pressure increases the settlement of the soil stratum, while constrain-ing horizontal displacement. The interaction between two wells becomes significant when the affected zone around each well exceeds half the length of the GH dissociation zone.

  11. Numerical Investigation of Hydrate Dissociation Performance in the South China Sea with Different Horizontal Well Configurations

    Directory of Open Access Journals (Sweden)

    Jing-Chun Feng

    2014-07-01

    Full Text Available Based on the available measurement data and literature on the hydrate deposits of the South China Sea, a numerical simulation with a new dual horizontal well system has been carried out. Warm brine stimulation combined with depressurization is employed as the production method. Two horizontal wells were situated in the same horizontal plane and they were placed in the middle of the Hydrate-Bearing Layer (HBL. The warm brine is injected from the left well (LW into the reservoir, and the right well (RW acted as the producer under constant pressure. The simulation results show that the effects of hydrate dissociation rate, gas to water ratio, and energy ratio are all better than the previous work in which the dual horizontal wells are placed in the same vertical plane. In addition, the sensitivity analysis indicates that a higher injection rate can enhance the hydrate dissociation rate and gas production rate, while a lower injection rate gives a more favorable gas to water ratio and energy ratio.

  12. Development of Ocean Bottom Multi-component Seismic System for Methane Hydrate Dissociation Monitoring

    Science.gov (United States)

    Takahashi, H.; Asakawa, E.; Hayashi, T.; Inamori, T.; Saeki, T.

    2011-12-01

    A 2D multi-component seismic survey was carried out in the Nankai Trough using the RSCS (Real-time Seismic Cable System) system in 2006. The RSCS is the newly developed ocean bottom cable system which is usable in more than 2000m water depth. The results of the PP and data PS components gave us much information of the methane hydrates bearing zone. Based on RSCS technology, we are developing a new monitoring system using multi-component seismic sensors to delineate the methane hydrate dissociation zone for the offshore methane hydrate production test scheduled in FY2012. Conventional RSCS is composed of three component gimbaled geophones which require a large volume inside the receiver. We will adopt accelerometers to achieve a small receiver that is 2/3 the size of conventional RSCS. The accelerometer data can be corrected into horizontal or vertical directions based on the gravity acceleration. The receiver case has a protective metallic exterior and the cable is protected with steel-screened armoring, allowing for burial usage using ROV for sub-seabed deployment. It will realize a unique survey style that leaves the system on the seabed between pre-test baseline survey and post-test repeated survey, which might be up to 6 months. The fixed location of the receiver is very important for time-lapse monitoring survey. We name the new system as DSS (Deep-sea Seismic System). A feasibility study to detect the methane hydrate dissociation with the DSS was carried out and we found that the methane hydrate dissociation could be detected with the DSS depending on the area of the dissociation. The first experiment of the DSS performance test in a marine area is planned in November 2011. The main features of DSS are described as follows: (1) Deep-sea /Ultra Deep-sea Operation Methane hydrate exists in equilibrium temperature and pressure holds at water depths greater than 500m. The system water depth resistance target up to 2000m. The receiver case has a protective

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

    Science.gov (United States)

    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.

  14. Pressurized laboratory experiments show no stable carbon isotope fractionation of methane during gas hydrate dissolution and dissociation.

    Science.gov (United States)

    Lapham, Laura L; Wilson, Rachel M; Chanton, Jeffrey P

    2012-01-15

    The stable carbon isotopic ratio of methane (δ(13)C-CH(4)) recovered from marine sediments containing gas hydrate is often used to infer the gas source and associated microbial processes. This is a powerful approach because of distinct isotopic fractionation patterns associated with methane production by biogenic and thermogenic pathways and microbial oxidation. However, isotope fractionations due to physical processes, such as hydrate dissolution, have not been fully evaluated. We have conducted experiments to determine if hydrate dissolution or dissociation (two distinct physical processes) results in isotopic fractionation. In a pressure chamber, hydrate was formed from a methane gas source at 2.5 MPa and 4 °C, well within the hydrate stability field. Following formation, the methane source was removed while maintaining the hydrate at the same pressure and temperature which stimulated hydrate dissolution. Over the duration of two dissolution experiments (each ~20-30 days), water and headspace samples were periodically collected and measured for methane concentrations and δ(13)C-CH(4) while the hydrate dissolved. For both experiments, the methane concentrations in the pressure chamber water and headspace increased over time, indicating that the hydrate was dissolving, but the δ(13)C-CH(4) values showed no significant trend and remained constant, within 0.5‰. This lack of isotope change over time indicates that there is no fractionation during hydrate dissolution. We also investigated previous findings that little isotopic fractionation occurs when the gas hydrate dissociates into gas bubbles and water due to the release of pressure. Over a 2.5 MPa pressure drop, the difference in the δ(13)C-CH(4) was dissociates and demonstrated that there is no fractionation when the hydrate dissolves. Therefore, measured δ(13)C-CH(4) values near gas hydrates are not affected by physical processes, and can thus be interpreted to result from either the gas source or

  15. Dissociation mechanisms of photoexcited molecular ions

    CERN Document Server

    Inglis, L C

    2003-01-01

    Photoionisation of gas phase molecules, in the energy range 8 - 40 eV, and the subsequent dissociation mechanisms have been investigated using threshold photoelectron spectroscopy and ion time-of-flight mass spectrometry. The excitation source used was monochromatic radiation, delivered by station 3.2 at the Daresbury Laboratory Synchrotron Radiation Source. These two techniques have also been combined in threshold photoelectron-photoion coincidence experiments, in order to record coincidence time-of-flight mass spectra and thereby determine breakdown curves. Such curves display the ion fragmentation as a function of internal energy. In addition, computer modelling techniques have been employed to gain some understanding of the unimolecular dissociations of energy selected molecular ions by establishing theoretical breakdown graphs, appearance energies, fragmentation pathways and dissociation rates. Ab initio quantum chemistry calculations have been carried out, generating ionisation and appearance energies, ...

  16. Possibility of submarine landslide triggering due to dissociation of hydrates - an approach through ring shear tests

    Science.gov (United States)

    Fukuoka, Hiroshi; Dok, Atitkagna

    2015-04-01

    In Japan, the MH21 Research Consortium is developing the advanced technology of mining submarine methane hydrates by reducing pressure of hydrates to induce dissociation and gasification of hydrates. However, assessment and prediction technology of dissociation is still under development through intensive study. On the other hands, authors have pointed out the possibility of large-scale submarine landslides by the sliding surface liquefaction of the hydrate bearing- layers. Author has tested dry-ice and silica-sands mixture specimen as a methane hydrate substitutes in a series of partially-drained high speed / stress-controlled ring shear tests. Their results strongly suggest the possibility of sliding surface liquefaction under strong seismic condition, while the possibility of extensive dissociation especially under mining by reducing pressure is not clear. Author modified the ring shear apparatus DPRI-7 of Kyoto University so that it can cool down the specimen and measure the specimen temperature during shearing. Silica sands #7 submerged in TBAB (Tetra-butyl-ammonium bromide) solution was used for the specimen. This TBAB solution was frozen at around room temperature of 8 - 12 degrees Celsius under 1 atmospheric pressure. A series of constant speed shearing test was conducted to examine the rate-effect. Frictional characteristics was achieved under 0.1 - 10 cm/s of shear speed which was changed in stepping-up and down. The results show rather the temperature effect was obvious than the speed. At the first shearing of the specimen immediately after frozen, extreme high peak stress was obtained. Then the residual shear strength showed medium peak at temperature of about 4 degrees, then gradually decreased up to about 10 degrees. The medium peak of shear strength may come from the generation of angular grains due to crushing the specimen during initial shearing. The decreasing thereafter may have resulted from further crushing, rounding of the hydrates and

  17. Monitoring the Methane Hydrate Dissociation by the Offshore Methane Hydrate Production Tests using Multi-component Seismic

    Science.gov (United States)

    Asakawa, Eiichi; Hayashi, Tsutomu; Tsukahara, Hitoshi; Takahashi, Hiroo; Saeki, Tatsuo

    2013-04-01

    We developed a new OBC (Ocean Bottom Cable), named as 'DSS' (Deep-sea Seismic System). The sensor has 3-component accelerometer and a hydrophone applicable for four-component (4C) seismic survey. Using the DSS, the methane hydrate dissociation zone will be tried to be monitored at the water depth of around 1000m during JOGMEC offshore methane hydrate production test in early 2013. Before the DSS, we had developed the RSCS (Real-time Seismic Cable System) with 3-component gimbaled geophones, and carried out a reflection seismic survey in the Nankai Trough in 2006. Referring this successful survey, we improved the RSCS to the DSS. The receiver size is reduced to 2/3 and the receiver case has a protective metallic exterior and the cable is protected with steel-screened armouring, allowing burial usage using ROV for sub-seabed deployment at the water depth up to 2000m. It will realize a unique survey style that leaves the system on the seabed between pre-test baseline survey and post-test repeated surveys, which might be up to 6 months. The fixed location of the receiver is very important for time-lapse monitoring survey. The DSS has totally 36 sensors and the sensor spacing is 26.5m. The total length is about 1km. We carried out the pre-test baseline survey between off Atsumi and Shima-peninsula in August, 2012.We located the DSS close to the production test well. The nearest sensor is 63m apart from the well. A newly developed real-time 3-D laying simulation system consisting of ADCP (Acoustic Doppler Current Profiler), transponders attached to the DSS, and real-time 3-D plotting system for transponder locations have been adopted. After we laid the cable, we buried the DSS using ROV (Remotely Operated Vehicle). The baseline survey included 2D/3D seismic surveys with shooting vessel and cable laying/observation ship. The resultant 2D section and 3D volume shows the good quality to delineate the methane hydrate concentrated zone. After the baseline survey, we have left

  18. Use of Computed X-ray Tomographic Data for Analyzing the Thermodynamics of a Dissociating Porous Sand/Hydrate Mixture

    Science.gov (United States)

    Freifeld, Barry M.; Kneafsey, Timothy J.; Tomutsa, Liviu; Stern, Laura A.; Kirby, Stephen H.

    2002-02-28

    X-ray computed tomography (CT) is a method that has been used extensively in laboratory experiments for measuring rock properties and fluid transport behavior. More recently, CT scanning has been applied successfully to detect the presence and study the behavior of naturally occurring hydrates. In this study, we used a modified medical CT scanner to image and analyze the progression of a dissociation front in a synthetic methane hydrate/sand mixture. The sample was initially scanned under conditions at which the hydrate is stable (atmospheric pressure and liquid nitrogen temperature, 77 K). The end of the sample holder was then exposed to the ambient air, and the core was continuously scanned as dissociation occurred in response to the rising temperature. CT imaging captured the advancing dissociation front clearly and accurately. The evolved gas volume was monitored as a function of time. Measured by CT, the advancing hydrate dissociation front was modeled as a thermal conduction problem explicitly incorporating the enthalpy of dissociation, using the Stefan moving-boundary-value approach. The assumptions needed to perform the analysis consisted of temperatures at the model boundaries. The estimated value for thermal conductivity of 2.6 W/m K for the remaining water ice/sand mixture is higher than expected based on conduction alone; this high value may represent a lumped parameter that incorporates the processes of heat conduction, methane gas convection, and any kinetic effects that occur during dissociation. The technique presented here has broad implications for future laboratory and field testing that incorporates geophysical techniques to monitor gas hydrate dissociation.

  19. The history and future trends of ocean warming-induced gas hydrate dissociation in the SW Barents Sea

    Science.gov (United States)

    Vadakkepuliyambatta, Sunil; Chand, Shyam; Bünz, Stefan

    2017-01-01

    The Barents Sea is a major part of the Arctic where the Gulf Stream mixes with the cold Arctic waters. Late Cenozoic uplift and glacial erosion have resulted in hydrocarbon leakage from reservoirs, evolution of fluid flow systems, shallow gas accumulations, and hydrate formation throughout the Barents Sea. Here we integrate seismic data observations of gas hydrate accumulations along with gas hydrate stability modeling to analyze the impact of warming ocean waters in the recent past and future (1960-2060). Seismic observations of bottom-simulating reflectors (BSRs) indicate significant thermogenic gas input into the hydrate stability zone throughout the SW Barents Sea. The distribution of BSR is controlled primarily by fluid flow focusing features, such as gas chimneys and faults. Warming ocean bottom temperatures over the recent past and in future (1960-2060) can result in hydrate dissociation over an area covering 0.03-38% of the SW Barents Sea.

  20. DNA under Force: Mechanics, Electrostatics, and Hydration

    Directory of Open Access Journals (Sweden)

    Jingqiang Li

    2015-02-01

    Full Text Available Quantifying the basic intra- and inter-molecular forces of DNA has helped us to better understand and further predict the behavior of DNA. Single molecule technique elucidates the mechanics of DNA under applied external forces, sometimes under extreme forces. On the other hand, ensemble studies of DNA molecular force allow us to extend our understanding of DNA molecules under other forces such as electrostatic and hydration forces. Using a variety of techniques, we can have a comprehensive understanding of DNA molecular forces, which is crucial in unraveling the complex DNA functions in living cells as well as in designing a system that utilizes the unique properties of DNA in nanotechnology.

  1. Theoretical Structures of Triflic Acid-Water Clusters and the Molecular Mechanism of Proton Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Paddison, S.J.; Pratt, L.R.; Zawodzinski, T.A.

    1998-11-01

    Structural and energetic information required for recently proposed quasi-chemical theories of solution chemistry have been obtained for clusters of water with triflic acid, CF{sub 3}SO{sub 3}H(H{sub 2}O){sub n} for n=1-6. Quantum mechanical calculations on the clusters indicate that the acid proton does not dissociate with n=1 or 2 hydrating water molecules, but does dissociate for n>=3 water molecule partners. The computed minimum energy structures indicate that both ''Eigen'' (H{sub 9}O{sub 4}{sup +}) (n=3,4,6) and ''Zundel'' (H{sub 5}O{sub 2}{sup +}) (n=5) structures are likely to play a role in the molecular mechanism of acid dissociation in Nafion{reg_sign}.

  2. Mechanism and kinetics of hydrated electron diffusion

    CERN Document Server

    Tay, Kafui A; Boutin, Anne; 10.1063/1.2964101

    2012-01-01

    Molecular dynamics simulations are used to study the mechanism and kinetics of hydrated electron diffusion. The electron center of mass is found to exhibit Brownian-type behavior with a diffusion coefficient considerably greater than that of the solvent. As previously postulated by both experimental and theoretical works, the instantaneous response of the electron to the librational motions of surrounding water molecules constitutes the principal mode of motion. The diffusive mechanism can be understood within the traditional framework of transfer diffusion processes, where the diffusive step is akin to the exchange of an extramolecular electron between neighboring water molecules. This is a second-order process with a computed rate constant of 5.0 ps^{-1} at 298 K. In agreement with experiment the electron diffusion exhibits Arrhenius behavior over the temperature range of 298-400 K. We compute an activation energy of 8.9 kJ/mol. Through analysis of Arrhenius plots and the application of a simple random walk...

  3. Mechanical properties of sand, silt, and clay containing tetrahydrofuran hydrate

    Science.gov (United States)

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

    2007-01-01

    The mechanical behavior of hydrate-bearing sediments subjected to large strains has relevance for the stability of the seafloor and submarine slopes, drilling and coring operations, and the analysis of certain small-strain properties of these sediments (for example, seismic velocities). This study reports on the results of comprehensive axial compression triaxial tests conducted at up to 1 MPa confining pressure on sand, crushed silt, precipitated silt, and clay specimens with closely controlled concentrations of synthetic hydrate. The results show that the stress-strain behavior of hydrate-bearing sediments is a complex function of particle size, confining pressure, and hydrate concentration. The mechanical properties of hydrate-bearing sediments at low hydrate concentration (probably 50% of pore space), the behavior becomes more independent of stress because the hydrates control both stiffness and strength and possibly the dilative tendency of sediments by effectively increasing interparticle coordination, cementing particles together, and filling the pore space. The cementation contribution to the shear strength of hydrate-bearing sediments decreases with increasing specific surface of soil minerals. The lower the effective confining stress, the greater the impact of hydrate formation on normalized strength.

  4. Accurate measurement of phase equilibria and dissociation enthalpies of HFC-134a hydrates in the presence of NaCl for potential application in desalination

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Dongyoung; Lee, Yohan; Choi, Wonjung; Seo, Yongwon [Ulsan National Institute of Science and Technology, Ulsan (Korea, Republic of); Lee, Seungmin [Korea Institute of Industrial Technology, Busan (Korea, Republic of)

    2016-04-15

    Phase equilibria, structure identification, and dissociation enthalpies of HFC-134a hydrates in the presence of NaCl are investigated for potential application in desalination. To verify the influence of NaCl on the thermodynamic hydrate stability of the HFC-134a hydrate, the three-phase (hydrate (H) - liquid water (L{sub W}) - vapor (V)) equilibria of the HFC-134a+NaCl (0, 3.5, and 8.0 wt%)+water systems are measured by both a conventional isochoric (pVT) method and a stepwise differential scanning calorimeter (DSC) method. Both pVT and DSC methods demonstrate reliable and consistent hydrate phase equilibrium points of the HFC-134a hydrates in the presence of NaCl. The HFC- 134a hydrate is identified as sII via powder X-ray diffraction. The dissociation enthalpies (ΔH{sub d}) of the HFC-134a hydrates in the presence of NaCl are also measured with a high pressure micro-differential scanning calorimeter. The salinity results in significant thermodynamic inhibition of the HFC-134a hydrates, whereas it has little effect on the dissociation enthalpy of the HFC-134a hydrates. The experimental results obtained in this study can be utilized as foundational data for the hydrate-based desalination process.

  5. Strengthening mechanism of cemented hydrate-bearing sand at microscales

    Science.gov (United States)

    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.

  6. Seismic time-lapse monitoring of potential gas hydrate dissociation around boreholes : could it be feasible? A conceptual 2D study linking geomechanical and seismic FD models

    Energy Technology Data Exchange (ETDEWEB)

    Pecher, I.; Yang, J.; Anderson, R.; Tohidi, B.; MacBeth, C. [Heriot-Watt Univ., Edinburgh (United Kingdom). Inst. of Petroleum Engineering; Freij-Ayoub, R.; Clennell, B. [CSIRO Petroleum, Bentley, WA (Australia)

    2008-07-01

    Dissociation of gas hydrate to water and potentially overpressured gas around boreholes may pose a hazard for deep-water hydrocarbon production. Strategies to mitigate this risk include monitoring for early detection of dissociation. Seismic methods are especially promising, primarily because of a high sensitivity of P-wave velocity to gas in the pore space of unconsolidated sediments. This paper presented a study that applied commonly used rock physics modeling to predict the seismic response to gas hydrate dissociation with a focus on P-impedance and performed sensitivity tests. The geomechanical model was translated into seismic models. In order to determine which parameters needed to be particularly well calibrated in experimental and modeling studies, the sensitivity of seismic properties to a variation of input parameters was estimated. The seismic response was predicted from dissociating gas hydrates using two-dimensional finite-difference wave-propagation modeling to demonstrate that despite the small predicted lateral extent of hydrate dissociation, its pronounced effect on seismic properties should allow detection with a seismic source on a drilling platform and receivers on the seafloor. The paper described the methods, models, and results of the study. It was concluded that the key factors for predicting the seismic response of sediments to hydrate dissociation were the mode of gas hydrate distribution, gas distribution in the sediments, gas saturation, and pore pressure. 33 refs., 3 tabs., 8 figs.

  7. Modelling of Gas Hydrate Dissociation During The Glacial-Inter-glacial Cycles, Case Study The Chatham Rise, New Zealand

    Science.gov (United States)

    Oluwunmi, P.; Pecher, I. A.; Archer, R.; Moridis, G. J.; Reagan, M. T.

    2015-12-01

    Seafloor depressions covering an area of >20,000 km2 on the Chatham Rise, south east of New Zealand, have been interpreted as pockmarks which are related to past fluid releases. It is proposed that the seafloor depressions were caused by sudden escape of overpressured gas generated by gas hydrate dissociation during glacial sea-level lowering. We are attempting to simulate the evolution of the gas hydrate system through glacial-interglacial cycles in the study area using TOUGH-Hydrate. The Chatham Rise offers a unique opportunity for studying the effect of depressurization from sealevel lowering to gas hydrate systems because it is a bathymetric barrier preventing the Subtropical Front separating subtropical and subantarctic waters from migrating during glacial-interglacial cycles. Hence, bottom-water temperatures can be assumed to remain constant. Recent results from paleoceanographic studies however, indicate that bottom-temperature may have varied locally. These temperature changes may have a more significant effect on the shallow gas hydrate system in the study area than the relatively gradual decrease of pressure associated with sealevel lowering.

  8. A statistical mechanical description of biomolecular hydration

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-02-01

    We present an efficient and accurate theoretical description of the structural hydration of biological macromolecules. The hydration of molecules of almost arbitrary size (tRNA, antibody-antigen complexes, photosynthetic reaction centre) can be studied in solution and in the crystal environment. The biomolecular structure obtained from x-ray crystallography, NMR, or modeling is required as input information. The structural arrangement of water molecules near a biomolecular surface is represented by the local water density analogous to the corresponding electron density in an x-ray diffraction experiment. The water-density distribution is approximated in terms of two- and three-particle correlation functions of solute atoms with water using a potentials-of-mean-force expansion.

  9. Comparison of the water change characteristics between the formation and dissociation of methane hydrate and the freezing and thawing of ice in sand

    Institute of Scientific and Technical Information of China (English)

    Peng Zhang; Qingbai Wu; Yingmei Wang

    2009-01-01

    Hydrate formation and dissociation processes are always accompanied by water migration in porous media, which is similar to the ice. In our study, a novel pF-meter sensor which could detect the changes of water content inside sand was first applied to hydrate formation and dissociation processes. It also can study the water change characteristics in the core scale of a partially saturated silica sand sample and compare the differences of water changes between the processes of formation and dissociation of methane hydrate and freezing and thawing of ice. The experimental results showed that the water changes in the processes of formation and dissociation of methane hydrate were basically similar to that of the freezing and thawing of ice in sand. When methane hydrate or ice was formed, water changes showed the decrease in water content on the whole and the pF values rose following the formation processes. However, there were very obvious differences between the ice thawing and hydrate dissociation.

  10. Composite model to reproduce the mechanical behaviour of methane hydrate bearing soils

    Science.gov (United States)

    De la Fuente, Maria

    2016-04-01

    Methane hydrate bearing sediments (MHBS) are naturally-occurring materials containing different components in the pores that may suffer phase changes under relative small temperature and pressure variations for conditions typically prevailing a few hundreds of meters below sea level. Their modelling needs to account for heat and mass balance equations of the different components, and several strategies already exist to combine them (e.g., Rutqvist & Moridis, 2009; Sánchez et al. 2014). These equations have to be completed by restrictions and constitutive laws reproducing the phenomenology of heat and fluid flows, phase change conditions and mechanical response. While the formulation of the non-mechanical laws generally includes explicitly the mass fraction of methane in each phase, which allows for a natural update of parameters during phase changes, mechanical laws are, in most cases, stated for the whole solid skeleton (Uchida et al., 2012; Soga et al. 2006). In this paper, a mechanical model is proposed to cope with the response of MHBS. It is based on a composite approach that allows defining the thermo-hydro-mechanical response of mineral skeleton and solid hydrates independently. The global stress-strain-temperature response of the solid phase (grains + hydrate) is then obtained by combining both responses according to energy principle following the work by Pinyol et al. (2007). In this way, dissociation of MH can be assessed on the basis of the stress state and temperature prevailing locally within the hydrate component. Besides, its structuring effect is naturally accounted for by the model according to patterns of MH inclusions within soil pores. This paper describes the fundamental hypothesis behind the model and its formulation. Its performance is assessed by comparison with laboratory data presented in the literature. An analysis of MHBS response to several stress-temperature paths representing potential field cases is finally presented. References

  11. Kinetics of formation and dissociation of sII hydrogen clathrate hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Duarte, A.R.C. [Delft Univ. of Technology, Delft (Netherlands). Dept. of Physical Chemistry and Molecular Thermodynamics; Peters, C. [Delft Univ. of Technology, Delft (Netherlands). Dept. of Physical Chemistry and Molecular Thermodynamics]|[Delft Univ. of Technology, Delft (Netherlands). Dept. of Process and Energy Laboratory for Process Equipment; Zevenbergen, J. [TNO Defense, Security and Safety, Rijswijk (Netherlands)

    2008-07-01

    The potential for storing hydrogen in its molecular form in clathrate hydrates was investigated in order to explore the possibility of using these solids as a safe hydrogen storing method for the transportation sector. This paper presented experimental data on the kinetics of hydrogen clathrate hydrate formation, with particular reference to the formation and decomposition of the hydrate in a pressure range from 5.5 to 15.0 MPa. Experiments were performed for a binary system using hydrogen (H{sub 2}) and tetrahydrofuran (THF), which forms structures sII clathrate hydrate. Pressure was shown to have a strong influence on induction time, the rate of hydrate formation, the number of moles consumed and the temperature at which the gas hydrates are formed. The time required for the hydrate to be formed was lower for high pressures, and the temperature needed for the first crystals to appear was higher. The rate of hydrate formation was also higher when the driving forces increased. The number of moles of hydrogen entrapped in the solid phase increased as the experimental pressure increased, indicating that higher pressures are preferable for the formation of hydrogen clathrate hydrate. For a finite period of time, more hydrate was formed when the pressure was high. The results of this study may be useful in determining the viability of hydrogen clathrate hydrates as a storage medium in the transportation sector. The entrapment of hydrogen in clathrate hydrates may provide a clean and environmentally sound alternative to metal hydrides. In addition, it is a reversible process that avoids the need for a chemical reaction for hydrogen uptake and release. 8 refs., 2 tabs., 8 figs.

  12. Comparing the symptoms and mechanisms of "dissociation" in dissociative identity disorder and borderline personality disorder.

    Science.gov (United States)

    Laddis, Andreas; Dell, Paul F; Korzekwa, Marilyn

    2017-01-01

    A total of 75 patients were diagnosed with the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised as having dissociative identity disorder (DID), and 100 patients were diagnosed with the Structured Interview for DSM-IV Personality as having borderline personality disorder (BPD). Both groups were administered the Multidimensional Inventory of Dissociation (MID). DID patients had significantly higher MID scores than BPD patients, different distributions of MID scores, and different MID subscale profiles in 3 ranges of MID scores (0-15, 15-30, 30-45). The core MID symptoms-exhibited at all ranges of MID scores-for DID patients (the presence of alters, identity confusion, and memory problems) and BPD patients (flashbacks, identity confusion, and memory problems) were ostensibly similar but were considered to be mostly produced by different underlying processes. Multiple regression analyses showed that the core MID symptoms of DID patients had different predictors than did the core MID symptoms of BPD patients. Alter identities seemed to generate most-but not all-dissociative phenomena in DID patients, whereas only the 24% highest scoring BPD patients (MID ≥45) seemed to manifest alter-driven dissociative experiences. Most BPD dissociative experiences appeared to be due to 5 other mechanisms: (a) BPD-specific, stress-driven, rapid shifts of self-state; (b and c) nondefensive disruptions of the framework of perceptual organization with or without an accompanying BPD-specific, dissociation-like disintegration of affective/neurocognitive functioning; (d) a defensive distancing or detachment from distress (i.e., simple depersonalization); and (e) Allen, Console, and Lewis's (1999) severe absorptive detachment.

  13. Investigation into the Formation and Adhesion of Cyclopentane Hydrates on Mechanically Robust Vapor-Deposited Polymeric Coatings.

    Science.gov (United States)

    Sojoudi, Hossein; Walsh, Matthew R; Gleason, Karen K; McKinley, Gareth H

    2015-06-09

    Blockage of pipelines by formation and accumulation of clathrate hydrates of natural gases (also called gas hydrates) can compromise project safety and economics in oil and gas operations, particularly at high pressures and low temperatures such as those found in subsea or arctic environments. Cyclopentane (CyC5) hydrate has attracted interest as a model system for studying natural gas hydrates, because CyC5, like typical natural gas hydrate formers, is almost fully immiscible in water; and thus CyC5 hydrate formation is governed not only by thermodynamic phase considerations but also kinetic factors such as the hydrocarbon/water interfacial area, as well as mass and heat transfer constraints, as for natural gas hydrates. We present a macroscale investigation of the formation and adhesion strength of CyC5 hydrate deposits on bilayer polymer coatings with a range of wettabilities. The polymeric bilayer coatings are developed using initiated chemical vapor deposition (iCVD) of a mechanically robust and densely cross-linked polymeric base layer (polydivinylbenzene or pDVB) that is capped with a covalently attached thin hydrate-phobic fluorine-rich top layer (poly(perfluorodecyl acrylate) or pPFDA). The CyC5 hydrates are formed from CyC5-in-water emulsions, and differential scanning calorimetry (DSC) is used to confirm the thermal dissociation properties of the solid hydrate deposits. We also investigate the adhesion of the CyC5 hydrate deposits on bare and bilayer polymer-coated silicon and steel substrates. Goniometric measurements with drops of CyC5-in-water emulsions on the coated steel substrates exhibit advancing contact angles of 148.3 ± 4.5° and receding contact angles of 142.5 ± 9.8°, indicating the strongly emulsion-repelling nature of the iCVD coatings. The adhesion strength of the CyC5 hydrate deposits is reduced from 220 ± 45 kPa on rough steel substrates to 20 ± 17 kPa on the polymer-coated steel substrates. The measured strength of CyC5 hydrate

  14. Mechanisms Leading to Co-Existence of Gas Hydrate in Ocean Sediments [Part 2 of 2

    Energy Technology Data Exchange (ETDEWEB)

    Bryant, Steven; Juanes, Ruben

    2011-12-31

    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

  15. Mechanisms Leading to Co-Existence of Gas Hydrate in Ocean Sediments [Part 1 of 2

    Energy Technology Data Exchange (ETDEWEB)

    Bryant, Steven; Juanes, Ruben

    2011-12-31

    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

  16. 0℃以下含SDS的甲烷水合物生成方式及过程对其分解速率的影响%The Dependence of the Dissociation Rate of Methane-SDS Hydrate below Ice Point on Its Manners of Forming and Processing

    Institute of Scientific and Technical Information of China (English)

    王秀林; 陈卫东; 陈光进; 孙长宇; 杨兰英; 马庆兰; 陈俊; 刘鹏; 唐绪龙; 赵焕伟

    2009-01-01

    The dissociation rates of methane hydrates formed with and without the presence of sodium dodecyl sulfate (methane-SDS hydrates), were measured under atmospheric pressure and temperatures below ice point to investigate the influence of the hydrate production conditions and manners upon its dissociation kinetic behavior. The experimental results demonstrated that the dissociation rate of methane hydrate below ice point is strongly dependent on the manners of hydrate formation and processing. The dissociation rate of hydrate formed quiescently was lower than that of hydrate formed with stirring; the dissociation rate of hydrate formed at lower pressure was higher than that of hydrate formed at higher pressure; the compaction of hydrate after its formation lowered its sta-bility, i.e., increased its dissociation rate. The stability of hydrate could be increased by prolonging the time period for which hydrate was held at formation temperature and pressure before it was cooled down, or by prolonging the time period for which hydrate was held at dissociation temperature and formation pressure before it was depressurized to atmospheric pressure. It was found that the dissociation rate of methane hydrate varied with the temperature (ranging from 245.2 to 272.2 K) anomalously as reported on the dissociation of methane hydrate without the presence of surfactant as kinetic promoter. The dissociation rate at 268 K was found to be the lowest when the manners and conditions at which hydrates were formed and processed were fixed.

  17. Mechanisms Leading to Co-Existence of Gas Hydrate in Ocean Sediments [Part 2 of 2

    Energy Technology Data Exchange (ETDEWEB)

    Bryant, Steven; Juanes, Ruben

    2011-12-31

    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

  18. A non-steady-state condition in sediments at the gas hydrate stability boundary off West Spitsbergen: Evidence for gas hydrate dissociation or just dynamic methane transport

    Science.gov (United States)

    Treude, Tina; Krause, Stefan; Bertics, Victoria; Steinle, Lea; Niemann, Helge; Liebetrau, Volker; Feseker, Tomas; Burwicz, Ewa; Krastel, Sebastian; Berndt, Christian

    2015-04-01

    , and sediment surface concentrations of CH4, SO4, DIC, and POC) were able to show that the observed twin sulfate-methane transition zones are an ephemeral phenomenon occurring during increase of methane production in the sediment, which can be introduced by, e.g., gas hydrate dissociation. References Berndt, C., T. Feseker, T. Treude, S. Krastel, V. Liebetrau, H. Niemann, V. J. Bertics, I. Dumke, K. Dunnbier, B. Ferre, C. Graves, F. Gross, K. Hissmann, V. Huhnerbach, S. Krause, K. Lieser, J. Schauer and L. Steinle (2014). "Temporal constraints on hydrate-controlled methane seepage off svalbard." Science 343: 284-287. Westbrook, G. K., K. E. Thatcher, E. J. Rohling, A. M. Piotrowski, H. Pälike, A. H. Osborne, E. G. Nisbet, T. A. Minshull, M. Lanoiselle, R. H. James, V. Hühnerbach, D. Green, R. E. Fisher, A. J. Crocker, A. Chabert, C. Bolton, A. Beszczynska-Möller, C. Berndt and A. Aquilina (2009). "Escape of methane gas from the seabed along the West Spitsbergen continental margin." Geophys. Res. Let. 36: doi:10.1029/2009GL039191.

  19. Evidence for large methane releases to the atmosphere from deep-sea gas-hydrate dissociation during the last glacial episode

    Science.gov (United States)

    de Garidel-Thoron, Thibault; Beaufort, Luc; Bassinot, Franck; Henry, Pierre

    2004-01-01

    Past atmospheric methane-concentration oscillations recorded in polar ice cores vary together with rapid global climatic changes during the last glacial episode. In the “clathrate gun hypothesis,” massive releases of deep-sea methane from marine gas-hydrate dissociation led to these well known, global, abrupt warmings in the past. If evidence for such releases in the water column exists, however, the mechanism and eventual transfer to the atmosphere has not yet been documented clearly. Here we describe a high-resolution marine-sediment record of stable carbon isotopic changes from the Papua Gulf, off Papua New Guinea, which exhibits two extremely depleted excursions (down to -9‰) at ≈39,000 and ≈55,000 years. Morphological, isotopic, and trace metal evidence dismisses authigenic calcite as the main source of depleted carbon. Massive methane release associated with deep-sea gas-hydrate dissociation is the most likely cause for such large depletions of δ13C. The absence of a δ13C gradient in the water column during these events implies that the methane rose through the entire water column, reaching the sea–air interface and thus the atmosphere. Foraminiferal δ18O composition suggests that the rise of the methane in the water column created an upwelling flow. These inferred emission events suggest that during the last glacial episode, this process was likely widespread, including tropical regions. Thus, the release of methane from the ocean floor into the atmosphere cannot be dismissed as a strong positive feedback in climate dynamics processes. PMID:15197255

  20. Fundamentals of Natural Gas and Species Flows from Hydrate Dissociation-Applications to Safety and Sea Floor Instability

    Energy Technology Data Exchange (ETDEWEB)

    Ahmadi, Goodarz

    2005-09-01

    Natural gas production from the dissociation of methane hydrate in a confined reservoir by a depressurizing down-hole well was studied. The case that the well pressure was kept constant was treated and two different linearization schemes in an axisymmetric configuration were used in the analysis. For different fixed well pressures and reservoir temperatures, approximate self-similar solutions were obtained. Distributions of temperature, pressure and gas velocity field across the reservoir were evaluated. The distance of the decomposition front from the well and the natural gas production rate as functions of time were also computed. Time evolutions of the resulting profiles were presented in graphical forms and their differences with the constant well output results were studied. It was shown that the gas production rate was a sensitive function of well pressure and reservoir temperature. The sensitivity of the results to the linearization scheme used was also studied.

  1. The impact of hydrate saturation on the mechanical, electrical, and thermal properties of hydrate-bearing sand, silts, and clay

    Energy Technology Data Exchange (ETDEWEB)

    Santamarina, J.C. [Georgia Inst. of Technology, Atlanta, GA (United States). School of Civil and Environmental Engineering; Ruppel, C. [United States Geological Survey, Woods Hole, MA (United States)

    2008-07-01

    A study was conducted to provide an internally-consistent, systematically-acquired database that could help in evaluating gas hydrate reservoirs. Other objectives were to assist in geomechanical analyses, hazards evaluation and the development of methane hydrate production techniques in sandy lithologies and fine-grained sediments that exist in the northern Gulf of Mexico. An understanding of the physical properties of hydrate-bearing sediments facilitates the interpretation of geophysical field data, borehole and slope stability analyses, and reservoir simulation and production models. This paper reported on the key findings derived from 5 years of laboratory experiments conducted on synthetic samples of sand, silts, or clays subjected to various confining pressures. The samples contained controlled saturations of tetrahydrofuran hydrate formed from the dissolved phase. This internally-consistent data set was used to conduct a comprehensive analysis of the trends in geophysical and geotechnical properties as a function of hydrate saturation, soil characteristics, and other parameters. The experiments emphasized measurements of seismic velocities, electrical conductivity and permittivity, large strain deformation and strength, and thermal conductivity. The impact of hydrate formation technique on the resulting physical properties measurements were discussed. The data set was used to identify systematic effects of sediment characteristics, hydrate concentration, and state of stress. The study showed that the electrical properties of hydrate-bearing sediments are less sensitive to the method used to form hydrate in the laboratory than to hydrate saturation. It was concluded that mechanical properties are strongly influenced by both soil properties and the hydrate loci. Since the thermal conductivity depends on the interaction of several factors, it cannot be readily predicted by volume average formulations. 23 refs., 2 tabs., 9 figs.

  2. Formation mechanism of authigenic gypsum in marine methane hydrate settings: Evidence from the northern South China Sea

    Science.gov (United States)

    Lin, Qi; Wang, Jiasheng; Algeo, Thomas J.; Su, Pibo; Hu, Gaowei

    2016-09-01

    During the last decade, gypsum has been discovered widely in marine methane hydrate-bearing sediments. However, whether this gypsum is an in-situ authigenic precipitate remains controversial. The GMGS2 expedition carried out in 2013 by the Guangzhou Marine Geological Survey (GMGS) in the northern South China Sea provided an excellent opportunity for investigating the formation of authigenic minerals and, in particular, the relationship between gypsum and methane hydrate. In this contribution, we analyzed the morphology and sulfur isotope composition of gypsum and authigenic pyrite as well as the carbon and oxygen isotopic compositions of authigenic carbonate in a drillcore from Site GMGS2-08. These methane-derived carbonates have characteristic carbon and oxygen isotopic compositions (δ13C: -57.9‰ to -27.3‰ VPDB; δ18O: +1.0‰ to +3.8‰ VPDB) related to upward seepage of methane following dissociation of underlying methane hydrates since the Late Pleistocene. Our data suggest that gypsum in the sulfate-methane transition zone (SMTZ) of this core precipitated as in-situ authigenic mineral. Based on its sulfur isotopic composition, the gypsum sulfur is a mixture of sulfate derived from seawater and from partial oxidation of authigenic pyrite. Porewater Ca2+ ions for authigenic gypsum were likely generated from carbonate dissolution through acidification produced by oxidation of authigenic pyrite and ion exclusion during methane hydrate formation. This study thus links the formation mechanism of authigenic gypsum with the oxidation of authigenic pyrite and evolution of underlying methane hydrates. These findings suggest that authigenic gypsum may be a useful proxy for recognition of SMTZs and methane hydrate zones in modern and ancient marine methane hydrate geo-systems.

  3. Effects of Geomechanical Mechanism on the Gas Production Behavior: A Simulation Study of Class-3 Type Four-Way-Closure Ridge Hydrate Deposit Offshore Southwestern Taiwan

    Science.gov (United States)

    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

  4. Hydrate dissolution as a potential mechanism for pockmark formation in the Niger delta

    Science.gov (United States)

    Sultan, N.; Marsset, B.; Ker, S.; Marsset, T.; Voisset, M.; Vernant, A. M.; Bayon, G.; Cauquil, E.; Adamy, J.; Colliat, J. L.; Drapeau, D.

    2010-08-01

    Based on acquired geophysical, geological and geotechnical data and modeling, we suggest hydrate dissolution to cause sediment collapse and pockmark formation in the Niger delta. Very high-resolution bathymetry data acquired from the Niger delta reveal the morphology of pockmarks with different shapes and sizes going from a small ring depression surrounding an irregular floor to more typical pockmarks with uniform depression. Geophysical data, in situ piezocone measurements, piezometer measurements and sediment cores demonstrate the presence of a common internal architecture of the studied pockmarks: inner sediments rich in gas hydrates surrounded by overpressured sediments. The temperature, pressure and salinity conditions of the studied area have allowed us to exclude the process of gas-hydrate dissociation (gas hydrate turns into free gas/water mixture) as a trigger of the observed pockmarks. Based on numerical modeling, we demonstrate that gas-hydrate dissolution (gas hydrate becomes mixture of water and dissolved gas) under a local decrease of the gas concentration at the base of the gas-hydrate occurrence zone (GHOZ) can explain the excess pore pressure and fluid flow surrounding the central hydrated area and the sediment collapse at the border of the GHOZ. The different deformation (or development) stages of the detected pockmarks confirm that a local process such as the amount of gas flow through faults rather than a regional one is at the origin of those depressions.

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

    Science.gov (United States)

    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

  6. Mechanisms of Peptide Fragmentation from Time-and Energy-Resolved Surface-Induced Dissociation Studies: Dissociation of Angiotensin Analogs

    Energy Technology Data Exchange (ETDEWEB)

    Laskin, Julia; Bailey, Thomas H.; Futrell, Jean H.

    2006-03-01

    Energetics and mechanism of dissociation of singly protonated angiotensin III (RVYIHPF) and its analogs RVYIFPF, RVYIYPF, RVYIHAF, and RVYIHDF was studied using surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially configured for studying ion activation by collisions with surfaces. The energetics and dynamics of peptide fragmentation were deduced by modeling the time- and energy-resolved survival curves for each precursor ion using an RRKM based approach developed in our laboratory. Fragmentation mechanisms were inferred from comparison of time- and energy-resolved fragmentation efficiency curves (TFECs) of different fragment ions followed by RRKM modeling of dissociation of angiotensin III into six major families of fragment ions. Detailed modeling demonstrated that dissociation of these peptides is dominated by loss of ammonia from the precursor ion and characterized by a high energy barrier of 1.6 eV. Loss of NH3 and subsequent rearrangement of the MH-NH3 ion results in proton mobilization and release of ca. 30 kcal/mol into internal excitation of the MH-NH3 ion. The resulting highly excited ion accesses a variety of non-specific dissociation pathways with very high rate constants. Fast fragmentation of excited MH-NH3 ion forms a variety of abundant bn-NH3 and an-NH3 fragment ions. Abundant XH and HX internal fragments are also formed, reflecting the stability of histidine-containing diketopiperazine structures.

  7. Mechanisms of peptide fragmentation from time- and energy-resolved surface-induced dissociation studies: Dissociation of angiotensin analogs

    Science.gov (United States)

    Laskin, Julia; Bailey, Thomas H.; Futrell, Jean H.

    2006-03-01

    Energetics and mechanism of dissociation of singly protonated angiotensin III (RVYIHPF) and its analogs RVYIFPF, RVYIYPF, RVYIHAF and RVYIHDF was studied using surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially configured for studying ion activation by collisions with surfaces. The energetics and dynamics of peptide fragmentation were deduced by modeling the time- and energy-resolved survival curves for each precursor ion using an RRKM-based approach developed in our laboratory. Fragmentation mechanisms were inferred from comparison of time- and energy-resolved fragmentation efficiency curves (TFECs) of different fragment ions followed by RRKM modeling of dissociation of angiotensin III into six major families of fragment ions. Detailed modeling demonstrated that dissociation of these peptides is dominated by loss of ammonia from the precursor ion and characterized by a high-energy barrier of 1.6 eV. Loss of NH3 and subsequent rearrangement of the MH+-NH3 ion results in proton mobilization and release of ca. 30 kcal/mol into internal excitation of the MH+-NH3 ion. The resulting highly excited ion accesses a variety of non-specific dissociation pathways with very high rate constants. Fast fragmentation of excited MH+-NH3 ion forms a variety of abundant bn-NH3 and an-NH3 fragment ions. Abundant XH and HX internal fragments are also formed, reflecting the stability of histidine-containing diketopiperazine structures.

  8. Hydrate bearing clayey sediments: Formation and gas production concepts

    KAUST Repository

    Jang, Jaewon

    2016-06-20

    Hydro-thermo-chemo and mechanically coupled processes determine hydrate morphology and control gas production from hydrate-bearing sediments. Force balance, together with mass and energy conservation analyses anchored in published data provide robust asymptotic solutions that reflect governing processes in hydrate systems. Results demonstrate that hydrate segregation in clayey sediments results in a two-material system whereby hydrate lenses are surrounded by hydrate-free water-saturated clay. Hydrate saturation can reach ≈2% by concentrating the excess dissolved gas in the pore water and ≈20% from metabolizable carbon. Higher hydrate saturations are often found in natural sediments and imply methane transport by advection or diffusion processes. Hydrate dissociation is a strongly endothermic event; the available latent heat in a reservoir can sustain significant hydrate dissociation without triggering ice formation during depressurization. The volume of hydrate expands 2-to-4 times upon dissociation or CO2single bondCH4 replacement. Volume expansion can be controlled to maintain lenses open and to create new open mode discontinuities that favor gas recovery. Pore size is the most critical sediment parameter for hydrate formation and gas recovery and is controlled by the smallest grains in a sediment. Therefore any characterization must carefully consider the amount of fines and their associated mineralogy.

  9. Using open hole and cased-hole resistivity logs to monitor gas hydrate dissociation during a thermal test in the mallik 5L-38 research well, Mackenzie Delta, Canada

    Science.gov (United States)

    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

  10. Dissociable mechanisms underlying individual differences in visual working memory capacity.

    Science.gov (United States)

    Gulbinaite, Rasa; Johnson, Addie; de Jong, Ritske; Morey, Candice C; van Rijn, Hedderik

    2014-10-01

    Individuals scoring relatively high on measures of working memory tend to be more proficient at controlling attention to minimize the effect of distracting information. It is currently unknown whether such superior attention control abilities are mediated by stronger suppression of irrelevant information, enhancement of relevant information, or both. Here we used steady-state visual evoked potentials (SSVEPs) with the Eriksen flanker task to track simultaneously the attention to relevant and irrelevant information by tagging target and distractors with different frequencies. This design allowed us to dissociate attentional biasing of perceptual processing (via SSVEPs) and stimulus processing in the frontal cognitive control network (via time-frequency analyses of EEG data). We show that while preparing for the upcoming stimulus, high- and low-WMC individuals use different strategies: High-WMC individuals show attentional suppression of the irrelevant stimuli, whereas low-WMC individuals demonstrate attentional enhancement of the relevant stimuli. Moreover, behavioral performance was predicted by trial-to-trial fluctuations in strength of distractor-suppression for high-WMC participants. We found no evidence for WMC-related differences in cognitive control network functioning, as measured by midfrontal theta-band power. Taken together, these findings suggest that early suppression of irrelevant information is a key underlying neural mechanism by which superior attention control abilities are implemented.

  11. QUANTUM MECHANICAL STUDY OF THE COMPETITIVE HYDRATION BETWEEN PROTONATED QUINAZOLINE AND LI+, NA+, AND CA2+ IONS

    Science.gov (United States)

    Hydration reactions are fundamental to many biological functions and environmental processes. The energetics of hydration of inorganic and organic chemical species influences their fate and transport behavior in the environment. In this study, gas-phase quantum mechanical calcula...

  12. Clathrate Hydrates of Isopentane + Carbon Dioxide and Isopentane + Methane: Experimental Measurements of Dissociation Conditions Hydrates (clathrates d’isopentane + dioxyde de carbone et d’isopentane + méthane : Déterminations expérimentales des conditions de dissociation

    Directory of Open Access Journals (Sweden)

    Mohammadi A.H.

    2010-11-01

    Full Text Available In this work, experimental dissociation data for clathrate hydrates of isopentane + carbon dioxide and isopentane + methane are reported in the temperature ranges of (273.5-282.4 and (275.5-285.7 K, respectively. The experimental data were generated using an isochoric pressure-search method. The reliability of this method is examined by generating new dissociation data for clathrate hydrates of isopentane + methane and comparing them with the experimental data reported in the literature. The acceptable agreement demonstrates the reliability of the experimental method used in this work. The experimental data for all measured systems are finally compared with the corresponding experimental data in the absence of isopentane reported in the literature to identify its promotion effects. Des données expérimentales de dissociation d’hydrates d’isopentane + dioxyde de carbone et d’isopentane + méthane sont respectivement présentées ici dans les gammes de température (273.5-282.4 et (275.5-285.7 K. Ces valeurs expérimentales ont été générées en utilisant une méthode isochore de recherche d’une discontinuité de pression. La fiabilité de cette méthode est examinée grâce à la production de données nouvelles pour la dissociation des hydrates de méthane + isopentane et à leur comparaison à des données expérimentales disponibles dans la littérature. L’accord tout à fait acceptable permet de garantir la fiabilité de la méthode expérimentale utilisée. Les valeurs expérimentales de tous les systèmes mesurés sont finalement comparées aux données expérimentales correspondantes de la littérature, obtenues toutefois en l’absence d’isopentane, et ce afin de quantifier ses effets promoteurs de formation d’hydrates.

  13. An application of the novel quantum mechanical/molecular mechanical method combined with the theory of energy representation: An ionic dissociation of a water molecule in the supercritical water.

    Science.gov (United States)

    Takahashi, Hideaki; Satou, Wataru; Hori, Takumi; Nitta, Tomoshige

    2005-01-22

    A novel quantum chemical approach recently developed has been applied to an ionic dissociation of a water molecule (2H(2)O-->H(3)O(+)+OH(-)) in ambient and supercritical water. The method is based on the quantum mechanical/molecular mechanical (QM/MM) simulations combined with the theory of energy representation (QM/MM-ER), where the energy distribution function of MM solvent molecules around a QM solute serves as a fundamental variable to determine the hydration free energy of the solute according to the rigorous framework of the theory of energy representation. The density dependence of the dissociation free energy in the supercritical water has been investigated for the density range from 0.1 to 0.6 g/cm(3) with the temperature fixed at a constant. It has been found that the product ionic species significantly stabilizes in the high density region as compared with the low density. Consequently, the dissociation free energy decreases monotonically as the density increases. The decomposition of the hydration free energy has revealed that the entropic term (-TDeltaS) strongly depends on the density of the solution and dominates the behavior of the dissociation free energy with respect to the variation of the density. The increase in the entropic term in the low density region can be attributed to the decrease in the translational degrees of freedom brought about by the aggregation of solvent water molecules around the ionic solute.

  14. Atomistic modeling of structure II gas hydrate mechanics: Compressibility and equations of state

    Directory of Open Access Journals (Sweden)

    Thomas M. Vlasic

    2016-08-01

    Full Text Available This work uses density functional theory (DFT to investigate the poorly characterized structure II gas hydrates, for various guests (empty, propane, butane, ethane-methane, propane-methane, at the atomistic scale to determine key structure and mechanical properties such as equilibrium lattice volume and bulk modulus. Several equations of state (EOS for solids (Murnaghan, Birch-Murnaghan, Vinet, Liu were fitted to energy-volume curves resulting from structure optimization simulations. These EOS, which can be used to characterize the compressional behaviour of gas hydrates, were evaluated in terms of their robustness. The three-parameter Vinet EOS was found to perform just as well if not better than the four-parameter Liu EOS, over the pressure range in this study. As expected, the Murnaghan EOS proved to be the least robust. Furthermore, the equilibrium lattice volumes were found to increase with guest size, with double-guest hydrates showing a larger increase than single-guest hydrates, which has significant implications for the widely used van der Waals and Platteeuw thermodynamic model for gas hydrates. Also, hydrogen bonds prove to be the most likely factor contributing to the resistance of gas hydrates to compression; bulk modulus was found to increase linearly with hydrogen bond density, resulting in a relationship that could be used predictively to determine the bulk modulus of various structure II gas hydrates. Taken together, these results fill a long existing gap in the material chemical physics of these important clathrates.

  15. Atomistic modeling of structure II gas hydrate mechanics: Compressibility and equations of state

    Science.gov (United States)

    Vlasic, Thomas M.; Servio, Phillip; Rey, Alejandro D.

    2016-08-01

    This work uses density functional theory (DFT) to investigate the poorly characterized structure II gas hydrates, for various guests (empty, propane, butane, ethane-methane, propane-methane), at the atomistic scale to determine key structure and mechanical properties such as equilibrium lattice volume and bulk modulus. Several equations of state (EOS) for solids (Murnaghan, Birch-Murnaghan, Vinet, Liu) were fitted to energy-volume curves resulting from structure optimization simulations. These EOS, which can be used to characterize the compressional behaviour of gas hydrates, were evaluated in terms of their robustness. The three-parameter Vinet EOS was found to perform just as well if not better than the four-parameter Liu EOS, over the pressure range in this study. As expected, the Murnaghan EOS proved to be the least robust. Furthermore, the equilibrium lattice volumes were found to increase with guest size, with double-guest hydrates showing a larger increase than single-guest hydrates, which has significant implications for the widely used van der Waals and Platteeuw thermodynamic model for gas hydrates. Also, hydrogen bonds prove to be the most likely factor contributing to the resistance of gas hydrates to compression; bulk modulus was found to increase linearly with hydrogen bond density, resulting in a relationship that could be used predictively to determine the bulk modulus of various structure II gas hydrates. Taken together, these results fill a long existing gap in the material chemical physics of these important clathrates.

  16. Identification of a mechanism of transformation of clathrate hydrate structures I to II or H.

    Science.gov (United States)

    Yoshioki, Shuzo

    2012-07-01

    Binary mixed-gas hydrates including methane and other guest gases demonstrate a structural transition between the sI and sII phases. Under increasing pressure pure methane hydrate exhibits a phase transition first from sI to sII and then to sH. But the mechanism of the transformation from sI to sII or sH has not yet been identified. Recently, molecular dynamics simulations of methane hydrates suggest there may exist uncommon 15-hedral cages (5¹²6³), linking the sI and sII cages. In addition, xenon hydrate involving 15-hedral cages has been synthesized and named an hsI hydrate. Based on the hsI cages, we propose a mechanism for the transition of sI to sII or sH at atomic level resolution. The sI hydrate is first transformed to hsI, and hsI is further transformed to sII. Upon compression, hsI is transformed to sH owing to depletion of atomic layers. The mechanism of transformation speculated here calls for experimental verification.

  17. Dissociating neural mechanisms of temporal sequencing and processing phonemes.

    Science.gov (United States)

    Gelfand, Jenna R; Bookheimer, Susan Y

    2003-06-01

    Using fMRI, we sought to determine whether the posterior, superior portion of Broca's area performs operations on phoneme segments specifically or implements processes general to sequencing discrete units. Twelve healthy volunteers performed two sequence manipulation tasks and one matching task, using strings of syllables and hummed notes. The posterior portion of Broca's area responded specifically to the sequence manipulation tasks, independent of whether the stimuli were composed of phonemes or hummed notes. In contrast, the left supramarginal gyrus was somewhat more specific to sequencing phoneme segments. These results suggest a functional dissociation of the canonical left hemisphere language regions encompassing the "phonological loop," with the left posterior inferior frontal gyrus responding not to the sound structure of language but rather to sequential operations that may underlie the ability to form words out of dissociable elements.

  18. Simulation of gas production from hydrate reservoir by the combination of warm water flooding and depressurization

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Gas production from hydrate reservoir by the combination of warm water flooding and depressurization is proposed,which can overcome the deficiency of single production method.Based on the combination production method,the physical and mathematical models are developed to simulate the hydrate dissociation.The mathematical model can be used to analyze the effects of the flow of multiphase fluid,the kinetic process of hydrate dissociation,the endothermic process of hydrate dissociation,ice-water phase equilibrium,the convection and conduction on the hydrate dissociation and gas and water production.The mechanism of gas production by the combination of warm water flooding and depressurization is revealed by the numerical simulation.The evolutions of such physical variables as pressure,temperature,saturations and gas and water rates are analyzed.Numerical results show that under certain conditions the combination method has the advantage of longer stable period of high gas rate than the single producing method.

  19. Dissociable brain mechanisms for processing social exclusion and rule violation.

    Science.gov (United States)

    Bolling, Danielle Z; Pitskel, Naomi B; Deen, Ben; Crowley, Michael J; McPartland, James C; Mayes, Linda C; Pelphrey, Kevin A

    2011-02-01

    Social exclusion inherently involves an element of expectancy violation, in that we expect other people to follow the unwritten rule to include us in social interactions. In this functional magnetic resonance imaging (fMRI) study, we employed a unique modification of an interactive virtual ball-tossing game called "Cyberball" (Williams et al., 2000) and a novel paradigm called "Cybershape," in which rules are broken in the absence of social exclusion, to dissociate brain regions that process social exclusion from rule violations more generally. Our Cyberball game employed an alternating block design and removed evoked responses to events when the participant was throwing the ball in inclusion to make this condition comparable to exclusion, where participants did not throw. With these modifications, we replicated prior findings of ventral anterior cingulate cortex (vACC), insula, and posterior cingulate cortex activity evoked by social exclusion relative to inclusion. We also identified exclusion-evoked activity in the hippocampi, left ventrolateral prefrontal cortex, and left middle temporal gyrus. Comparing social exclusion and rule violation revealed a functional dissociation in the active neural systems as well as differential functional connectivity with vACC. Some overlap was observed in regions differentially modulated by social exclusion and rule violation, including the vACC and lateral parietal cortex. These overlapping brain regions showed different activation during social exclusion compared to rule violation, each relative to fair play. Comparing activation patterns to social exclusion and rule violation allowed for the dissociation of brain regions involved in the experience of exclusion versus expectancy violation.

  20. Dissociative mechanism of F-actin thermal denaturation.

    Science.gov (United States)

    Mikhailova, V V; Kurganov, B I; Pivovarova, A V; Levitsky, D I

    2006-11-01

    We have applied differential scanning calorimetry to investigate thermal unfolding of F-actin. It has been shown that the thermal stability of F-actin strongly depends on ADP concentration. The transition temperature, T(m), increases with increasing ADP concentration up to 1 mM. The T(m) value also depends on the concentration of F-actin: it increases by almost 3 degrees C as the F-actin concentration is increased from 0.5 to 2.0 mg/ml. Similar dependence of the T(m) value on protein concentration was demonstrated for F-actin stabilized by phalloidin, whereas it was much less pronounced in the presence of AlF4(-). However, T(m) was independent of protein concentration in the case of monomeric G-actin. The results suggest that at least two reversible stages precede irreversible thermal denaturation of F-actin; one of them is dissociation of ADP from actin subunits, and another is dissociation of subunits from the ends of actin filaments. The model explains why unfolding of F-actin depends on both ADP and protein concentration.

  1. Clathrate hydrates in nature.

    Science.gov (United States)

    Hester, Keith C; Brewer, Peter G

    2009-01-01

    Scientific knowledge of natural clathrate hydrates has grown enormously over the past decade, with spectacular new findings of large exposures of complex hydrates on the sea floor, the development of new tools for examining the solid phase in situ, significant progress in modeling natural hydrate systems, and the discovery of exotic hydrates associated with sea floor venting of liquid CO2. Major unresolved questions remain about the role of hydrates in response to climate change today, and correlations between the hydrate reservoir of Earth and the stable isotopic evidence of massive hydrate dissociation in the geologic past. The examination of hydrates as a possible energy resource is proceeding apace for the subpermafrost accumulations in the Arctic, but serious questions remain about the viability of marine hydrates as an economic resource. New and energetic explorations by nations such as India and China are quickly uncovering large hydrate findings on their continental shelves.

  2. The Mechanical Properties and Hydration Characteristics of Cement Pastes Containing Added-calcium Coal Gangue

    Institute of Scientific and Technical Information of China (English)

    LI Dongxu; SONG Xuyan

    2008-01-01

    The mechanical properties of several kinds of coal gangue calcined with limestone were Researched so as to find the optimum way of calcinations with limestone. Mierostructure and property of hydration process of cement pastes containing added-calcium coal gangue were analyzed by means of scanning electron microscope (SEM) and method of mercury in trusion poremeasurement (MIP), etc. The experiment can approve those results: when proper amounst of gypsum and fluorite were taken as mineralizers in the course of calcinations of added-calcium coal gangue, activity of coal gangue can be effectively improved. The results of mechanical property and structural characteristic such as hydration process, hydration product and microstructure etc. of cement pastes containing added-calcium coal gangue are consistent.

  3. Effect of Hydration Aging and Water Binder Ratio on Microstructure and Mechanical Properties of Sprayed Concrete

    Institute of Scientific and Technical Information of China (English)

    NIU Ditao; WANG Jiabin; WANG Yan

    2015-01-01

    In order to study the durability of sprayed concrete (shotcrete), effects of different hydration aging and water-binder ratio (w/b) on the microstructure of cement paste and basic mechanical properties of test specimens were investigated. The phase composition, mass percentage of ettringite and portland in hydration production and microstructure were characterized by X-ray diffraction (XRD), thermo gravimetry-differential scanning calorimetry (TG-DSC) and scanning electron microscopy (SEM), respectively. The experimental results showed that changes in phase composition was more signiifcant than those of water-binder ratio. With hydration aging and water-binder ratio increased, the mass percentage of ettringite and portland was decreased from 4.42%, 1.49% to 3.31%, 1.35%, respectively and the microstructure of paste was signiifcantly compacted. Likewise, the mechanical properties including cubic compressive strength and splitting tensile strength were rised obviously.

  4. Nonequilibrium dissociation mechanisms in low temperature nitrogen and carbon monoxide plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Capitelli, Mario [Department of Chemistry, University of Bari (Italy); CNR IMIP, Bari (Italy); Colonna, Gianpiero, E-mail: gianpiero.colonna@ba.imip.cnr.it [CNR IMIP, Bari (Italy); D’Ammando, Giuliano [Department of Chemistry, University of Bari (Italy); Laporta, Vincenzo [CNR IMIP, Bari (Italy); Department of Physics and Astronomy, University College of London (United Kingdom); Laricchiuta, Annarita [CNR IMIP, Bari (Italy)

    2014-06-25

    Highlights: • The role of vibrational excitation in affecting N{sub 2} dissociation is put in evidence. • Calculations with new complete sets of e-N{sub 2} cross sections have been performed. • Vibrational mechanism dominates e-N{sub 2} dissociation for E/N < 50 Td. • Vibrational and electron dissociation mechanisms are competitive for E/N > 50 Td. - Abstract: The role of vibrational excitation in affecting the dissociation under discharge conditions characterized by reduced electric field E/N ⩽ 80 Td has been investigated in N{sub 2}. The kinetic calculations have been performed using a self-consistent approach, solving at the same time the master equation for the composition and the distribution of internal states (vibrational and electronic) and the Boltzmann equation for the electron energy distribution function. The results show that vibrational mechanisms involving heavy particle excited states dominate electron impact dissociation mechanisms involving the whole vibrational ladder for E/N < 50 Td, the two mechanisms being competitive for E/N > 50 Td.

  5. The kinetics and mechanism of dissociation of metal carbonyls in high infrared laser fields

    Science.gov (United States)

    Langsam, Y.; Ronn, A. M.

    1981-01-01

    The method of laser induced dielectric breakdown has been used to study the dissociation of three metal carbonyls. Following non-resonant excitation by a TEA CO 2 laser, amorphous micro-metallic particles are deposited. The identity of the various species within a laser induced plasma for a series of related reactant molecules, has been determined using infrared and visible real time fluorescence techniques. Based upon the energetics of dissociation and the relative magnitudes of the rates of activation and deactivation for various collision partners of the plasma fluorescence, an energy transfer map as well as probable mechanisms are proposed. The kinetics of a variety of chemical reactions under plasma conditions are discussed in terms of elementary collision theory. It is shown that the internal vibration manifold of the metal carbonyls is equilibrated prior to the dissociation in agreement with the majority of laser induced multiphoton dissociation experiments.

  6. Mechanical behavior of a composite interface: Calcium-silicate-hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Palkovic, Steven D.; Moeini, Sina; Büyüköztürk, Oral, E-mail: obuyuk@mit.edu [Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Yip, Sidney [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

    2015-07-21

    The generalized stacking fault (GSF) is a conceptual procedure historically used to assess shear behavior of defect-free crystalline structures through molecular dynamics or density functional theory simulations. We apply the GSF technique to the spatially and chemically complex quasi-layered structure of calcium-silicate-hydrates (C-S-H), the fundamental nanoscale binder within cementitious materials. A failure plane is enforced to calculate the shear traction-displacement response along a composite interface containing highly confined water molecules, hydroxyl groups, and calcium ions. GSF simulations are compared with affine (homogeneous) shear simulations, which allow strain to localize naturally in response to the local atomic environment. Comparison of strength and deformation behavior for the two loading methods shows the composite interface controls bulk shear deformation. Both models indicate the maximum shear strength of C-S-H exhibits a normal-stress dependency typical of cohesive-frictional materials. These findings suggest the applicability of GSF techniques to inhomogeneous structures and bonding environments, including other layered systems such as biological materials containing organic and inorganic interfaces.

  7. Zero kinetic energy photoelectron spectroscopy of tryptamine and the dissociation pathway of the singly hydrated cation cluster.

    Science.gov (United States)

    Gu, Quanli; Knee, J L

    2012-09-14

    The relative ionization energies of tryptamine conformations are determined by zero kinetic energy photoelectron spectroscopy and photoionization efficiency measurements. The relative cationic conformational stabilities are compared to the published results for the neutral molecule. In the cation, the interaction strength changes significantly between amino group and either the phenyl or the pyrrole moiety of the indole chromophore where most of the positive charge is located, leading to different conformational structures and relative conformer energies in the cation. In particular, the measured adiabatic ionization potential of isomer B is 60,928 ± 5 cm(-1), at least 400 cm(-1) higher than any of the 6 other tryptamine isomers which all have ionization potentials within 200 cm(-1) of each other. In addition to the monomer, measurements were made on the A conformer of the tryptamine(+)-H(2)O complex including the ionization threshold and cation dissociation energy measured using a threshold photoionization fragmentation method. The water cluster exhibits an unexpectedly high ionization potential of 60,307 ± 100 cm(-1), close to the conformer A monomer of 60 320 ± 100 cm(-1). It also exhibits surprisingly low dissociation energy of 1750 ± 150 cm(-1) compared to other H-bonding involved cation-H(2)O complexes which are typically several thousands of wavenumbers higher. Quantum chemical calculations indicate that upon ionization the structure of the parent molecule in the water complex remains mostly unchanged due to the rigid intermolecular double hydrogen bonded water molecule bridging the monomer backbone and its side chain thus leading to the high ionization potential in the water cluster. The surprisingly low dissociation energy measured in the cationic water complex is attributed to the formation of a much more stable structural isomer H(+) in the exit channel.

  8. Hole-doping of mechanically exfoliated graphene by confined hydration layers

    NARCIS (Netherlands)

    Bollmann, Tjeerd Rogier Johannes; Antipina, L.Y.; Temmen, M.; Reichling, M.; Sorokin, P.B.

    2015-01-01

    By the use of non-contact atomic force microscopy (NC-AFM) and Kelvin probe force microscopy (KPFM), we measure the local surface potential of mechanically exfoliated graphene on the prototypical insulating hydrophilic substrate of CaF2(111). Hydration layers confined between the graphene and the Ca

  9. Hole-doping of mechanically exfoliated graphene by confined hydration layers

    NARCIS (Netherlands)

    Bollmann, T.R.J.; Antipina, L.Y.; Temmen, M.; Reichling, M.; Sorokin, P.B.

    2015-01-01

    By the use of non-contact atomic force microscopy (NC-AFM) and Kelvin probe force microscopy (KPFM), we measure the local surface potential of mechanically exfoliated graphene on the prototypical insulating hydrophilic substrate of CaF2(111). Hydration layers confined between the graphene and the Ca

  10. Hole-doping of mechanically exfoliated graphene by confined hydration layers

    NARCIS (Netherlands)

    Bollmann, Tjeerd Rogier Johannes; Antipina, L.Y.; Temmen, M.; Reichling, M.; Sorokin, P.B.

    2015-01-01

    By the use of non-contact atomic force microscopy (NC-AFM) and Kelvin probe force microscopy (KPFM), we measure the local surface potential of mechanically exfoliated graphene on the prototypical insulating hydrophilic substrate of CaF2(111). Hydration layers confined between the graphene and the

  11. Hydration mechanism and leaching behavior of bauxite-calcination-method red mud-coal gangue based cementitious materials

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Na; Li, Hongxu [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Beijing Key Laboratory of Rare and Precious Metals Green Recycling and Extraction, University of Science and Technology Beijing, Beijing 100083 (China); Liu, Xiaoming, E-mail: liuxm@ustb.edu.cn [School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Beijing Key Laboratory of Rare and Precious Metals Green Recycling and Extraction, University of Science and Technology Beijing, Beijing 100083 (China)

    2016-08-15

    Highlights: • Nanocrystalline regions in size of ∼5 nm were found in the amorphous C-A-S-H gel. • A hydration model was proposed to clarify the hydration mechanism. • The developed cementitious materials are environmentally acceptable. - Abstract: A deep investigation on the hydration mechanism of bauxite-calcination-method red mud-coal gangue based cementitious materials was conducted from viewpoints of hydration products and hydration heat analysis. As a main hydration product, the microstructure of C-A-S-H gel was observed using high resolution transmission electron microscopy. It was found that the C-A-S-H gel is composed of amorphous regions and nanocrystalline regions. Most of regions in the C-A-S-H gel are amorphous with continuous distribution, and the nanocrystalline regions on scale of ∼5 nm are dispersed irregularly within the amorphous regions. The hydration heat of red mud-coal gangue based cementitious materials is much lower than that of the ordinary Portland cement. A hydration model was proposed for this kind of cementitious materials, and the hydration process mainly consists of four stages which are dissolution of materials, formation of C-A-S-H gels and ettringite, cementation of hydration products, and polycondensation of C-A-S-H gels. There are no strict boundaries among these four basic stages, and they proceed crossing each other. Moreover, the leaching toxicity tests were also performed to prove that the developed red mud-coal gangue based cementitious materials are environmentally acceptable.

  12. Adsorption of hydrated hydroxide and hydronium ions on Ag(1 1 1). A quantum mechanical investigation

    Science.gov (United States)

    Patrito, E. M.; Paredes-Olivera, P.

    2003-03-01

    In this paper we have studied comparatively the adsorption of hydroxide and hydronium ions, extending our previous study on hydronium adsorption [J. Phys. Chem. B. 105 (2001) 7227] and emphasizing the adsorption of hydroxide. The calculations were performed on the 111 surface of silver using ab initio quantum mechanical methods (Hartree-Fock+Moller-Plesset second order perturbation theory). The adsorption was investigated for the bare and the hydrated ions (up to three water molecules). Binding energies, equilibrium structures and charge transfer processes were investigated. While the successive hydration of hydronium detaches the ion from the surface, the hydrated hydroxide anion remains specifically adsorbed. Charge transfer processes between the adsorbates and the surface were studied using electron density difference plots and effective charges obtained from Mulliken populations and from surface-dipole moment curves. The energetics of the surface reactions leading to the formation of the hydrated hydronium and hydroxide ions from the bare adsorbed ions and water molecules was also investigated. Both reactions are exothermic mainly due to the formation of strong hydrogen bonds. The effect of an external homogeneous electric field perpendicular to the surface on different adsorbate properties was investigated for the bare and hydrated hydroxide ion in order to model the environment of the electrical double layer. The electric field affects the orientation of the water molecules on the surface and the hydroxide surface distance.

  13. Hydration of the cyanide ion: an ab initio quantum mechanical charge field molecular dynamics study.

    Science.gov (United States)

    Moin, Syed Tarique; Hofer, Thomas S

    2014-12-21

    This paper presents an ab initio quantum mechanical charge field molecular dynamics simulation study of the cyanide anion (CN(-)) in aqueous solution where hydrogen bond formation plays a dominant role in the hydration process. Preferential orientation of water hydrogens compared to oxygen atoms was quantified in terms of radial, angular as well as coordination number distributions. All structural results indicate that the water hydrogens are attracted towards CN(-) atoms, thus contributing to the formation of the hydration layer. Moreover, a clear picture of the local arrangement of water molecules around the ellipsoidal CN(-) ion is provided via angular-radial distribution and spatial distribution functions. Apart from the structural analysis, the evaluation of water dynamics in terms of ligand mean residence times and H-bond correlation functions indicates the weak structure making capacity of the CN(-) ion. The similar values of H-bond lifetimes obtained for the NHwat and CHwat bonds indicate an isokinetic behaviour of these H-bonds, since there is a very small difference in the magnitude of the lifetimes. On the other hand, the H-bond lifetimes between water molecules of the hydration shell, and between solute and solvent evidence the slightly stable hydration of the CN(-). Overall, the H-bonding dominates in the hydration process of the cyanide anion enabling it to become soluble in the aqueous environment associated to chemical and biological processes.

  14. Dissociable mechanisms of cognitive control in prefrontal and premotor cortex.

    Science.gov (United States)

    Chambers, Christopher D; Bellgrove, Mark A; Gould, Ian C; English, Therese; Garavan, Hugh; McNaught, Elizabeth; Kamke, Marc; Mattingley, Jason B

    2007-12-01

    Intelligent behavior depends on the ability to suppress inappropriate actions and resolve interference between competing responses. Recent clinical and neuroimaging evidence has demonstrated the involvement of prefrontal, parietal, and premotor areas during behaviors that emphasize conflict and inhibition. It remains unclear, however, whether discrete subregions within this network are crucial for overseeing more specific inhibitory demands. Here we probed the functional specialization of human prefrontal cortex by combining repetitive transcranial magnetic stimulation (rTMS) with integrated behavioral measures of response inhibition (stop-signal task) and response competition (flanker task). Participants undertook a combined stop-signal/flanker task after rTMS of the inferior frontal gyrus (IFG) or dorsal premotor cortex (dPM) in each hemisphere. Stimulation of the right IFG impaired stop-signal inhibition under conditions of heightened response competition but did not influence the ability to suppress a competing response. In contrast, stimulation of the right dPM facilitated execution but had no effect on inhibition. Neither of these results was observed during rTMS of corresponding left-hemisphere regions. Overall, our findings are consistent with existing evidence that the right IFG is crucial for inhibitory control. The observed double dissociation of neurodisruptive effects between the right IFG and right dPM further implies that response inhibition and execution rely on distinct neural processes despite activating a common cortical network.

  15. The crucial effect of early-stage gelation on the mechanical properties of cement hydrates

    Science.gov (United States)

    Ioannidou, Katerina; Kanduč, Matej; Li, Lunna; Frenkel, Daan; Dobnikar, Jure; Del Gado, Emanuela

    2016-07-01

    Gelation and densification of calcium-silicate-hydrate take place during cement hydration. Both processes are crucial for the development of cement strength, and for the long-term evolution of concrete structures. However, the physicochemical environment evolves during cement formation, making it difficult to disentangle what factors are crucial for the mechanical properties. Here we use Monte Carlo and Molecular Dynamics simulations to study a coarse-grained model of cement formation, and investigate the equilibrium and arrested states. We can correlate the various structures with the time evolution of the interactions between the nano-hydrates during the preparation of cement. The novel emerging picture is that the changes of the physicochemical environment, which dictate the evolution of the effective interactions, specifically favour the early gel formation and its continuous densification. Our observations help us understand how cement attains its unique strength and may help in the rational design of the properties of cement and related materials.

  16. Geochemical and sedimentological evidence for the massive dissociation and formation of subsurface gas hydrates on the Umitaka Spur, eastern margin of Japan Sea

    Science.gov (United States)

    Hiruta, A.; Matsumoto, R.; Snyder, G.; Tomaru, H.; Aoyama, C.; Machiyama, H.; Hiromatsu, M.; Hiruta, T.

    2006-12-01

    The Umitaka (UT) spur in Japan Sea is characterized by subsurface gas chimneys, seafloor gas hydrate, methane-induced carbonate nodules, BSRs, methane plumes, pockmarks and mounds[1]. These indicate strong methane flux and active seepages on the UT spur. Thick pile of organic-rich Neogene strata in the UT spur area are considered as hydrocarbon source rocks for oil and natural gas reservoirs of Niigata gas and oil fields[2]. Methane plumes, approximately 600 m high, are concentrated in central and north part of the UT spur[3]. Gas hydrates (G.H.) have been recovered from the plume sites. Sediment cores (3.5~9m) recovered on and around the UT spur are grey to olive black silt and clay with occasional thin ash layers. C-14 age of planktonic foraminifera indicates that the deepest sediment in 9m piston core is at most 30ky.BP.. Sulfate concentration in pore water decreases linearly with depth toward zero (SMI: sulfate methane interface) at 1.5 to 3.5 mbsf at every coring site. Alkalinity increases rapidly downward to SMI, showing mirror image of sulfate pattern. Delta 13C values of DIC becomes ~-20 permil VPDB around SMI depth. These data strongly indicate coupled anoxic oxidation of methane and sulfate reduction in shallow sediments. The methane flux calculated from the depth profile of sulfate is about 4 times stronger than that of the Blake Ridge. Chloride concentrations in pore water linearly increase or linearly decrease with depth in some cores. Linearly- increasing and decreasing patterns of chloride concentration likely reflect diffusion of chloride between bottom sea water and subsurface brine and less saline water pools at depths, respectively. Formation of brine pools is explained as the results of rapid gas hydrate formation while the buildup of freshwater pools is caused by a massive gas hydrate dissociation, which was probably triggered by a sea-level fall and shoaling of BGHS during the LGM. Carbonate geochemistry: Methane derived, calcite nodules (-28

  17. Is Submarine Groundwater Discharge a Gas Hydrate Formation Mechanism on the Circum-Arctic Shelf?

    Science.gov (United States)

    Frederick, J. M.; Buffett, B. A.

    2015-12-01

    Methane hydrate is an ice-like solid that can sequester large quantities of methane gas in marine sediments along most continental margins where thermodynamic conditions permit its formation. Along the circum-Arctic shelf, relict permafrost-associated methane hydrate deposits formed when non-glaciated portions of the shelf experienced subaerial exposure during ocean transgressions. Gas hydrate stability and the permeability of circum-Arctic shelf sediments to gas migration is closely linked with relict submarine permafrost. Heat flow observations on the Alaskan North Slope and Canadian Beaufort Shelf suggest the movement of groundwater offshore, but direct observations of groundwater flow do not exist. Submarine discharge, an offshore flow of fresh, terrestrial groundwater, can affect the temperature and salinity field in shelf sediments, and may be an important factor in submarine permafrost and gas hydrate evolution on the Arctic continental shelf. Submarine groundwater discharge may also enhance the transport of organic matter for methanogenesis within marine sediments. Because it is buoyancy-driven, the velocity field contains regions with a vertical (upward) component as groundwater flows offshore. This combination of factors makes submarine groundwater discharge a potential mechanism controlling permafrost-associated gas hydrate evolution on the Arctic continental shelf. In this study, we quantitatively investigate the feasibility of submarine groundwater discharge as a control on permafrost-associated gas hydrate formation on the Arctic continental shelf, using the Canadian Beaufort Shelf as an example. We have developed a shelf-scale, two-dimensional numerical model based on the finite volume method for two-phase flow of pore fluid and methane gas within Arctic shelf sediments. The model tracks the evolution of the pressure, temperature, salinity, methane gas, methane hydrate, and permafrost fields given imposed boundary conditions, with latent heat of

  18. Ionic mechanisms of burst firing in dissociated Purkinje neurons.

    Science.gov (United States)

    Swensen, Andrew M; Bean, Bruce P

    2003-10-22

    Cerebellar Purkinje neurons have intrinsic membrane properties that favor burst firing, seen not only during complex spikes elicited by climbing fiber input but also with direct electrical stimulation of cell bodies. We examined the ionic conductances that underlie all-or-none burst firing elicited in acutely dissociated mouse Purkinje neurons by short depolarizing current injections. Blocking voltage-dependent calcium entry by cadmium or replacement of external calcium by magnesium enhanced burst firing, but it was blocked by cobalt replacement of calcium, probably reflecting block of sodium channels. In voltage-clamp experiments, we used the burst waveform of each cell as a voltage command and used ionic substitutions and pharmacological manipulations to isolate tetrodotoxin (TTX)-sensitive sodium current, P-type and T-type calcium current, hyperpolarization-activated cation current (Ih), voltage-activated potassium current, large-conductance calcium-activated potassium current, and small-conductance calcium-activated potassium (SK) current. Measured near the middle of the first interspike interval, TTX-sensitive sodium current carried the largest inward current, and T-type calcium current was also substantial. Current through P-type channels was large immediately after a spike but decayed rapidly. These inward currents were opposed by substantial components of voltage-dependent and calcium-dependent potassium current. Termination of the burst is caused partly by decay of sodium current, together with a progressive buildup of SK current after the first interspike interval. Although burst firing depends on the net balance between multiple large currents flowing after a spike, it is surprisingly robust, probably reflecting complex interactions between the exact voltage waveform and voltage and calcium dependence of the various currents.

  19. Conditional dissociation as a punishment mechanism in the evolution of cooperation

    Science.gov (United States)

    Qu, Xinglong; Zhou, Changli; Cao, Zhigang; Yang, Xiaoguang

    2016-05-01

    Recent studies show that conditional dissociation, a.k.a. post-interaction partner-refusal, can promote the emergence and stability of cooperation. However, in most of these studies, players' strategies are restricted to pure ones, which is obviously inconsistent with many biological and economic situations. Another concern with line of these studies is that conditional dissociation is often combined with other mechanisms. These mechanisms may favor cooperation per se, leaving it unclear whether conditional dissociation is indeed a key factor. In this paper, we study a clean model, pruning all the factors other than conditional dissociation that may favor cooperation. We find that conditional dissociation, which could be viewed as a variant of peer punishment, does promote cooperation, no matter whether mixed strategies are allowed or not. This confirms the previous findings in the literature. In addition, compared with the pure strategy scenario, cooperators are less competitive when mixed strategies are allowed. Our main finding is supported by both the numerical simulations and the theoretical analysis of Neutrally Stable Strategy. We also find that cooperative behavior is favored when waiting time and/or the population's lifespan are longer.

  20. 海底天然气水合物分解对海洋钻井安全的影响%The Influence of Subsea Natural Gas Hydrate Dissociation on the Safety of Offshore Drilling

    Institute of Scientific and Technical Information of China (English)

    宫智武; 张亮; 程海清; 刘延民; 任韶然

    2015-01-01

    When subsea natural gas hydrate (NGH) dissociation is encountered ,offshore drilling safe-ty is notably influenced .Gas production performances of NGH were analyzed and gas production after hy-drate deposition was estimated under different drilling conditions according to the dynamics and thermody-namics of NGH dissociation . The calculations were based on the fundamental characteristics of subsea NGH ,which provided the basis for evaluating quantitatively the influence of natural gas hydrate dissocia-tion on the safety of offshore drilling .The results showed that as drilling proceeded through hydrate bear-ing zones ,gas production rate and cumulative gas production of hydrate dissociation tends to rise ,and that the gas production was in a squared exponential relationship with the NGH dissociation radius under cer-tain NGH saturation .NGH dissociation rate rose exponentially with the increase of the temperature differ-ence between drilling fluid and NGH sediment ,and drilling through hydrate layers in shallow water tended to break it down and as water depth and wellbore pressure rised ,NGH dissociation became more difficult . Increasing the drilling rate was preferable for reducing NGH dissociation when drilling through hydrate layers .It was demonstrated that NGH control during offshore drilling should focus on NGH prediction be-fore drilling ,and that drilling fluid density and temperature adjustment and essential well control measures should be taken to ensure drilling safety under the condition of certain gas hydrate decomposition.%为分析天然气水合物分解对海洋钻井安全的影响,根据海底天然气水合物特征,结合天然气水合物分解动力学和热力学条件,研究了不同钻井工况下天然气水合物分解产气规律,估算了天然气水合物分解后的产气量。结果表明,在钻进天然气水合物层过程中,天然气水合物分解产气速率和累计产气量逐渐增大;在天然气水合物

  1. The mechanism of the dehydration of alcohols and the hydration of alkenes in acid solution

    Science.gov (United States)

    Vinnik, M. I.; Obraztsov, P. A.

    1990-01-01

    Kinetic data for the hydration of unsaturated compounds, the dehydration of alcohols, and the isotope exchange of the oxygen atom in alcohols and aqueous solutions of strong acids are analysed to establish the detailed mechanisms of these reactions. The catalytic action of the acid is caused not only by its ability to protonate the reactant but also by the possibility of the formation of reactive complexes of the reactant with the acid hydrates or the molecules of the undissociated acids. Equations are presented whereby the influence of the ionising capacity of the medium on the effective rate constants for the reactions indicated can be taken into account quantitatively. The question of the involvement of carbonium ions as reactive intermediates in reactions involving the dehydration of alcohols, the hydration of unsaturated compounds, and the isotope exchange of the oxygen atom in alcohols is examined. Complexes of the reactant with a solvated proton, the acid molecules, and the acid hydrates are the intermediates in these reactions. The relative contributions of the complexes to the effective rate constant depend on the acid concentration in the aqueous solution. The bibliography includes 65 references

  2. Hydration mechanisms of two polymorphs of synthetic ye'elimite

    Energy Technology Data Exchange (ETDEWEB)

    Cuesta, A.; Álvarez-Pinazo, G. [Departamento de Química Inorgánica, Universidad de Málaga, Campus Teatinos S/N. 29071-Málaga (Spain); Sanfélix, S.G. [Unidad Técnica de Investigación de Materiales, AIDICO, Avda. Benjamín Franklin, 17 Paterna, Valencia (Spain); Peral, I. [ALBA-CELLS Synchrotron, Carretera BP 1413, Km. 3.3, E-08290 Cerdanyola, Barcelona (Spain); Aranda, M.A.G. [Departamento de Química Inorgánica, Universidad de Málaga, Campus Teatinos S/N. 29071-Málaga (Spain); ALBA-CELLS Synchrotron, Carretera BP 1413, Km. 3.3, E-08290 Cerdanyola, Barcelona (Spain); De la Torre, A.G., E-mail: mgd@uma.es [Departamento de Química Inorgánica, Universidad de Málaga, Campus Teatinos S/N. 29071-Málaga (Spain)

    2014-09-15

    Ye'elimite is the main phase in calcium sulfoaluminate cements and also a key phase in sulfobelite cements. However, its hydration mechanism is not well understood. Here we reported new data on the hydration behavior of ye'elimite using synchrotron and laboratory powder diffraction coupled to the Rietveld methodology. Both internal and external standard methodologies have been used to determine the overall amorphous contents. We have addressed the standard variables: water-to-ye'elimite ratio and additional sulfate sources of different solubilities. Moreover, we report a deep study of the role of the polymorphism of pure ye'elimites. The hydration behavior of orthorhombic stoichiometric and pseudo-cubic solid-solution ye'elimites is discussed. In the absence of additional sulfate sources, stoichiometric-ye'elimite reacts slower than solid-solution-ye'elimite, and AFm-type phases are the main hydrated crystalline phases, as expected. Moreover, solid-solution-ye'elimite produces higher amounts of ettringite than stoichiometric-ye'elimite. However, in the presence of additional sulfates, stoichiometric-ye'elimite reacts faster than solid-solution-ye'elimite.

  3. Structural and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from alite hydration in the presence of sodium and potassium hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Mendoza, Oscar, E-mail: oamendoz@unal.edu.co [Grupo del Cemento y Materiales de Construcción (CEMATCO). Universidad Nacional de Colombia, Facultad de Minas, Medellín (Colombia); Giraldo, Carolina [Cementos Argos S.A., Medellín (Colombia); Camargo, Sergio S. [Engenharia Metalúrgica e de Materiais, Universidade Federal do Rio de Janeiro/COPPE, Rio de Janeiro (Brazil); Tobón, Jorge I. [Grupo del Cemento y Materiales de Construcción (CEMATCO). Universidad Nacional de Colombia, Facultad de Minas, Medellín (Colombia)

    2015-08-15

    This research evaluates the effect of sodium and potassium hydroxide on the structure and nano-mechanical properties of Calcium Silicate Hydrate (C-S-H) formed from the hydration of pure alite. Monoclinic (MIII) alite was synthesized and hydrated, using water-to-alite ratios of 0.5 and 0.6 and additions of 10% NaOH and KOH by weight of alite. Based on results of X-ray diffraction, isothermal calorimetry, thermogravimetric analysis, Nuclear Magnetic Resonance and nanoindentation, two different effects of the alkaline hydroxides on the hydration reaction of alite, both at early and later ages, can be identified: (i) a differentiated hydration process, attributed to an enhancement in calcium hydroxide (CH) precipitation and a stimulation of the C-S-H nuclei; and (ii) an increase in the elastic modulus of the C-S-H aggregations, attributed to an electrostatic attraction between positive charges from the alkaline cations and negative charges from the C-S-H structure.

  4. Nanoscale Charge Balancing Mechanism in Alkali Substituted Calcium-Silicate-Hydrate Gels

    CERN Document Server

    Özçelik, V Ongun

    2016-01-01

    Alkali-activated materials and related alternative cementitious systems are sustainable material technologies that have the potential to substantially lower CO$_2$ emissions associated with the construction industry. However, the impact of augmenting the chemical composition of the material on the main binder phase, calcium-silicate-hydrate gel, is far from understood, particularly since this binder phase is disordered at the nanoscale. Here, we reveal the presence of a charge balancing mechanism at the molecular level, which leads to stable structures when alkalis (i.e., Na or K) are incorporated into a calcium-silicate-hydrate gel, as modeled using crystalline 14{\\AA} tobermorite. These alkali containing charge balanced structures possess superior mechanical properties compared to their charge unbalanced counterparts. Our results, which are based on first-principles simulations using density functional theory, include the impact of charge balancing on the optimized geometries of the new model phases, format...

  5. Effect of superplasticizers on the hydration kinetic and mechanical properties of Portland cement pastes

    Directory of Open Access Journals (Sweden)

    Safaa M.A. El-Gamal

    2012-04-01

    Full Text Available Hydration of ordinary Portland cement in the presence of two different types of superplasticizers namely sodium lignosulfonate (LS and naphthalene sulfonate-formaldehyde condensate (NSF was studied using different experimental techniques. Superplasticized ordinary Portland cement pastes were prepared using the values of standard water of consistency with different additions of each type of superplasticizers used. Pastes were hydrated for different time intervals under normal curing conditions. The results reveal that both superplasticizers increase the workability and reduce the standard water of consistency. This results in an improvement in the mechanical properties of superplasticized cement pastes at all ages of the hydration–hardening process. Naphthalene sulfonate-formaldehyde condensate was found to have the higher efficiency in improving the mechanical properties of the hardened pastes than that of sodium lignosulfonate superplasticizer.

  6. Hydration study of mechanically activated mixtures of Portland cement and fly ash

    Directory of Open Access Journals (Sweden)

    GORDANA STEFANOVIC

    2007-06-01

    Full Text Available Fly ash (FA can be used in cement mixtures with certain limitations. The problem of the mentioned mixtures lies in the insufficient activity of the particles of FA in the reactions which are important for the establishment of the mechanical characteristics of cement. This is particularly true for the hydration reactions. As a result of this, cement pastes formed by mixing ash and clinker have worse characteristics compared to those of pure Portland cement (PC, especially in the early period of setting. As is well known, FA can be a good solution for the neutralization of the negative effects generated due to the creation of free Ca(OH2 during the hydration of PC, provided that the problems with the low activity of FAare overcome. For the experiments in this study, a mixture of Portland cement and fly ash was used, the content of ash in the mixture being 30 % and 50 %. Mechanical activation was performed in a vibrating ring mill. The goal of this study was to demonstrate, through experimental results, that during the mechanical activation of a PC and FAmixture, the components in the mixture which mostly affect the direction, rate and range of hydration reactions occurring in the mixture had been activated. The values of the compressive strength of the activated and non-activated mixtures and the changes of their specific surface area proved that during the grinding process, the mixture PC+FA had been mechanically activated. The highest increase of compressivestrength was achieved in the early period of setting, which indicates an improvement in the early hydration of the mixture. XRD, DTA and TG analyses showed that the alite (C3S and belite (C2S from the PC and a part of the fly ash were activated.

  7. Dissociation between spatial and temporal integration mechanisms in Vernier fusion.

    Science.gov (United States)

    Drewes, Jan; Zhu, Weina; Melcher, David

    2014-12-01

    The visual system constructs a percept of the world across multiple spatial and temporal scales. This raises the questions of whether different scales involve separate integration mechanisms and whether spatial and temporal factors are linked via spatio-temporal reference frames. We investigated this using Vernier fusion, a phenomenon in which the features of two Vernier stimuli presented in close spatio-temporal proximity are fused into a single percept. With increasing spatial offset, perception changes dramatically from a single percept into apparent motion and later, at larger offsets, into two separately perceived stimuli. We tested the link between spatial and temporal integration by presenting two successive Vernier stimuli presented at varying spatial and temporal offsets. The second Vernier either had the same or the opposite offset as the first. We found that the type of percept depended not only on spatial offset, as reported previously, but interacted with the temporal parameter as well. At temporal separations around 30-40 ms the majority of trials were perceived as motion, while above 70 ms predominantly two separate stimuli were reported. The dominance of the second Vernier varied systematically with temporal offset, peaking around 40 ms ISI. Same-offset conditions showed increasing amounts of perceived separation at large ISIs, but little dependence on spatial offset. As subjects did not always completely fuse stimuli, we separated trials by reported percept (single/fusion, motion, double/segregation). We found systematic indications of spatial fusion even on trials in which subjects perceived temporal segregation. These findings imply that spatial integration/fusion may occur even when the stimuli are perceived as temporally separate entities, suggesting that the mechanisms responsible for temporal segregation and spatial integration may not be mutually exclusive.

  8. Tetrahydrofuran hydrate decomposition characteristics in porous media

    Science.gov (United States)

    Song, Yongchen; Wang, Pengfei; Wang, Shenglong; Zhao, Jiafei; Yang, Mingjun

    2016-12-01

    Many tetrahydrofuran (THF) hydrate properties are similar to those of gas hydrates. In the present work THF hydrate dissociation in four types of porous media is studied. THF solution was cooled to 275.15 K with formation of the hydrate under ambient pressure, and then it dissociated under ambient conditions. THF hydrate dissociation experiments in each porous medium were conducted three times. Magnetic resonance imaging (MRI) was used to obtain images. Decomposition time, THF hydrate saturation and MRI mean intensity (MI) were measured and analyzed. The experimental results showed that the hydrate decomposition time in BZ-4 and BZ-3 was similar and longer than that in BZ-02. In each dissociation process, the hydrate decomposition time of the second and third cycles was shorter than that of the first cycle in BZ-4, BZ-3, and BZ-02. The relationship between THF hydrate saturation and time is almost linear.

  9. Observation of ice sheet formation on methane and ethane gas hydrates using a scanning confocal microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Nagao, J.; Shimomura, N.; Ebinuma, T.; Narita, H. [National Inst. of Advanced Industrial Science and Technology, Toyohira, Sapporo (Japan). Methane Hydrate Research Lab.

    2008-07-01

    Interest in gas hydrates has increased in recent years due to the discovery of large deposits under the ocean floor and in permafrost regions. Natural gas hydrates, including methane, is expected to become a new energy source and a medium for energy storage and transportation. Gas hydrates consist of an open network of water molecules that are hydrogen-bonded in a similar manner to ice. Gas molecules are interstitially engaged under high pressures and low temperatures. Although the dissociation temperature of methane hydrate under atmospheric pressure is about 193 K, studies have shown that methane hydrate can be stored at atmospheric pressure and 267 K for 2 years. Because of this phenomenon, known as self-preservation, transportation and storage of methane hydrate can occur at temperature conditions milder than those for liquefied methane gas at atmospheric pressure. This study examined the surface changes of methane and ethane hydrates during dissociation using an optical microscope and confocal scanning microscope (CSM). This paper reported on the results when the atmospheric gas pressure was decreased. Ice sheets formed on the surfaces of methane and ethane gas hydrates due to depressurizing dissociation of methane and ethane hydrates when the methane and ethane gas pressures were decreased at designated temperatures. The dissociation of methane gas hydrate below below 237 K resulted in the generation of small ice particles on the hydrate surface. A transparent ice sheet formed on the hydrate surface above 242 K. The thickness of the ice sheet on the methane hydrate surface showed the maximum of ca. 30 {mu}m at 253 K. In the case of ethane hydrates, ice particles and ice sheets formed below 262 and 267 respectively. Since the ice particles and ice sheets were formed by water molecules generated during the gas hydrate dissociation, the mechanism of ice sheet formation depends on the dissociation rate of hydrate, ice particle sintering rate, and water molecule

  10. Hole-doping of mechanically exfoliated graphene by confined hydration layers

    Institute of Scientific and Technical Information of China (English)

    Tjeerd R. J. Bollmann[1,2; Liubov Yu. Antipina[3,4; Matthias Temmen[2; Michael Reichling[2; Pavel B. Sorokin[5

    2015-01-01

    By the use of non-contact atomic force microscopy (NC-AFM) and Kelvin probe force microscopy (KPFM), we measure the local surface potential of mechanically exfoliated graphene on the prototypical insulating hydrophilic substrate of CAF2(111). Hydration layers confined between the graphene and the CaF2 substrate, resulting from the graphene's preparation under ambient conditions on the hydrophilic substrate surface, are found to electronically modify the graphene as the material's electron density transfers from graphene to the hydration layer. Density functional theory (DFT) calculations predict that the first 2 to 3 water layers adjacent to the graphene hole-dope the graphene by several percent of a unit charge per unit cell.

  11. Dissociative diffusion mechanism in vacancy-rich materials according to mass action kinetics

    Science.gov (United States)

    Biderman, N. J.; Sundaramoorthy, R.; Haldar, Pradeep; Lloyd, J. R.

    2016-05-01

    Two sets of diffusion-reaction numerical simulations using a finite difference method (FDM) were conducted to investigate fast impurity diffusion via interstitial sites in vacancy-rich materials such as Cu(In,Ga)Se2 (CIGS) and Cu2ZnSn(S, Se)4 (CZTSSe or CZTS) via the dissociative diffusion mechanism where the interstitial diffuser ultimately reacts with a vacancy to produce a substitutional. The first set of simulations extends the standard interstitial-limited dissociative diffusion theory to vacancy-rich material conditions where vacancies are annihilated in large amounts, introducing non-equilibrium vacancy concentration profiles. The second simulation set explores the vacancy-limited dissociative diffusion where impurity incorporation increases the equilibrium vacancy concentration. In addition to diffusion profiles of varying concentrations and shapes that were obtained in all simulations, some of the profiles can be fitted with the constant- and limited-source solutions of Fick's second law despite the non-equilibrium condition induced by the interstitial-vacancy reaction. The first set of simulations reveals that the dissociative diffusion coefficient in vacancy-rich materials is inversely proportional to the initial vacancy concentration. In the second set of numerical simulations, impurity-induced changes in the vacancy concentration lead to distinctive diffusion profile shapes. The simulation results are also compared with published data of impurity diffusion in CIGS. According to the characteristic properties of diffusion profiles from the two set of simulations, experimental detection of the dissociative diffusion mechanism in vacancy-rich materials may be possible.

  12. Dissociative diffusion mechanism in vacancy-rich materials according to mass action kinetics

    Directory of Open Access Journals (Sweden)

    N. J. Biderman

    2016-05-01

    Full Text Available Two sets of diffusion-reaction numerical simulations using a finite difference method (FDM were conducted to investigate fast impurity diffusion via interstitial sites in vacancy-rich materials such as Cu(In,GaSe2 (CIGS and Cu2ZnSn(S, Se4 (CZTSSe or CZTS via the dissociative diffusion mechanism where the interstitial diffuser ultimately reacts with a vacancy to produce a substitutional. The first set of simulations extends the standard interstitial-limited dissociative diffusion theory to vacancy-rich material conditions where vacancies are annihilated in large amounts, introducing non-equilibrium vacancy concentration profiles. The second simulation set explores the vacancy-limited dissociative diffusion where impurity incorporation increases the equilibrium vacancy concentration. In addition to diffusion profiles of varying concentrations and shapes that were obtained in all simulations, some of the profiles can be fitted with the constant- and limited-source solutions of Fick’s second law despite the non-equilibrium condition induced by the interstitial-vacancy reaction. The first set of simulations reveals that the dissociative diffusion coefficient in vacancy-rich materials is inversely proportional to the initial vacancy concentration. In the second set of numerical simulations, impurity-induced changes in the vacancy concentration lead to distinctive diffusion profile shapes. The simulation results are also compared with published data of impurity diffusion in CIGS. According to the characteristic properties of diffusion profiles from the two set of simulations, experimental detection of the dissociative diffusion mechanism in vacancy-rich materials may be possible.

  13. Hydration mechanism and leaching behavior of bauxite-calcination-method red mud-coal gangue based cementitious materials.

    Science.gov (United States)

    Zhang, Na; Li, Hongxu; Liu, Xiaoming

    2016-08-15

    A deep investigation on the hydration mechanism of bauxite-calcination-method red mud-coal gangue based cementitious materials was conducted from viewpoints of hydration products and hydration heat analysis. As a main hydration product, the microstructure of C-A-S-H gel was observed using high resolution transmission electron microscopy. It was found that the C-A-S-H gel is composed of amorphous regions and nanocrystalline regions. Most of regions in the C-A-S-H gel are amorphous with continuous distribution, and the nanocrystalline regions on scale of ∼5nm are dispersed irregularly within the amorphous regions. The hydration heat of red mud-coal gangue based cementitious materials is much lower than that of the ordinary Portland cement. A hydration model was proposed for this kind of cementitious materials, and the hydration process mainly consists of four stages which are dissolution of materials, formation of C-A-S-H gels and ettringite, cementation of hydration products, and polycondensation of C-A-S-H gels. There are no strict boundaries among these four basic stages, and they proceed crossing each other. Moreover, the leaching toxicity tests were also performed to prove that the developed red mud-coal gangue based cementitious materials are environmentally acceptable.

  14. [Dynamic model of protein behavior in water. Possible mechanism of association and dissociation of specific complexes].

    Science.gov (United States)

    Kiaiviariainen, A I

    1979-01-01

    The proposed mechanism of association and dissociation of specific protein complex with ligands is based on the assumption that thermal fluctuations in the non-polar cavities of protein are interrelated due to the co-operative properties of macromolecules. The non-polar cavities, representing the active centres and clefts in the globule jump from the "open" state to the "closed" one with a certain amount of water being removed to the external medium. It is assumed that the association of ligand with the active centre is accompanied by stabilization of the chest state and destibilization of the open one, dissociation being a reverse process. A rapid change in the state of the active centre under the influence of ligand induces a slow relaxation process resulting in similar alterations in the state of the auxiliary non-polar cavities of protein. As a result, the binding constant of ligand increases, while the free energy of protein decreases. Expressions have been obtained which relate the rate constants of association, dissociation and the binding constant to the rate-constant of the nonpolar cavities transitions from the closed state to the open one, and vice versa. They gave a possibility for a qualitative interpretation of the effect of some specific and non-specific agents upon the stability of immunoglobulins, on the influence of salts upon the association and dissociation of antibody-antigene complexes and on the increase in the constant of binding between antibodies and haptens in the course of prolonged immunisation.

  15. Submarine Slope Failure Primed and Triggered by Bottom Water Warming in Oceanic Hydrate-Bearing Deposits

    Directory of Open Access Journals (Sweden)

    Tae-Hyuk Kwon

    2012-08-01

    Full Text Available Many submarine slope failures in hydrate-bearing sedimentary deposits might be directly triggered, or at least primed, by gas hydrate dissociation. It has been reported that during the past 55 years (1955–2010 the 0–2000 m layer of oceans worldwide has been warmed by 0.09 °C because of global warming. This raises the following scientific concern: if warming of the bottom water of deep oceans continues, it would dissociate natural gas hydrates and could eventually trigger massive slope failures. The present study explored the submarine slope instability of oceanic gas hydrate-bearing deposits subjected to bottom water warming. One-dimensional coupled thermal-hydraulic-mechanical (T-H-M finite difference analyses were performed to capture the underlying physical processes initiated by bottom water warming, which includes thermal conduction through sediments, thermal dissociation of gas hydrates, excess pore pressure generation, pressure diffusion, and hydrate dissociation against depressurization. The temperature rise at the seafloor due to bottom water warming is found to create an excess pore pressure that is sufficiently large to reduce the stability of a slope in some cases. Parametric study results suggest that a slope becomes more susceptible to failure with increases in thermal diffusivity and hydrate saturation and decreases in pressure diffusivity, gas saturation, and water depth. Bottom water warming can be further explored to gain a better understanding of the past methane hydrate destabilization events on Earth, assuming that more reliable geological data is available.

  16. Structural determinants of hydration, mechanics and fluid flow in freeze-dried collagen scaffolds.

    Science.gov (United States)

    Offeddu, G S; Ashworth, J C; Cameron, R E; Oyen, M L

    2016-09-01

    Freeze-dried scaffolds provide regeneration templates for a wide range of tissues, due to their flexibility in physical and biological properties. Control of structure is crucial for tuning such properties, and therefore scaffold functionality. However, the common approach of modeling these scaffolds as open-cell foams does not fully account for their structural complexity. Here, the validity of the open-cell model is examined across a range of physical characteristics, rigorously linking morphology to hydration and mechanical properties. Collagen scaffolds with systematic changes in relative density were characterized using Scanning Electron Microscopy, X-ray Micro-Computed Tomography and spherical indentation analyzed in a time-dependent poroelastic framework. Morphologically, all scaffolds were mid-way between the open- and closed-cell models, approaching the closed-cell model as relative density increased. Although pore size remained constant, transport pathway diameter decreased. Larger collagen fractions also produced greater volume swelling on hydration, although the change in pore diameter was constant, and relatively small at ∼6%. Mechanically, the dry and hydrated scaffold moduli varied quadratically with relative density, as expected of open-cell materials. However, the increasing pore wall closure was found to determine the time-dependent nature of the hydrated scaffold response, with a decrease in permeability producing increasingly elastic rather than viscoelastic behavior. These results demonstrate that characterizing the deviation from the open-cell model is vital to gain a full understanding of scaffold biophysical properties, and provide a template for structural studies of other freeze-dried biomaterials. Freeze-dried collagen sponges are three-dimensional microporous scaffolds that have been used for a number of exploratory tissue engineering applications. The characterization of the structure-properties relationships of these scaffolds is

  17. Parametric study of the physical properties of hydrate-bearing sand, silt, and clay sediments: 2. Small-strain mechanical properties

    Science.gov (United States)

    Lee, J. Y.; Francisca, F. M.; Santamarina, J. C.; Ruppel, C.

    2010-11-01

    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, σ'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

  18. Stereochemical mechanism of two sabinene hydrate synthases forming antipodal monoterpenes in thyme (Thymus vulgaris).

    Science.gov (United States)

    Krause, Sandra T; Köllner, Tobias G; Asbach, Julia; Degenhardt, Jörg

    2013-01-15

    The essential oil of Thymus vulgaris consists of a complex blend of mono- and sesquiterpenes that provides the plant with its characteristic aromatic odor. Several chemotypes have been described for thyme. In this study, we identified two enzymes of the sabinene hydrate chemotype which are responsible for the biosynthesis of its major monoterpene alcohols, (1S,2R,4S)-(Z)-sabinene hydrate and (1S,2S,4R)-(E)-sabinene hydrate. Both TPS6 and TPS7 are multiproduct enzymes that formed 16 monoterpenes and thus cover almost the whole monoterpene spectrum of the chemotype. Although the product spectra of both enzymes are similar, they form opposing enantiomers of their chiral products. Incubation of the enzymes with the potential reaction intermediates revealed that the stereospecificity of TPS6 and TPS7 is determined by the formation of the first intermediate, linalyl diphosphate. Since TPS6 and TPS7 shared an amino acid sequence identity of 85%, a mutagenesis study was employed to identify the amino acids that determine the stereoselectivity. One amino acid position had a major influence on the stereochemistry of the formed products. Based on comparative models of TPS6 and TPS7 protein structures with the GPP substrate docked in the active site pocket, the influence of this amino acid residue on the reaction mechanism is discussed.

  19. Role of Mechanical Stress in Regulating Airway Surface Hydration and Mucus Clearance Rates

    Science.gov (United States)

    Button, Brian; Boucher, Richard C.

    2008-01-01

    Effective clearance of mucus is a critical innate airway defense mechanism, and under appropriate conditions, can be stimulated to enhance clearance of inhaled pathogens. It has become increasingly clear that extracellular nucleotides (ATP and UTP) and nucleosides (adenosine) are important regulators of mucus clearance in the airways as a result of their ability to stimulate fluid secretion, mucus hydration, and cilia beat frequency (CBF). One ubiquitous mechanism to stimulate ATP release is through external mechanical stress. This article addresses the role of physiologically-relevant mechanical forces in the lung and their effects on regulating mucociliary clearance (MCC). The effects of mechanical forces on the stimulating ATP release, fluid secretion, CBF, and MCC are discussed. Also discussed is evidence suggesting that airway hydration and stimulation of MCC by stress-mediated ATP release may play a role in several therapeutic strategies directed at improving mucus clearance in patients with obstructive lung diseases, including cystic fibrosis (CF) and chronic obstructive pulmonary disease (COPD). PMID:18585484

  20. Theoretical investigation of the competitive mechanism between dissociation and ionization of H₂⁺ in intense field.

    Science.gov (United States)

    Yao, Hongbin; Zhao, Guangjiu

    2014-10-01

    The competitive mechanism between dissociation and ionization of hydrogen molecular ion in intense field has been theoretically investigated by using an accurate non-Born-Oppenheimer method. The relative yield of fragments indicates that the dissociation and ionization channels are competitive with the increasing laser intensity from 5.0 × 10(13) to 2.0 × 10(14) W/cm(2). In the case of intensity lower than 1.0 × 10(14) W/cm(2), the dissociation channel is dominant, with a minor contribution from ionization. The mechanism of dissociation includes the contributions from the bond softening, bond hardening, below-threshold dissociation, and above-threshold dissociation, which are strongly dependent on the laser intensity and initial vibrational state. Furthermore, the ionization dominates over the dissociation channel at the highest intensity of 2.0 × 10(14) W/cm(2). The reasonable origin of ionization is ascribed as the above-threshold Coulomb explosion, which has been demonstrated by the space-time dependent ionization rate. Moreover, the competition mechanism between dissociation and ionization channels are displayed on the total kinetic energy resolved (KER) spectra, which could be tested at current experimental conditions.

  1. Mechanism and Kinetics Analysis of NO/SO2/N2/O2 Dissociation Reactions in Non-Thermal Plasma

    Institute of Scientific and Technical Information of China (English)

    WANG Xinliang; LI Tingting; WEI Dongxiang; WEI Yanli; GU Fan

    2008-01-01

    The kinetics mechanism of the dissociation reactions in a NO/SO2/N2/O2 system was investigated in consideration of energetic electrons' impacts on a non-thermal plasma. A model was derived from the Boltzmann equation and molecule collision theory to predict the dissociation reaction rate coefficients. Upon comparison with available literature, the model was confirmed to be acceptably accurate in general. Several reaction rate coefficients of the NO/SO2/N2/O2 dissociation system were derived according to the Arrhenius formula. The activation energies of each plasma reaction were calculated by quantum chemistry methods. The relation between the dissociation reaction rate coefficient and electron temperature was established to describe the importance of each reaction and to predict relevant processes of gaseous chemical reactions. The sensitivity of the mechanism of NO/SO2/N2/O2 dissociation reaction in a non-thermal plasma was also analysed.

  2. Exploitation of subsea gas hydrate reservoirs

    Science.gov (United States)

    Janicki, Georg; Schlüter, Stefan; Hennig, Torsten; Deerberg, Görge

    2016-04-01

    Natural gas hydrates are considered to be a potential energy resource in the future. They occur in permafrost areas as well as in subsea sediments and are stable at high pressure and low temperature conditions. According to estimations the amount of carbon bonded in natural gas hydrates worldwide is two times larger than in all known conventional fossil fuels. Besides technical challenges that have to be overcome climate and safety issues have to be considered before a commercial exploitation of such unconventional reservoirs. The potential of producing natural gas from subsea gas hydrate deposits by various means (e.g. depressurization and/or injection of carbon dioxide) is numerically studied in the frame of the German research project »SUGAR«. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into a numerical model. The physics of the process leads to strong non-linear couplings between hydraulic fluid flow, hydrate dissociation and formation, hydraulic properties of the sediment, partial pressures and seawater solution of components and the thermal budget of the system described by the heat equation. This paper is intended to provide an overview of the recent development regarding the production of natural gas from subsea gas hydrate reservoirs. It aims at giving a broad insight into natural gas hydrates and covering relevant aspects of the exploitation process. It is focused on the thermodynamic principles and technological approaches for the exploitation. The effects occurring during natural gas production within hydrate filled sediment layers are identified and discussed by means of numerical simulation results. The behaviour of relevant process parameters such as pressure, temperature and phase saturations is described and compared for different strategies. The simulations are complemented by calculations for different safety relevant problems.

  3. Hole localization, water dissociation mechanisms, and band alignment at aqueous-titania interfaces

    Science.gov (United States)

    Lyons, John L.

    Photocatalytic water splitting is a promising method for generating clean energy, but materials that can efficiently act as photocatalysts are scarce. This is in part due to the fact that exposure to water can strongly alter semiconductor surfaces and therefore photocatalyst performance. Many materials are not stable in aqueous environments; in other cases, local changes in structure may occur, affecting energy-level alignment. Even in the simplest case, dynamic fluctuations modify the organization of interface water. Accounting for such effects requires knowledge of the dominant local structural motifs and also accurate semiconductor band-edge positions, making quantitative prediction of energy-level alignments computationally challenging. Here we employ a combined theoretical approach to study the structure, energy alignment, and hole localization at aqueous-titania interfaces. We calculate the explicit aqueous-semiconductor interface using ab initio molecular dynamics, which provides the fluctuating atomic structure, the extent of water dissociation, and the resulting electrostatic potential. For both anatase and rutile TiO2 we observe spontaneous water dissociation and re-association events that occur via distinct mechanisms. We also find a higher-density water layer occurring on anatase. In both cases, we find that the second monolayer of water plays a crucial role in controlling the extent of water dissociation. Using hybrid functional calculations, we then investigate the propensity for dissociated waters to stabilize photo-excited carriers, and compare the results of rutile and anatase aqueous interfaces. Finally, we use the GW approach from many-body perturbation theory to obtain the position of semiconductor band edges relative to the occupied 1b1 level and thus the redox levels of water, and examine how local structural modifications affect these offsets. This work was performed in collaboration with N. Kharche, M. Z. Ertem, J. T. Muckerman, and M. S

  4. Direct measurement of the correlated dynamics of the protein-backbone and proximal waters of hydration in mechanically strained elastin

    CERN Document Server

    Sun, Cheng; Huang, Jiaxin; Boutis, Gregory S

    2011-01-01

    We report on the direct measurement of the correlation times of the protein backbone carbons and proximal waters of hydration in mechanically strained elastin by nuclear magnetic resonance methods. The experimental data indicate a decrease in the correlation times of the carbonyl carbons as the strain on the biopolymer is increased. These observations are in good agreement with short 4ns molecular dynamics simulations of (VPGVG)3, a well studied mimetic peptide of elastin. The experimental results also indicate a reduction in the correlation time of proximal waters of hydration with increasing strain applied to the elastomer. A simple model is suggested that correlates the increase in the motion of proximal waters of hydration to the increase in frequency of libration of the protein backbone that develops with increasing strain. Together, the reduction in the protein entropy accompanied with the increase in entropy of the proximal waters of hydration with increasing strain, support the notion that the source ...

  5. Comparison of dissociation mechanism between collisionally activated dissociation and charge inversion using alkali metal targets for chlorophenol isomers

    Science.gov (United States)

    Hayakawa, Shigeo; Kawamura, Yoshiaki; Takahashi, Yutaka

    2005-11-01

    Chlorinated aromatic compounds are well-known environmental pollutants whose toxicities depend dramatically on the chlorine substitution pattern, making differentiation of chlorophenol isomers important for environmental analysis. Collisionally activated dissociation (CAD) spectra and charge inversion spectra of ortho-, meta-, and para-chlorophenols (ClC6H4OH) and their partially deuterated forms (ClC6H4OD) were measured using alkali metal targets. The peaks associated with C6H4O+ and C5H5Cl+ ions observed in the CAD spectra result from the loss of HCl and CO fragments, respectively, after the re-arrangement of the hydroxyl hydrogen atom. The peaks associated with C6H4OH- and ClC6H4O- ions observed in the charge inversion spectra result from Cl loss and from hydroxyl bond dissociation, respectively. Isomeric differentiation is possible based on the clear differences observed in the relative intensities of these pairs of peaks. Although the intensities of the peaks associated with C6H4O+ relative to those of C5H5Cl+ in the CAD spectra are independent of the target species, the intensities of the peaks associated with C6H4OH- relative to those of ClC6H4O- in the charge inversion spectra are target dependent. The isomeric dependence of the positive ion distribution patterns in the CAD spectra is proposed to be due to the differences in the rate of the hydrogen atom re-arrangement process. In contrast, the isomeric dependence of the negative ion distribution patterns in the charge inversion spectra is attributed to differences in the bond strength involved in the direct dissociation process in the neutral intermediate species.

  6. Influence of hydration and mechanical characterization of carious primary dentine using an ultra-micro indentation system (UMIS)

    NARCIS (Netherlands)

    Angker, Linny; Nijhof, Niels; Swain, Michael V.; Kilpatrick, Nicola M.

    2004-01-01

    The conditions under which mechanical properties of dentine are tested influence the values recorded. The aims of this study were to examine the effect of hydration on the mechanical properties of primary carious dentine and to provide information on changes in hardness and modulus of elasticity cha

  7. Mechanical switching and coupling between two dissociation pathways in a P-selectin adhesion bond

    Science.gov (United States)

    Evans, Evan; Leung, Andrew; Heinrich, Volkmar; Zhu, Cheng

    2004-08-01

    Many biomolecular bonds exhibit a mechanical strength that increases in proportion to the logarithm of the rate of force application. Consistent with exponential decrease in bond lifetime under rising force, this kinetically limited failure reflects dissociation along a single thermodynamic pathway impeded by a sharp free energy barrier. Using a sensitive force probe to test the leukocyte adhesion bond P-selectin glycoprotein ligand 1 (PSGL-1)-P-selectin, we observed a linear increase of bond strength with each 10-fold increase in the rate of force application from 300 to 30,000 pN/sec, implying a single pathway for failure. However, the strength and lifetime of PSGL-1-P-selectin bonds dropped anomalously when loaded below 300 pN/sec, demonstrating unexpectedly faster dissociation and a possible second pathway for failure. Remarkably, if first loaded by a "jump" in force to 20-30 pN, the bonds became strong when subjected to a force ramp as slow as 30 pN/sec and exhibited the same single-pathway kinetics under all force rates. Applied in this way, a new "jump/ramp" mode of force spectroscopy was used to show that the PSGL-1-P-selectin bond behaves as a mechanochemical switch where force history selects between two dissociation pathways with markedly different properties. Furthermore, replacing PSGL-1 by variants of its 19-aa N terminus and by the crucial tetrasaccharide sialyl LewisX produces dramatic changes in the failure kinetics, suggesting a structural basis for the two pathways. The two-pathway switch seems to provide a mechanism for the "catch bond" response observed recently with PSGL-1-P-selectin bonds subjected to small-constant forces.

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

    Science.gov (United States)

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

    2003-01-01

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

  9. Studying methane migration mechanisms at Walker Ridge, Gulf of Mexico, via 3D methane hydrate reservoir modeling

    Energy Technology Data Exchange (ETDEWEB)

    Nole, Michael [University of Texas at Austin; Daigle, Hugh [University of Texas at Austin; Mohanty, Kishore [University of Texas at Austin; Cook, Ann [Ohio State University; Hillman, Jess [Ohio State University

    2015-12-15

    . 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.

  10. TOUGH+Hydrate v1.0 User's Manual: A Code for the Simulation of System Behavior in Hydrate-Bearing Geologic Media

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-03-01

    TOUGH+HYDRATE v1.0 is a new code for the simulation of the behavior of hydrate-bearing geologic systems. By solving the coupled equations of mass and heat balance, TOUGH+HYDRATE can model the non-isothermal gas release, phase behavior and flow of fluids and heat under conditions typical of common natural CH{sub 4}-hydrate deposits (i.e., in the permafrost and in deep ocean sediments) in complex geological media at any scale (from laboratory to reservoir) at which Darcy's law is valid. TOUGH+HYDRATE v1.0 includes both an equilibrium and a kinetic model of hydrate formation and dissociation. The model accounts for heat and up to four mass components, i.e., water, CH{sub 4}, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dissociation or formation, phase changes and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects and inhibitor-induced effects. TOUGH+HYDRATE is the first member of TOUGH+, the successor to the TOUGH2 [Pruess et al., 1991] family of codes for multi-component, multiphase fluid and heat flow developed at the Lawrence Berkeley National Laboratory. It is written in standard FORTRAN 95, and can be run on any computational platform (workstation, PC, Macintosh) for which such compilers are available.

  11. Invasion of drilling mud into gas-hydrate-bearing sediments. Part I: effect of drilling mud properties

    Science.gov (United States)

    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

  12. Massive Dissociation of Subsurface Gas Hydrates and Collapse of Gas Hydrate Mounds during the LGM in the Eastern Margin of Japan Sea: Evidence from Benthic Forams and U/Th ages of Authigenic Carbonates

    Science.gov (United States)

    Matsumoto, R.; Takeuchi, E.; Sanno, R.

    2008-12-01

    A number of gigantic methane plumes, ca. 600 m high, and massive blocks of gas hydrate, ca. 0.5 m x 1.0 m, have been observed on the Umitaka spur and Joetsu knoll, eastern margin of Japan Sea. Large pockmarks and mounds, ca. 0.5 km in diameter, develop on the spur and knoll. The mounds exhibit rough morphological features characterized by small valleys of 5m wide, steep cliffs, crater-like depressions of 10 m in diameter, and scattered carbonate nodules and crusts of various size and shape with occasional gas hydrate blocks and veins and gas venting. To the contrary, pockmarks are inactive, partly filled by well-stratified mud without any indication of gas venting. 2D and 3D seismic surveys have recognized widely distributed BSRs at around 150 mbsf over the spur and knoll. Seismic profiles delineated deep gas chimney structures below the pockmarks and mounds. Unusual pull-up structures within gas chimneys indicate massive accumulation of gas hydrate. All these findings are likely to suggest that massive hydrate deposits both in gas chimneys at depths and hydrate mounds on the spur and knoll were collapsed and floated up to the sea surface, leaving big holes (= pockmarks) on the seafloor. Quantitative analysis of foraminiferal assemblage has revealed that the well laminated, burrow-free 17 to 22 ka sediments are substantially barren for benthic forams but for unusual species which has been believed to survive under high methane environments. Shells of such a few benthic formas from around 20 ka sediments are anomalously depleted in C-13. U-Th ages of authigenic carbonates of CH4-induced carbonate nodules and crusts are likely to center around 20 ka. Above line of evidences all suggest that gas hydrate system was collapsed and methane fluxes were enhanced during the last glacial maximum (LGM), presumably due to low stand of sea level and pressure release. Broken gas hydrate blocks are expected to float up to the sea surface to supply significant amount of methane to

  13. Molecular Mechanism of Mot1, a TATA-binding Protein (TBP)-DNA Dissociating Enzyme.

    Science.gov (United States)

    Viswanathan, Ramya; True, Jason D; Auble, David T

    2016-07-22

    The essential Saccharomyces cerevisiae ATPase Mot1 globally regulates transcription by impacting the genomic distribution and activity of the TATA-binding protein (TBP). In vitro, Mot1 forms a ternary complex with TBP and DNA and can use ATP hydrolysis to dissociate the TBP-DNA complex. Prior work suggested an interaction between the ATPase domain and a functionally important segment of DNA flanking the TATA sequence. However, how ATP hydrolysis facilitates removal of TBP from DNA is not well understood, and several models have been proposed. To gain insight into the Mot1 mechanism, we dissected the role of the flanking DNA segment by biochemical analysis of complexes formed using DNAs with short single-stranded gaps. In parallel, we used a DNA tethered cleavage approach to map regions of Mot1 in proximity to the DNA under different conditions. Our results define non-equivalent roles for bases within a broad segment of flanking DNA required for Mot1 action. Moreover, we present biochemical evidence for two distinct conformations of the Mot1 ATPase, the detection of which can be modulated by ATP analogs as well as DNA sequence flanking the TATA sequence. We also show using purified complexes that Mot1 dissociation of a stable, high affinity TBP-DNA interaction is surprisingly inefficient, suggesting how other transcription factors that bind to TBP may compete with Mot1. Taken together, these results suggest that TBP-DNA affinity as well as other aspects of promoter sequence influence Mot1 function in vivo.

  14. Mechanisms for O2 dissociation over the BaO (100) surface

    Science.gov (United States)

    Lu, Nai-Xia; Fu, Gang; Xu, Xin; Wan, Hui-Lin

    2008-01-01

    We have investigated the atomic and molecular oxygen adsorptions on the various sites of the BaO (100) surface with both cluster models and the periodic slab models. We found that the atomic oxygen prefers to adsorb on the surface O2- to form the closed-shell peroxides with the binding energies of 83-88kcal/mol. Such a high exothermicity provides a large driving force for the dissociation of molecular O2 on the BaO surfaces. As molecular oxygen approaches the BaO surfaces, the triplet ground state O2 molecule first binds electrostatically on top of the surface Ba2+ site. It further quenches to the singlet potential energy surface to form a covalently bonded O32- species. We proposed a plausible pathway in which the O32- species acts as the key precursor for further dissociation, leading eventually to the formation of surface peroxides O22-. This mechanism is helpful for the understanding of a series of related catalytic processes such as the oxidative coupling of methane, the NOx storage reduction, etc.

  15. Non-Isothermal, Multi-phase, Multi-component Flows through Deformable Methane Hydrate Reservoirs

    CERN Document Server

    Gupta, Shubhangi; Wohlmuth, Barbara

    2015-01-01

    We present a hydro-geomechanical model for subsurface methane hydrate systems. Our model considers kinetic hydrate phase change and non-isothermal, multi-phase, multi-component flow in elastically deforming soils. The model accounts for the effects of hydrate phase change and pore pressure changes on the mechanical properties of the soil, and also for the effect of soil deformation on the fluid-solid interaction properties relevant to reaction and transport processes (e.g., permeability, capillary pressure, reaction surface area). We discuss a 'cause-effect' based decoupling strategy for the model and present our numerical discretization and solution scheme. We then identify the important model components and couplings which are most vital for a hydro-geomechanical hydrate simulator, namely, 1) dissociation kinetics, 2) hydrate phase change coupled with non-isothermal two phase two component flow, 3) two phase flow coupled with linear elasticity (poroelasticity coupling), and finally 4) hydrate phase change c...

  16. Study on molecular structure and hydration mechanism of Domyoji-ko starch by IR and NIR hetero 2D analysis

    Science.gov (United States)

    Katayama, Norihisa; Kondo, Miyuki; Miyazawa, Mitsuhiro

    2010-06-01

    The hydration structure of starch molecule in Domyoji-ko, which is made from gluey rice, was investigated by hetero 2D correlation analysis of IR and NIR spectroscopy. The feature near 1020 cm -1 in the IR spectra of Domyoji-ko is changed by rehydration process, indicating that the molecular structure of amylopectin in the starch has been varied by the hydration without heating. The intensity of a band at 4770 cm -1 in NIR spectra is decreasing with the increasing of either the heating time with water or rehydration time without heating. These results suggest that the hydration of Domyoji-ko has proceeded in similar mechanisms on these processes. The generalized hetero 2D IR-NIR correlation analysis for rehydration of Domyoji-ko has supported the assignments for NIR bands concerning the gelatinization of starch.

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

    Energy Technology Data Exchange (ETDEWEB)

    Moridis, George J. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kowalsky, Michael B. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Pruess, Karsten [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2012-08-01

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

  18. Le problème des hydrates dans le contexte de la production et du transport polyphasiques des pétroles bruts et des gaz naturels. Première partie : physico-chimie de la formation et de la dissociation des hydrates Hydrates Problem Within the Framework of Multiphase Production and Transport of Crude Oils and Natural Gases. Part One: Physical-Chemistry of Hydrates Formation and Dissociation

    Directory of Open Access Journals (Sweden)

    Behar E.

    2006-11-01

    Full Text Available L'exploitation en mer des gisements de combustibles fossiles fluides a amplifié le besoin d'accroître nos connaissances sur les hydrates qui sont susceptibles de boucher les installations de production, de traitement et de transport. Dans cette publication, la structure moléculaire des hydrates I, II et H est rappelée, ensuite l'analyse physico-chimique de leur formation est succinctement décrite tant sur les plans thermodynamique que cinétique. Enfin, les remèdes possibles aux problèmes rencontrés par les compagnies opératrices sont indiqués, essentiellement les inhibiteurs thermodynamiques classiques tels que les alcools ou les sels qui diminuent la température de formation des hydrates, et les additifs dispersants qui évitent la croissance et/ou l'agglomération des cristaux. Pour terminer, une boucle pilote de circulation originale est présentée, ses caractéristiques qui permettent la validation des additifs dispersants dans des conditions hydrodynamiques et physico-chimiques représentatives étant soulignées. Offshore exploitation of fossil fluid fuels has emphasized the need of improving our knowledge on hydrates which can plug production, treatment and transport facilities. In this paper, the molecular structure of I, II and H hydrates is recalled, then the physical-chemistry of their formation is briefly reviewed from both the thermodynamic and the kinetic points of view. Finally, the possible remedies to the problems met by operating companies are described, mainly classical thermodynamic inhibitors such as alcohols or salts which decrease the hydrates formation temperature, and dispersant additives which avoid crystals growth and/or agglomeration. At last an original circulation loop at pilot scale is presented, its characteristics which allow the testing of dispersant additives under representative hydrodynamic and physico-chemical conditions being outlined.

  19. Threshold collision-induced dissociation of Sr(2+)(H(2)O)(x) complexes (x=1-6): An experimental and theoretical investigation of the complete inner shell hydration energies of Sr(2+).

    Science.gov (United States)

    Carl, D R; Chatterjee, B K; Armentrout, P B

    2010-01-28

    The sequential bond energies of Sr(2+)(H(2)O)(x) complexes, where x=1-6, are determined by threshold collision-induced dissociation using a guided ion beam tandem mass spectrometer equipped with an electrospray ionization source. The electrospray source produces an initial distribution of Sr(2+)(H(2)O)(x) complexes, where x=6-9. Smaller Sr(2+)(H(2)O)(x) complexes, where x=1-5, are accessed using a recently developed in-source fragmentation technique that takes place in the high pressure region of a rf-only hexapole ion guide. This work constitutes the first experimental study for the complete inner shell of any multiply charged ion. The kinetic energy dependent cross sections are determined over a wide energy range to monitor all possible dissociation products and are modeled to obtain 0 and 298 K binding energies for loss of a single water molecule. These binding energies decrease monotonically for the Sr(2+)(H(2)O) complex to Sr(2+)(H(2)O)(6). Our experimental results agree well with previous literature results obtained by equilibrium and kinetic studies for x=5 and 6. Because there has been limited theory for the hydration of Sr(2+), we also present an in-depth theoretical study on the energetics of the Sr(2+)(H(2)O)(x) systems by employing several levels of theory with multiple effective core potentials for Sr and different basis sets for the water molecules.

  20. Sorption mechanisms of zinc to calcium silicate hydrate: X-ray absorption fine structure (XAFS) investigation.

    Science.gov (United States)

    Ziegler, F; Scheidegger, A M; Johnson, C A; Dähn, R; Wieland, E

    2001-04-01

    In this study, X-ray absorption fine structure (XAFS) spectroscopy has been used to further elucidate the binding mechanisms of Zn(II) to calcium silicate hydrate (C-S-H), the quantitatively most important cement mineral. Such knowledge is essential for the assessment of the longterm behavior of cement-stabilized waste materials. XAFS spectra of the Zn(II) equilibrated with C-S-H(I) for up to 28 days are best modeled by tetrahedral coordination of Zn(II) by four O atoms in the first atomic shell. Beyond the first coordination shell, data analysis of more highly concentrated samples suggests the presence of two distinct Zn distances and possibly the presence of an Si shell. On the basis of the comparison with a set of reference compounds, this coordination environment can be reasonably related to the structure of hemimorphite, a naturally occurring zinc silicate, and/or the presence of gamma-Zn(OH)2. At the lowest Zn uptake, the above fitting approach failed and data could be described best with a Zn-Si and a Zn-Ca shell. Previous work has been able to show that Zn(II) diffuses into the C-S-H(I) particles and does not form discrete precipitates, so the findings appear to confirm the incorporation of Zn(II) in the interlayer of C-S-H(I).

  1. Experimental investigation of the complete inner shell hydration energies of Ca2+: threshold collision-induced dissociation of Ca(2+)(H2O)x Complexes (x = 2-8).

    Science.gov (United States)

    Carl, Damon R; Armentrout, P B

    2012-04-19

    The sequential bond energies of Ca(2+)(H(2)O)(x) complexes, where x = 1-8, are measured by threshold collision-induced dissociation (TCID) in a guided ion beam tandem mass spectrometer. From an electrospray ionization source that produces an initial distribution of Ca(2+)(H(2)O)(x) complexes where x = 6-8, complexes down to x = 2 are formed using an in-source fragmentation technique. Ca(2+)(H(2)O) cannot be formed in this source because charge separation into CaOH(+) and H(3)O(+) is a lower energy pathway than simple water loss from Ca(2+)(H(2)O)(2). The kinetic energy dependent cross sections for dissociation of Ca(2+)(H(2)O)(x) complexes, where x = 2-9, are examined over a wide energy range to monitor all dissociation products and are modeled to obtain 0 and 298 K binding energies. Analysis of both primary and secondary water molecule losses from each sized complex provides thermochemistry for the sequential hydration energies of Ca(2+) for x = 1-8 and the first experimental values for x = 1-4. Additionally, the thermodynamic onsets leading to the charge separation products from Ca(2+)(H(2)O)(2) and Ca(2+)(H(2)O)(3) are determined for the first time. Our experimental results for x = 1-6 agree well with previously calculated binding enthalpies as well as quantum chemical calculations performed here. Agreement for x = 1 is improved when the basis set on calcium includes core correlation.

  2. Threshold collision-induced dissociation of hydrated magnesium: experimental and theoretical investigation of the binding energies for Mg(2+)(H2O)x complexes (x=2-10).

    Science.gov (United States)

    Carl, Damon R; Armentrout, Peter B

    2013-03-18

    The sequential bond energies of Mg(2+)(H2O)x complexes, in which x=2-10, are measured by threshold collision-induced dissociation in a guided ion beam tandem mass spectrometer. From an electrospray ionization source that produces an initial distribution of Mg(2+)(H2O)x complexes in which x=7-10, complexes down to x=3 are formed by using an in-source fragmentation technique. Complexes smaller than Mg(2+)(H2O)3 cannot be formed in this source because charge separation into MgOH(+)(H2O) and H3O(+) is a lower-energy pathway than simple water loss from Mg(2+)(H2O)3. The kinetic energy dependent cross sections for dissociation of Mg(2+)(H2O)x complexes, in which x=3-10, are examined over a wide energy range to monitor all dissociation products and are modeled to obtain 0 and 298 K binding energies. Analysis of both primary and secondary water molecule losses from each sized complex provides thermochemistry for the sequential hydration energies of Mg(2+) for x=2-10 and the first experimental values for x=2-4. Additionally, the thermodynamic onsets leading to the charge-separation products from Mg(2+)(H2O)3 and Mg(2+)(H2O)4 are determined for the first time. Our experimental results for x=3-7 agree well with quantum chemical calculations performed here and previously calculated binding enthalpies, as well as previous measurements for x=6. The present values for x=7-10 are slightly lower than previous experimental results and theory, but within experimental uncertainties.

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

    Science.gov (United States)

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

    1997-01-01

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

  4. Force measurements reveal how small binders perturb the dissociation mechanisms of DNA duplex sequences

    Science.gov (United States)

    Burmistrova, Anastasia; Fresch, Barbara; Sluysmans, Damien; de Pauw, Edwin; Remacle, Françoise; Duwez, Anne-Sophie

    2016-06-01

    The force-driven separation of double-stranded DNA is crucial to the accomplishment of cellular processes like genome transactions. Ligands binding to short DNA sequences can have a local stabilizing or destabilizing effect and thus severely affect these processes. Although the design of ligands that bind to specific sequences is a field of intense research with promising biomedical applications, so far, their effect on the force-induced strand separation has remained elusive. Here, by means of AFM-based single molecule force spectroscopy, we show the co-existence of two different mechanisms for the separation of a short DNA duplex and demonstrate how they are perturbed by small binders. With the support of Molecular Dynamics simulations, we evidence that above a critical pulling rate one of the dissociation pathways becomes dominant, with a dramatic effect on the rupture forces. Around the critical threshold, we observe a drop of the most probable rupture forces for ligand-stabilized duplexes. Our results offer a deep understanding of how a stable DNA-ligand complex behaves under force-driven strand separation.The force-driven separation of double-stranded DNA is crucial to the accomplishment of cellular processes like genome transactions. Ligands binding to short DNA sequences can have a local stabilizing or destabilizing effect and thus severely affect these processes. Although the design of ligands that bind to specific sequences is a field of intense research with promising biomedical applications, so far, their effect on the force-induced strand separation has remained elusive. Here, by means of AFM-based single molecule force spectroscopy, we show the co-existence of two different mechanisms for the separation of a short DNA duplex and demonstrate how they are perturbed by small binders. With the support of Molecular Dynamics simulations, we evidence that above a critical pulling rate one of the dissociation pathways becomes dominant, with a dramatic effect

  5. Geomechanical Performance of Hydrate-Bearing Sediment in Offshore Environments

    Energy Technology Data Exchange (ETDEWEB)

    Stephen Holditch; Tad Patzek; Jonny Rutqvist; George Moridis; Richard Plumb

    2008-03-31

    The objective of this multi-year, multi-institutional research project was to develop the knowledge base and quantitative predictive capability for the description of geomechanical performance of hydrate-bearing sediments (hereafter referred to as HBS) in oceanic environments. The focus was on the determination of the envelope of hydrate stability under conditions typical of those related to the construction and operation of offshore platforms. We have developed a robust numerical simulator of hydrate behavior in geologic media by coupling a reservoir model with a commercial geomechanical code. We also investigated the geomechanical behavior of oceanic HBS using pore-scale models (conceptual and mathematical) of fluid flow, stress analysis, and damage propagation. The objective of the UC Berkeley work was to develop a grain-scale model of hydrate-bearing sediments. Hydrate dissociation alters the strength of HBS. In particular, transformation of hydrate clusters into gas and liquid water weakens the skeleton and, simultaneously, reduces the effective stress by increasing the pore pressure. The large-scale objective of the study is evaluation of geomechanical stability of offshore oil and gas production infrastructure. At Lawrence Berkeley National Laboratory (LBNL), we have developed the numerical model TOUGH + Hydrate + FLAC3D to evaluate how the formation and disassociation of hydrates in seafloor sediments affects seafloor stability. Several technical papers were published using results from this model. LBNL also developed laboratory equipment and methods to produce realistic laboratory samples of sediments containing gas hydrates so that mechanical properties could be measured in the laboratory. These properties are required to run TOUGH + Hydrate + FLAC3D to evaluate seafloor stability issues. At Texas A&M University we performed a detailed literature review to determine what gas hydrate formation properties had been measured and reported in the literature. We

  6. Dominant Alcohol-Protein Interaction via Hydration-Enabled Enthalpy-Driven Binding Mechanism.

    Science.gov (United States)

    Chong, Yuan; Kleinhammes, Alfred; Tang, Pei; Xu, Yan; Wu, Yue

    2015-04-30

    Water plays an important role in weak associations of small drug molecules with proteins. Intense focus has been on binding-induced structural changes in the water network surrounding protein binding sites, especially their contributions to binding thermodynamics. However, water is also tightly coupled to protein conformations and dynamics, and so far little is known about the influence of water-protein interactions on ligand binding. Alcohols are a type of low-affinity drugs, and it remains unclear how water affects alcohol-protein interactions. Here, we present alcohol adsorption isotherms under controlled protein hydration using in situ NMR detection. As functions of hydration level, Gibbs free energy, enthalpy, and entropy of binding were determined from the temperature dependence of isotherms. Two types of alcohol binding were found. The dominant type is low-affinity nonspecific binding, which is strongly dependent on temperature and the level of hydration. At low hydration levels, this nonspecific binding only occurs above a threshold of alcohol vapor pressure. An increased hydration level reduces this threshold, with it finally disappearing at a hydration level of h ≈ 0.2 (g water/g protein), gradually shifting alcohol binding from an entropy-driven to an enthalpy-driven process. Water at charged and polar groups on the protein surface was found to be particularly important in enabling this binding. Although further increase in hydration has smaller effects on the changes of binding enthalpy and entropy, it results in a significant negative change in Gibbs free energy due to unmatched enthalpy-entropy compensation. These results show the crucial role of water-protein interplay in alcohol binding.

  7. Dissociable neural mechanisms for goal-directed versus incidental memory reactivation.

    Science.gov (United States)

    Kuhl, Brice A; Johnson, Marcia K; Chun, Marvin M

    2013-10-09

    Remembering a past event involves reactivation of distributed patterns of neural activity that represent the features of that event-a process that depends on associative mechanisms supported by medial temporal lobe structures. Although efficient use of memory requires prioritizing those features of a memory that are relevant to current behavioral goals (target features) over features that may be goal-irrelevant (incidental features), there remains ambiguity concerning how this is achieved. We tested the hypothesis that although medial temporal lobe structures may support reactivation of both target and incidental event features, frontoparietal cortex preferentially reactivates those features that match current goals. Here, human participants were cued to remember either the category (face/scene) to which a picture belonged (category trials) or the location (left/right) in which a picture appeared (location trials). Multivoxel pattern analysis of fMRI data were used to measure reactivation of category information as a function of its behavioral relevance (target vs incidental reactivation). In ventral/medial temporal lobe (VMTL) structures, incidental reactivation was as robust as target reactivation. In contrast, frontoparietal cortex exhibited stronger target than incidental reactivation; that is, goal-modulated reactivation. Reactivation was also associated with later memory. Frontoparietal biases toward target reactivation predicted subsequent memory for target features, whereas incidental reactivation in VMTL predicted subsequent memory for nontested features. These findings reveal a striking dissociation between goal-modulated reactivation in frontoparietal cortex and incidental reactivation in VMTL.

  8. Fragmentation Patterns and Mechanisms of Singly and Doubly Protonated Peptoids Studied by Collision Induced Dissociation.

    Science.gov (United States)

    Ren, Jianhua; Tian, Yuan; Hossain, Ekram; Connolly, Michael D

    2016-04-01

    Peptoids are peptide-mimicking oligomers consisting of N-alkylated glycine units. The fragmentation patterns for six singly and doubly protonated model peptoids were studied via collision-induced dissociation tandem mass spectrometry. The experiments were carried out on a triple quadrupole mass spectrometer with an electrospray ionization source. Both singly and doubly protonated peptoids were found to fragment mainly at the backbone amide bonds to produce peptoid B-type N-terminal fragment ions and Y-type C-terminal fragment ions. However, the relative abundances of B- versus Y-ions were significantly different. The singly protonated peptoids fragmented by producing highly abundant Y-ions and lesser abundant B-ions. The Y-ion formation mechanism was studied through calculating the energetics of truncated peptoid fragment ions using density functional theory and by controlled experiments. The results indicated that Y-ions were likely formed by transferring a proton from the C-H bond of the N-terminal fragments to the secondary amine of the C-terminal fragments. This proton transfer is energetically favored, and is in accord with the observation of abundant Y-ions. The calculations also indicated that doubly protonated peptoids would fragment at an amide bond close to the N-terminus to yield a high abundance of low-mass B-ions and high-mass Y-ions. The results of this study provide further understanding of the mechanisms of peptoid fragmentation and, therefore, are a valuable guide for de novo sequencing of peptoid libraries synthesized via combinatorial chemistry. Graphical Abstract ᅟ.

  9. Molecular mechanisms of decomposition of hydrated Na+Cl- ion pairs under planar nanopore conditions

    Science.gov (United States)

    Shevkunov, S. V.

    2017-02-01

    The decomposition of Na+Cl- ion pairs under the conditions of a nanoscopic planar pore with structureless walls in a material contact with water vapor at 298 K is simulated by Monte Carlo method. The transition from the state of a contact ion pair (CIP) to the state of solvent-separated ion pair (SSIP) is shown to occur as a result of an increase in the vapor pressure over a pore after exceeding the threshold number of molecules in a hydrate shell. It is found that the planar form of a molecular cluster under the conditions of a narrow pore does not level an abrupt structural transition and the formation of hydrogen bonds in the hydrate shell starts after three molecules are added. The hydrogen bond length under pore conditions is found to be resistant to variations in the hydrate shell size and coincides with that in water under normal conditions.

  10. Bond dissociation mechanism of ethanol during carbon nanotube synthesis via alcohol catalytic CVD technique: Ab initio molecular dynamics simulation

    Science.gov (United States)

    Oguri, Tomoya; Shimamura, Kohei; Shibuta, Yasushi; Shimojo, Fuyuki; Yamaguchi, Shu

    2014-03-01

    Dissociation of ethanol on a nickel cluster is investigated by ab initio molecular dynamics simulation to reveal the bond dissociation mechanism of carbon source molecules during carbon nanotube synthesis. C-C bonds in only CHxCO fragments are dissociated on the nickel cluster, whereas there is no preferential structure among the fragments for C-O bond dissociation. The dissociation preference is uncorrelated with the bond dissociation energy of corresponding bonds in freestanding molecules but is correlated with the energy difference between fragment molecules before and after dissociation on the nickel surface. Moreover, carbon-chain formation occurs after C-C bond dissociation in a continuous simulation. What determines the chirality of CNTs? What happens at the dissociation stage of carbon source molecules? Regarding the former question, many researchers have pointed out the good epitaxial relationship between a graphite network and a close-packed facet (i.e., fcc(1 1 1) or hcp(0 0 0 1)) of transition metals [17-19]. Therefore, the correlation between the chirality of CNTs and the angle of the step edge on metal (or metal carbide) surfaces has been closely investigated [20-22]. In association with this geometric matching, the epitaxial growth of graphene on Cu(1 1 1) and Ni(1 1 1) surfaces has recently been achieved via CCVD technique [23-25], which is a promising technique for the synthesis of large-area and monolayer graphene.Regarding the latter question, it is empirically known that the yield and quality of CNT products strongly depend on the choice of carbon source molecules and additives. For example, it is well known that the use of ethanol as carbon source molecules yields a large amount of SWNTs without amorphous carbons (called the alcohol CCVD (ACCVD) technique) compared with the CCVD process using hydrocarbons [4]. Moreover, the addition of a small amount of water dramatically enhances the activity and lifetime of the catalytic metal (called the

  11. On the modulation effect of pulsing and static magnetic fields and mechanical vibrations on barley seed hydration.

    Science.gov (United States)

    Amyan, Armine; Ayrapetyan, Sinerik

    2004-01-01

    The changes of wet and dry weights of barley seed in different periods of swelling were studied in seeds treated with Extremely Low Frequency Electromagnetic Fields (ELF EMF), Static Magnetic Fields (SMF) and Mechanical Vibrations (MV) in cold (4 degrees C) and warm (20 degrees C) distilled water as well as in seeds non-treated (control). The metabolic dependent seed hydration, dry weight loss and water binding in seed were modulated by preliminary EMF, SMF and MV-induced treatment of distilled water. The specific electrical conductivity (SEC) of control and treated distilled water was measured before the seed incubation. Frequency and intensity "windows" (i.e. range of frequency or intensity) for the effect of EMF, MV and SMF (correspondingly) on seed hydration, solubility and water binding in seed were studied. These "windows" were different in various phases of seed swelling. It is suggested that water structure modification is the result of valence angle changes (SMF and EMF) and dipole molecules vibration (EMF and MV) has different effects on the process of hydration, solubility and water binding in seed. These results are important from the point of understanding the mechanisms of the biological effect of EMF, as well as from the point of agriculture.

  12. Handbook of gas hydrate properties and occurrence

    Energy Technology Data Exchange (ETDEWEB)

    Kuustraa, V.A.; Hammershaimb, E.C.

    1983-12-01

    This handbook provides data on the resource potential of naturally occurring hydrates, the properties that are needed to evaluate their recovery, and their production potential. The first two chapters give data on the naturally occurring hydrate potential by reviewing published resource estimates and the known and inferred occurrences. The third and fourth chapters review the physical and thermodynamic properties of hydrates, respectively. The thermodynamic properties of hydrates that are discussed include dissociation energies and a simplified method to calculate them; phase diagrams for simple and multi-component gases; the thermal conductivity; and the kinetics of hydrate dissociation. The final chapter evaluates the net energy balance of recovering hydrates and shows that a substantial positive energy balance can theoretically be achieved. The Appendices of the Handbook summarize physical and thermodynamic properties of gases, liquids and solids that can be used in designing and evaluating recovery processes of hydrates. 158 references, 67 figures, 47 tables.

  13. Unraveling the reaction mechanism on nitrile hydration catalyzed by [Pd(OH2)4]2+: insights from theory.

    Science.gov (United States)

    Tílvez, Elkin; Menéndez, María I; López, Ramón

    2013-07-01

    Density functional theory methodologies combined with continuum and discrete-continuum descriptions of solvent effects were used to investigate the [Pd(OH2)4](2+)-catalyzed acrylonitrile hydration to yield acrylamide. According to our results, the intramolecular hydroxide attack mechanism and the external addition mechanism of a water molecule with rate-determining Gibbs energy barriers in water solution of 27.6 and 28.3 kcal/mol, respectively, are the most favored. The experimental kinetic constants of the hydration started by hydroxide, k(OH), and water, k(H2O), attacks for the cis-[Pd(en)(OH2)2](2+)-catalyzed dichloroacetonitrile hydration rendered Gibbs energy barriers whose energy difference, 0.7 kcal/mol, is the same as that obtained in the present study. Our investigation reveals the nonexistence of the internal attack of a water ligand for Pd-catalyzed nitrile hydration. At the low pHs used experimentally, the equilibrium between [Pd(OH2)3(nitrile)](2+) and [Pd(OH2)2(OH)(nitrile)](+) is completely displaced to [Pd(OH2)3(nitrile)](2+). Experimental studies in these conditions stated that water acts as a nucleophile, but they could not distinguish whether it was a water ligand, an external water molecule, or a combination of both possibilities. Our theoretical explorations clearly indicate that the external water mechanism becomes the only operative one at low pHs. On the basis of this mechanistic proposal it is also possible to ascribe an (1)H NMR signal experimentally detected to the presence of a unidentate iminol intermediate and to explain the influence of nitrile concentration reported experimentally for nitriles other than acrylonitrile in the presence of aqua-Pd(II) complexes. Therefore, our theoretical point of view on the mechanism of nitrile hydration catalyzed by aqua-Pd(II) complexes can shed light on these relevant processes at a molecular level as well as afford valuable information that can help in designing new catalysts in milder and more

  14. Physical chemistry of hydrated molecular sieves: combined study of theoretical and experimental approaches. Understanding and outlooks of hydration mechanism of alumino phosphates; Physico-chimie des tamis moleculaires hydrates: etude combinee experience/theorie. Comprehension et previsions des mecanismes d'hydratation des aluminophosphates

    Energy Technology Data Exchange (ETDEWEB)

    Poulet, G. [Institut universitaire de technologie, 74 - Annecy-le-Vieux (France); Sautet, Ph. [Ecole Nationale Superieure de Lyon, 69 (France); Centre National de la Recherche Scientifique (CNRS), 69 - Villeurbanne (France); Tuel, A. [Institut de Recherches sur le Catalyse, UPR 5401, 69 - Villeurbanne (France)

    2005-01-01

    Microporous alumino-phosphates AlPO{sub 4}-n have drawn considerable attention due to their potential to act as heterogeneous catalysts and molecular sieves. Hydration of these compounds usually modifies the coordination of framework aluminium species and causes a reversible structure deformation. Here, a combined use of experimental tools and of a theoretical approach based on the density functional theory (DFT) contributes to a better knowledge of the interactions between water molecule and AlPO{sub 4}-n frameworks. Information on the behaviour of water in the pores has been obtained from the study of a model compound, AlPO{sub 4}-34. A dehydration/re-hydration mechanism has been proposed as well as a partially hydrated phase, in agreement with solid-state NMR and X-ray diffraction results. Then, a complete experimental study (infrared spectroscopy, X-ray diffraction, thermal analysis, NMR) has been supplemented by static or dynamic theoretical approaches to get information on the calcined re-hydrated AlPO{sub 4}-18 phase. (authors)

  15. Fluid-solid coupling model for studying wellbore instability in drilling of gas hydrate bearing sediments

    Institute of Scientific and Technical Information of China (English)

    程远方; 李令东; 崔青

    2013-01-01

    As the oil or gas exploration and development activities in deep and ultra-deep waters become more and more, encountering gas hydrate bearing sediments (HBS) is almost inevitable. The variation in temperature and pressure can destabilize gas hydrate in nearby formation around the borehole, which may reduce the strength of the formation and result in wellbore instability. A non-isothermal, transient, two-phase, and fluid-solid coupling mathematical model is proposed to simulate the complex stability performance of a wellbore drilled in HBS. In the model, the phase transition of hydrate dissociation, the heat exchange between drilling fluid and formation, the change of mechanical and petrophysical properties, the gas-water two-phase seepage, and its interaction with rock deformation are considered. A finite element simulator is developed, and the impact of drilling mud on wellbore instability in HBS is simulated. Results indicate that the re-duction in pressure and the increase in temperature of the drilling fluid can accelerate hydrate decomposition and lead to mechanical properties getting worse tremendously. The cohesion decreases by 25% when the hydrate totally dissociates in HBS. This easily causes the wellbore instability accordingly. In the first two hours after the formation is drilled, the regions of hydrate dissociation and wellbore instability extend quickly. Then, with the soaking time of drilling fluid increasing, the regions enlarge little. Choosing the low temperature drilling fluid and increasing the drilling mud pressure appropriately can benefit the wellbore stability of HBS. The established model turns out to be an efficient tool in numerical studies of the hydrate dissociation behavior and wellbore stability of HBS.

  16. Microstructure, Porosity and Mechanical Property Relationships of Calcium-Silicate-Hydrate

    Science.gov (United States)

    1991-02-15

    34Hydrothermal Synthesis of Clinoptilolite and Comments on the Assemblage of Phillipsite- clinoptilolite -mordenite," Pergamon Press, Oxford and New York, pp...35 Discussion................................................. 48 Part 1IH. Zeolite Synthesis ...52 Previous Glass Hydration Work ... 53 Zeolite Synthesis from Synthetic Glasses 10 and I1 I .. 55 Results............................56 S Zeolite

  17. A Study of Concrete Hydration and Dielectric Relaxation Mechanism Using Ground Penetrating Radar and Short-Time Fourier Transform

    Directory of Open Access Journals (Sweden)

    Lai WL

    2010-01-01

    Full Text Available Abstract Ground penetrating radar (GPR was used to characterize the frequency-dependent dielectric relaxation phenomena in ordinary Portland cement (OPC hydration in concrete changing from fresh to hardened state. The study was experimented by measuring the changes of GPR A-scan waveforms over a period of 90 days, and processed the waveforms with short-time Fourier transform (STFT in joint time-frequency analysis (JTFA domain rather than a conventional time or frequency domain alone. The signals of the direct wave traveled at the concrete surface and the reflected wave from an embedded steel bar were transformed with STFT, in which the changes of peak frequency over ages were tracked. The peak frequencies were found to increase with ages and the patterns were found to match closely with primarily the well-known OPC hydration process and secondarily, the evaporation effect. The close match is contributed to the simultaneous effects converting free to bound water over time, on both conventional OPC hydration and dielectric relaxation mechanisms.

  18. Experimental characterization of production behavior accompanying the hydrate reformation in methane hydrate bearing sediments

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, T.; Kang, J.M.; Nguyen, H.T. [Seoul National Univ., Seoul (Korea, Republic of); Park, C. [Kangwon National Univ., (Korea, Republic of); Lee, J. [Korea Inst., of Geoscience and Mineral Resources (Korea, Republic of)

    2010-07-01

    This study investigated the production behaviour associated with gas hydrate reformation in methane hydrate-bearing sediment by hot-brine injection. A range of different temperature and brine injection rates were used to analyze the pressure and temperature distribution, the gas production behaviour and the movement of the dissociation front. The study showed that hydrate reformation reduces the production rate considerably at an early time. However, gas production increases during the dissociation, near the outlet because the dissociated methane around the inlet is consumed in reforming the hydrate and increases the hydrate saturation around the outlet. Higher temperature also increases the gas production rate and the speed of the dissociation front. 12 refs., 2 tabs., 4 figs.

  19. Testing a coupled hydro-thermo-chemo-geomechanical model for gas hydrate bearing sediments using triaxial compression lab experiments

    CERN Document Server

    Gupta, Shubhangi; Haeckel, Matthias; Helmig, Rainer; Wohlmuth, Barbara

    2015-01-01

    The presence of gas hydrates influences the stress-strain behavior and increases the load-bearing capacity of sub-marine sediments. This stability is reduced or completely lost when gas hydrates become unstable. Since natural gas hydrate reservoirs are considered as potential resources for gas production on industrial scales, there is a strong need for numerical production simulators with geomechanical capabilities. To reliably predict the mechanical behavior of gas hydrate-bearing sediments during gas production, numerical tools must be sufficiently calibrated against data from controlled experiments or field tests, and the models must consider thermo-hydro-chemo-mechanical process coupling in a suitable manner. In this study, we perform a controlled triaxial volumetric strain test on a sediment sample in which methane hydrate is first formed under controlled isotropic effective stress and then dissociated via depressurization under controlled total stress. Sample deformations were kept small, and under thes...

  20. Research data supporting "Structural Determinants of Hydration, Mechanics and Fluid Flow in Collagen Scaffolds"

    OpenAIRE

    Offeddu, Giovanni S.; Ashworth, Jennifer C; Cameron, Ruth E.; Oyen, Michelle L.

    2016-01-01

    The following data files are provided: Summary of results: numerical values used to plot each figure in the manuscript, as well as single measurements for each parameter when applicable. Raw indentation data: the load vs. time curves obtained by spherical indentation for the dry and hydrated samples. CT Analysis: Ellipse fit data giving the pore size analysis for each condition, scaling analysis for calculation of percolation diameter, 3D analysis giving the specific surface area for each sam...

  1. 3-D basin-scale reconstruction of natural gas hydrate system of the Green Canyon, Gulf of Mexico

    Science.gov (United States)

    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.

  2. Development of Alaskan gas hydrate resources

    Energy Technology Data Exchange (ETDEWEB)

    Kamath, V.A.; Sharma, G.D.; Patil, S.L.

    1991-06-01

    The research undertaken in this project pertains to study of various techniques for production of natural gas from Alaskan gas hydrates such as, depressurization, injection of hot water, steam, brine, methanol and ethylene glycol solutions through experimental investigation of decomposition characteristics of hydrate cores. An experimental study has been conducted to measure the effective gas permeability changes as hydrates form in the sandpack and the results have been used to determine the reduction in the effective gas permeability of the sandpack as a function of hydrate saturation. A user friendly, interactive, menu-driven, numerical difference simulator has been developed to model the dissociation of natural gas hydrates in porous media with variable thermal properties. A numerical, finite element simulator has been developed to model the dissociation of hydrates during hot water injection process.

  3. Bond breaks of nucleotides by dissociative electron transfer of nonequilibrium prehydrated electrons: a new molecular mechanism for reductive DNA damage.

    Science.gov (United States)

    Wang, Chun-Rong; Nguyen, Jenny; Lu, Qing-Bin

    2009-08-19

    DNA damage is a central mechanism in the pathogenesis and treatment of human diseases, notably cancer. Little is known about reductive DNA damage in causing genetic mutations during oncogenesis and killing cancer cells during radiotherapy. The prehydrated electron (e(-)(pre)) has the highest yield among all the radicals generated in cells during ionizing radiation and has subpicosecond lifetimes (10(-13) s) and energies below 0 eV, but its role in DNA damage is unknown. In this work, our real-time measurements by femtosecond time-resolved laser spectroscopy have revealed that while adenine and cytosine can effectively trap an e(-)(pre) to form stable anions, thymidine and especially guanine are highly susceptible to dissociative electron transfer of e(-)(pre), leading to bond dissociation in DNA. Our finding demonstrates a dissociative electron transfer pathway for reductive DNA damage that might be related to various diseases such as cancer and stroke. Moreover, this finding challenges the conventional notion that damage to the genome is mainly induced by the oxidizing OH* radical and might eventually lead to improved radiotherapy of cancer and radioprotection of humans.

  4. Dissociated Steroids

    Directory of Open Access Journals (Sweden)

    Matthew C. Catley

    2007-01-01

    Full Text Available Glucocorticoids (GCs are some of the most important drugs in clinical use today. They are mainly used to suppress disease-related inflammation and are widely used for the treatment of many inflammatory diseases including asthma and arthritis. However, GCs are also associated with debilitating side effects that place limitations on the long-term use of these drugs. The development of a GC with reduced side effects would allow more effective treatments for patients who require long-term suppression of inflammation. GCs exert their effects by binding and activating the GC receptor (GR. The activated receptor then binds GC response elements (GREs in the promoter of genes, and activates transcription (transactivation or interferes with the activation of transcription by inhibiting the transactivating function of other transcription factors, such as AP-1 and NF-ĸB (transrepression. Transrepression is believed to be responsible for the majority of the beneficial anti-inflammatory effects of GCs, whereas transactivation is believed to play a bigger role in the unwanted side effects of GCs. Compounds that can dissociate the transactivation function of GCs from the transrepression function may, therefore, have an improved therapeutic index. A number of these dissociated corticosteroids have been developed. In vitro assays using these compounds appear to show good dissociation. However, in vivo, the dissociation appears to be lost and these compounds still produce many of the side effects associated with conventional GCs. A better understanding of the molecular mechanisms behind GC-induced effects would allow the design of novel selective GR modulators with an improved therapeutic index.

  5. The effect of hydrate saturation on water retention curves in hydrate-bearing sediments

    Science.gov (United States)

    Mahabadi, Nariman; Zheng, Xianglei; Jang, Jaewon

    2016-05-01

    The experimental measurement of water retention curve in hydrate-bearing sediments is critically important to understand the behavior of hydrate dissociation and gas production. In this study, tetrahydrofuran (THF) is selected as hydrate former. The pore habit of THF hydrates is investigated by visual observation in a transparent micromodel. It is confirmed that THF hydrates are not wetting phase on the quartz surface of the micromodel and occupy either an entire pore or part of pore space resulting in change in pore size distribution. And the measurement of water retention curves in THF hydrate-bearing sediments with hydrate saturation ranging from Sh = 0 to Sh = 0.7 is conducted for excess water condition. The experimental results show that the gas entry pressure and the capillary pressure increase with increasing hydrate saturation. Based on the experimental results, fitting parameters for van Genuchten equation are suggested for different hydrate saturation conditions.

  6. Structural and dynamical aspects of the unsymmetric hydration of Sb(III): an ab initio quantum mechanical charge field molecular dynamics simulation.

    Science.gov (United States)

    Lim, Len Herald V; Bhattacharjee, Anirban; Asam, S Sikander; Hofer, Thomas S; Randolf, Bernhard R; Rode, Bernd M

    2010-03-01

    An ab initio quantum mechanical charge field molecular dynamics (QMCF MD) simulation was performed to investigate the behavior of the Sb(3+) ion in aqueous solution. The simulation reveals a significant influence of the residual valence shell electron density on the solvation structure and dynamics of Sb(3+). A strong hemidirectional behavior of the ligand binding pattern is observed for the first hydration shell extending up to the second hydration layer. The apparent domain partitioned structural behavior was probed by solvent reorientational kinetics and three-body distribution functions. The three-dimensional hydration space was conveniently segmented such that domains having different properties were properly resolved. The approach afforded a fair isolation of localized solvent structural and dynamical motifs that Sb(3+) seems to induce to a remarkable degree. Most intriguing is the apparent impact of the lone pair electrons on the second hydration shell, which offers insight into the mechanistic aspects of hydrogen bonding networks in water. Such electronic effects observed in the hydration of Sb(3+) can only be studied by applying a suitable quantum mechanical treatment including first and second hydration shell as provided by the QMCF ansatz.

  7. Influence of supplementary cementitious materials on water transport kinetics and mechanical properties of hydrated lime and cement mortars

    Directory of Open Access Journals (Sweden)

    Ince, C.

    2015-06-01

    Full Text Available The purpose of this paper is an investigation of the possible role of supplementary cementitious materials (SCMs on water transport kinetics and mechanical properties of hydrated lime (CL90 and Portland cement (PC mortars. The properties of hydrated lime are significantly different from those of cement and therefore modifying fresh and hardened properties of these mortars are vital for mortar/substrate optimisation in masonry construction. The parameters investigated in this paper often are the main barriers to the use of hydrated lime in construction practice. The results show that transfer sorptivity and time to dewater freshly-mixed hydrated lime mortars can be modified when binder is partially replaced with SCMs. Compressive strength of CL90 mortars is increased systematically with the increased replacement levels of SCMs and the results are supported with the microstructural images. The ability to modify the water transport kinetics and mechanical properties allows compatibility between the mortar and the substrate unit in masonry construction.El objetivo de este artículo es investigar el papel de los materiales cementantes suplementarios (SCMs en la cinética de transporte del agua y en las propiedades mecánicas de los morteros de cal hidratada (CL90 y cemento Portland. Las propiedades de la cal hidratada son significativamente diferentes a las del cemento y por lo tanto el control de las propiedades de los morteros frescos y endurecidos es fundamental en la optimización mortero/substrato en albañilería. Los parámetros estudiados en este trabajo son a menudo las principales barreras para el uso de la cal hidratada en la práctica de la construcción. Los resultados indican que la absortividad y el tiempo necesario para deshidratar morteros de cal hidratada recién mezclados pueden ser controlados cuando el conglomerante es parcialmente remplazado por SCMs. La resistencia a compresión de los morteros CL90 aumenta sistem

  8. Formation of porous gas hydrates

    CERN Document Server

    Salamatin, Andrey N

    2015-01-01

    Gas hydrates grown at gas-ice interfaces are examined by electron microscopy and found to have a submicron porous texture. Permeability of the intervening hydrate layers provides the connection between the two counterparts (gas and water molecules) of the clathration reaction and makes further hydrate formation possible. The study is focused on phenomenological description of principal stages and rate-limiting processes that control the kinetics of the porous gas hydrate crystal growth from ice powders. Although the detailed physical mechanisms involved in the porous hydrate formation still are not fully understood, the initial stage of hydrate film spreading over the ice surface should be distinguished from the subsequent stage which is presumably limited by the clathration reaction at the ice-hydrate interface and develops after the ice grain coating is finished. The model reveals a time dependence of the reaction degree essentially different from that when the rate-limiting step of the hydrate formation at...

  9. Strong-field dissociation of CS2+ via a pump/dump-like mechanism

    Science.gov (United States)

    Severt, T.; Zohrabi, M.; Betsch, K. J.; Ablikim, U.; Jochim, Bethany; Carnes, K. D.; Zeng, S.; Esry, B. D.; Ben-Itzhak, I.; Uhlíková, T.

    2014-05-01

    Laser-induced dissociation of the quasi-bound electronic ground state of CS2+ is investigated in intense laser pulses (stretching at an energy above the potential barrier, the emission of a second photon is stimulated by the same laser pulse, most likely at the Condon point. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy, Grants DE-FG02-86ER13491 and DE-FG02-09ER16115. TU supported by GACR and MetaCentrum.

  10. New insight into hydration and aging mechanisms of paper by the line shape analysis of proton NMR spectra

    Science.gov (United States)

    Mallamace, D.; Vasi, S.; Missori, M.; Corsaro, C.

    2016-05-01

    The action of water within biological systems is strictly linked either with their physical chemical properties and with their functions. Cellulose is one of the most studied biopolymers due to its biological importance and its wide use in manufactured products. Among them, paper is mainly constituted by an almost equimolar ratio of cellulose and water. Therefore the study of the behavior of water within pristine and aged paper samples can help to shed light on the degradation mechanisms that irremediably act over time and spoil paper. In this work we present Nuclear Magnetic Resonance (NMR) experiments on modern paper samples made of pure cellulose not aged and artificially aged as well as on ancient paper samples made in 1413 in Perpignan (France). The line shape parameters of the proton NMR spectra were studied as a function of the hydration content. Results indicate that water in aged samples is progressively involved in the hydration of the byproducts of cellulose degradation. This enhances the degradation process itself through the progressive consumption of the cellulose amorphous regions.

  11. Hydration free energies using semiempirical quantum mechanical Hamiltonians and a continuum solvent model with multiple atomic-type parameters.

    Science.gov (United States)

    Anisimov, Victor M; Cavasotto, Claudio N

    2011-06-23

    To build the foundation for accurate quantum mechanical (QM) simulation of biomacromolecules in an aqueous environment, we undertook the optimization of the COnductor-like Screening MOdel (COSMO) atomic radii and atomic surface tension coefficients for different semiempirical Hamiltonians adhering to the same computational conditions recently followed in the simulation of biomolecular systems. This optimization was achieved by reproducing experimental hydration free energies of a set consisting of 507 neutral and 99 ionic molecules. The calculated hydration free energies were significantly improved by introducing a multiple atomic-type scheme that reflects different chemical environments. The nonpolar contribution was treated according to the scaled particle Claverie-Pierotti formalism. Separate radii and surface tension coefficient sets have been developed for AM1, PM3, PM5, and RM1 semiempirical Hamiltonians, with an average unsigned error for neutral molecules of 0.64, 0.66, 0.73, and 0.71 kcal/mol, respectively. Free energy calculation of each molecule took on average 0.5 s on a single processor. The new sets of parameters will enhance the quality of semiempirical QM calculations using COSMO in biomolecular systems. Overall, these results further extend the utility of QM methods to chemical and biological systems in the condensed phase.

  12. Using magnetic resonance imaging to monitor CH4 hydrate formation and spontaneous conversion of CH4 hydrate to CO2 hydrate in porous media.

    Science.gov (United States)

    Baldwin, Bernard A; Stevens, Jim; Howard, James J; Graue, Arne; Kvamme, Bjorn; Aspenes, Erick; Ersland, Geir; Husebø, Jarle; Zornes, David R

    2009-06-01

    Magnetic resonance imaging was used to monitor and quantify methane hydrate formation and exchange in porous media. Conversion of methane hydrate to carbon dioxide hydrate, when exposed to liquid carbon dioxide at 8.27 MPa and approximately 4 degrees C, was experimentally demonstrated with MRI data and verified by mass balance calculations of consumed volumes of gases and liquids. No detectable dissociation of the hydrate was measured during the exchange process.

  13. Molecular mechanisms, thermodynamics, and dissociation kinetics of knob-hole interactions in fibrin

    CERN Document Server

    Kononova, Olga; Zhmurov, Artem; Alekseenko, Andrey; Cheng, Chai-Ho; Agarwal, Silvi; Marx, Kenneth A; Weisel, John W; Barsegov, Valeri

    2015-01-01

    Polymerization of fibrin, the primary structural protein of blood clots and thrombi, occurs through binding of knobs 'A' and 'B' in the central nodule of fibrin monomer to complementary holes 'a' and 'b' in the beta- and gamma-nodules, respectively, of another monomer. We characterized the A:a and B:b knob-hole interactions under varying solution conditions using Molecular Dynamics simulations of the structural models of fibrin(ogen) fragment D complexed with synthetic peptides GPRP (knob 'A' mimetic) and GHRP (knob 'B' mimetic). The strength of A:a and B:b knob-hole complexes was roughly equal, decreasing with pulling force; yet, the dissociation kinetics were sensitive to variations in acidity (pH=5-7) and temperature (T=25-37 C). There were similar structural changes in holes 'a' and 'b' during forced dissociation of the knob-hole complexes: elongation of loop I, stretching of interior region, and translocation of the moveable flap. The disruption of the knob-hole interactions was not an "all-or-none" tran...

  14. Dynamic morphology of gas hydrate on a methane bubble in water: Observations and new insights for hydrate film models

    Science.gov (United States)

    Warzinski, Robert P.; Lynn, Ronald; Haljasmaa, Igor; Leifer, Ira; Shaffer, Frank; Anderson, Brian J.; Levine, Jonathan S.

    2014-10-01

    Predicting the fate of subsea hydrocarbon gases escaping into seawater is complicated by potential formation of hydrate on rising bubbles that can enhance their survival in the water column, allowing gas to reach shallower depths and the atmosphere. The precise nature and influence of hydrate coatings on bubble hydrodynamics and dissolution is largely unknown. Here we present high-definition, experimental observations of complex surficial mechanisms governing methane bubble hydrate formation and dissociation during transit of a simulated oceanic water column that reveal a temporal progression of deep-sea controlling mechanisms. Synergistic feedbacks between bubble hydrodynamics, hydrate morphology, and coverage characteristics were discovered. Morphological changes on the bubble surface appear analogous to macroscale, sea ice processes, presenting new mechanistic insights. An inverse linear relationship between hydrate coverage and bubble dissolution rate is indicated. Understanding and incorporating these phenomena into bubble and bubble plume models will be necessary to accurately predict global greenhouse gas budgets for warming ocean scenarios and hydrocarbon transport from anthropogenic or natural deep-sea eruptions.

  15. Reaction mechanism between "memory effect" and induction time of gas hydrate formation

    Institute of Scientific and Technical Information of China (English)

    SUN Deng-lin; WU Qiang; ZHANG Bao-yong

    2008-01-01

    Using visual experimental apparatus,one system(T40,1×10-3 mol/L,nonadded with coal)and another system(T40,2×10-3 mol/L,added with coal)were experimented with for three times and two times.respectively.Five groups of P-T experimental parameters were obtained using the data logger system and analyzed combined with the video information of the experiments.Maior conclustions show that the induction time is shortened by 10-20 times in the experimental system containing residual pentahedral ring structures;"memory effect"can accelerate the dynamic progress and improve the thermodynamic conditions of gas hydrate formation.

  16. Numerical simulations of sand production in interbedded hydrate-bearing sediments during depressurization

    Science.gov (United States)

    Uchida, Shun; Lin, Jeen-Shang; Myshakin, Evgeniy; Seol, Yongkoo; Collett, Timothy S.; Boswell, Ray

    2017-01-01

    Geomechanical behavior of hydrate-bearing sediments during gas production is complex, involving changes in hydrate-dependent mechanical properties. When interbedded clay layers are present, the complexity is more pronounced because hydrate dissociation tends to occur preferentially in the sediments adjacent to the clay layers due to clay layers acting as a heat source. This would potentially lead to shearing deformation along the sand/clay contacts and may contribute to solid migration, which hindered past field-scale gas production tests. This paper presents a near-wellbore simulation of sand/clay interbedded hydrate-bearing sediments that have been subjected to depressurization and discusses the effect of clay layers on sand production.

  17. Simulation of subsea gas hydrate exploitation

    Science.gov (United States)

    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

  18. Gas hydrate, fluid flow and free gas: Formation of the bottom-simulating reflector

    Science.gov (United States)

    Haacke, R. Ross; Westbrook, Graham K.; Hyndman, Roy D.

    2007-09-01

    Gas hydrate in continental margins is commonly indicated by a prominent bottom-simulating seismic reflector (BSR) that occurs a few hundred metres below the seabed. The BSR marks the boundary between sediments containing gas hydrate above and free gas below. Most of the reflection amplitude is caused by the underlying free gas. Gas hydrate can occur without a BSR, however, and the controls on its formation are not well understood. Here we describe two complementary mechanisms for free gas accumulation beneath the gas hydrate stability zone (GHSZ). The first is the well-recognised hydrate recycling mechanism that generates gas from dissociating hydrate when the base of the GHSZ moves upward relative to hydrate-bearing sediment. The second is a recently identified mechanism in which the relationship between the advection and diffusion of dissolved gas with the local solubility curve allows the liquid phase to become saturated in a thick layer beneath the GHSZ when hydrate is present near its base. This mechanism for gas production (called the solubility-curvature mechanism) is possible in systems where the influence of diffusion becomes important relative to the influence of advection and where the gas-water solubility decreases to a minimum several hundred metres below the GHSZ. We investigate a number of areas in which gas hydrate occurs to determine where gas formation is dominated by the solubility-curvature mechanism and where it is dominated by hydrate recycling. We show that the former is dominant in areas with low rates of upward fluid flow (such as old, rifted continental margins), low rates of seafloor uplift, and high geothermal gradient and/or pressure. Conversely, free-gas formation is dominated by hydrate recycling where there are rapid rates of upward fluid flow and seabed uplift (such as in subduction zone accretionary wedges). Using these two mechanisms to investigate the formation of free gas beneath gas hydrate in continental margins, we are able

  19. Electron microscopic evidence for the myosin head lever arm mechanism in hydrated myosin filaments using the gas environmental chamber

    Energy Technology Data Exchange (ETDEWEB)

    Minoda, Hiroki [Department of Applied Physics, Tokyo University of Agriculture and Technology, Koganeishi, Tokyo184-8588 (Japan); CREST, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012 (Japan); Okabe, Tatsuhiro; Inayoshi, Yuhri [Department of Applied Physics, Tokyo University of Agriculture and Technology, Koganeishi, Tokyo184-8588 (Japan); Miyakawa, Takuya; Miyauchi, Yumiko; Tanokura, Masaru [Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, University of Tokyo, Bunkyo-ku, Tokyo 113-0032 (Japan); Katayama, Eisaku [Graduate School of Medicine, Institute of Medical Science, University of Tokyo, Minato-ku, Tokyo 108-8639 (Japan); Wakabayashi, Takeyuki [Department of Biosciences, School of Science and Engineering, Teikyo University, Utsunomiya, Tochigiken 320-8551 (Japan); Akimoto, Tsuyoshi [Department of Physiology, School of Medicine, Teikyo University, Itabashi-ku, Tokyo 173-8605 (Japan); Sugi, Haruo, E-mail: sugi@kyf.biglobe.ne.jp [Department of Physiology, School of Medicine, Teikyo University, Itabashi-ku, Tokyo 173-8605 (Japan)

    2011-02-25

    Research highlights: {yields} We succeeded in recording structural changes of hydrated myosin cross-bridges. {yields} We succeeded in position-marking the cross-bridges with site-directed antibodies. {yields} We recorded cross-bridge movement at different regions in individual cross-bridge. {yields} The movement was smallest at the cross-bridge-subfragment two boundary. {yields} The results provide evidence for the cross-bridge lever arm mechanism. -- Abstract: Muscle contraction results from an attachment-detachment cycle between the myosin heads extending from myosin filaments and the sites on actin filaments. The myosin head first attaches to actin together with the products of ATP hydrolysis, performs a power stroke associated with release of hydrolysis products, and detaches from actin upon binding with new ATP. The detached myosin head then hydrolyses ATP, and performs a recovery stroke to restore its initial position. The strokes have been suggested to result from rotation of the lever arm domain around the converter domain, while the catalytic domain remains rigid. To ascertain the validity of the lever arm hypothesis in muscle, we recorded ATP-induced movement at different regions within individual myosin heads in hydrated myosin filaments, using the gas environmental chamber attached to the electron microscope. The myosin head were position-marked with gold particles using three different site-directed antibodies. The amplitude of ATP-induced movement at the actin binding site in the catalytic domain was similar to that at the boundary between the catalytic and converter domains, but was definitely larger than that at the regulatory light chain in the lever arm domain. These results are consistent with the myosin head lever arm mechanism in muscle contraction if some assumptions are made.

  20. Compound Natural Gas Hydrate: A Natural System for Separation of Hydrate-Forming Gases

    Science.gov (United States)

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

    2007-12-01

    Natural processes that separate materials from a mixture may exert a major influence on the development of the atmospheres and surfaces of planets, moons, and other planetary bodies. Natural distillation and gravity separation, amongst others, are well known means of differentiating materials through liquid-gas partitioning. One of the least known attributes of clathrate (gas) hydrates is their potential effect on the evolution of planetary system oceans and atmospheres. Gas hydrates separate gases from mixtures of gases by concentrating preferred hydrate-forming materials (HFM) guests within the water-molecule cage structure of crystalline hydrate. Different HFMs have very different fields of stability. When multiple hydrate formers are present, a preference series based on their selective uptake exists. Compound hydrate, which is formed from two or more species of HFM, extract preferred HFM from a mixture in very different proportions to their relative percentages of the original mixture. These compound hydrates can have different formation and dissociation conditions depending on the evolution of the environment. That is, the phase boundary of the compound hydrate that is required for dissociation lies along a lower pressure - higher temperature course. Compound hydrates respond to variations in temperature, pressure, and HFM composition. On Earth, the primary naturally occurring hydrate of interest to global climate modeling is methane hydrate. Oceanic hydrate on Earth is the largest store of carbon in the biosphere that is immediately reactive to environmental change, and is capable of releasing large amounts of methane into the atmosphere over a short geological time span. Hydrate formation is essentially metastable and is very sensitive to environmental change and to gas flux. Where natural variations in temperature and pressure varies so that hydrate will form and dissociate in some cyclical manner, such as in oceans where sea level is capable of rising and

  1. Mechanically enforced bond dissociation reports synergistic influence of Mn2+ and Mg2+ on the interaction between integrin α7β1 and invasin

    DEFF Research Database (Denmark)

    Ligezowska, Agnieszka; Boye, Kristian; Eble, Johannes A.

    2011-01-01

    Integrins require the divalent ions magnesium and manganese for ligand recognition. Here we mechanically enforced bond dissociation to explore the influence of these ions on the mechanical strength of the specific bond between α7β1 integrin and its pathologically relevant ligand invasin. Upon add...

  2. Hydrated Ordinary Portland Cement as a Carbonic Cement: The Mechanisms, Dynamics, and Implications of Self-Sealing and CO2 Resistance in Wellbore Cements

    Energy Technology Data Exchange (ETDEWEB)

    Guthrie, George Drake Jr. [Los Alamos National Laboratory; Pawar, Rajesh J. [Los Alamos National Laboratory; Carey, James William [Los Alamos National Laboratory; Karra, Satish [Los Alamos National Laboratory; Harp, Dylan Robert [Los Alamos National Laboratory; Viswanathan, Hari S. [Los Alamos National Laboratory

    2017-07-28

    This report analyzes the dynamics and mechanisms of the interactions of carbonated brine with hydrated Portland cement. The analysis is based on a recent set of comprehensive reactive-transport simulations, and it relies heavily on the synthesis of the body of work on wellbore integrity that we have conducted for the Carbon Storage Program over the past decade.

  3. Complex admixtures of clathrate hydrates in a water desalination method

    Science.gov (United States)

    Simmons, Blake A.; Bradshaw, Robert W.; Dedrick, Daniel E.; Anderson, David W.

    2009-07-14

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

  4. HYDRATION MECHANISMS OF CALCIUM SULPHOALUMINATE C4A3S̄ , C4AS̄ PHASE AND ACTIVE BELITE β-C2S

    Directory of Open Access Journals (Sweden)

    H. EL-DIDAMONY

    2012-12-01

    Full Text Available Highly reactive belite and calcium sulphoaluminate as well as monosulphate mix were prepared from nano-materials at lower temperatures ~1250°C. The crystal size of these materials was 25, 16 and 27 nm as determined from the X-ray analysis. The sulphoaluminate belite cement is a recent type of cement prepared at lower temperature with good properties. The aim of the present work is to synthesize C4A3S̄, monosulphate mix C4AS̄ and active belite β-C2S. The hydration mechanism was studied by XRD and DSC techniques as well as by the determination of chemically combined water contents of cement pastes with curing time. The results reveal that ettringite is first formed hydrates in the monosulphate mix, which then converted into monosulphate hydrates. The results of DSC and XRD are in good agreement with those of combined water contents. On the other side, the rate of hydration of active belite increases linearly from 3 up to 90 days, whereas, the traditional belite hydrates increase with lower rate up to 90 days, due to the thermodynamic stability structure of traditional belite.

  5. Dimeric Arrangement of the Parathyroid Hormone Receptor and a Structural Mechanism for Ligand-induced Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Pioszak, Augen A.; Harikumar, Kaleeckal G.; Parker, Naomi R.; Miller, Laurence J.; Xu, H. Eric (Van Andel); (Mayo)

    2010-06-25

    The parathyroid hormone receptor (PTH1R) is a class B G protein-coupled receptor that is activated by parathyroid hormone (PTH) and PTH-related protein (PTHrP). Little is known about the oligomeric state of the receptor and its regulation by hormone. The crystal structure of the ligand-free PTH1R extracellular domain (ECD) reveals an unexpected dimer in which the C-terminal segment of both ECD protomers forms an {alpha}-helix that mimics PTH/PTHrP by occupying the peptide binding groove of the opposing protomer. ECD-mediated oligomerization of intact PTH1R was confirmed in living cells by bioluminescence and fluorescence resonance energy transfer experiments. As predicted by the structure, PTH binding disrupted receptor oligomerization. A receptor rendered monomeric by mutations in the ECD retained wild-type PTH binding and cAMP signaling ability. Our results are consistent with the hypothesis that PTH1R forms constitutive dimers that are dissociated by ligand binding and that monomeric PTH1R is capable of activating G protein.

  6. Dissociation of equilibrium points for color-discrimination and color-appearance mechanisms in incomplete chromatic adaptation.

    Science.gov (United States)

    Sato, Tomoharu; Nagai, Takehiro; Kuriki, Ichiro; Nakauchi, Shigeki

    2016-03-01

    We compared the color-discrimination thresholds and supra-threshold color differences (STCDs) obtained in complete chromatic adaptation (gray) and incomplete chromatic adaptation (red). The color-difference profiles were examined by evaluating the perceptual distances between various color pairs using maximum likelihood difference scaling. In the gray condition, the chromaticities corresponding with the smallest threshold and the largest color difference were almost identical. In contrast, in the red condition, they were dissociated. The peaks of the sensitivity functions derived from the color-discrimination thresholds and STCDs along the L-M axis were systematically different between the adaptation conditions. These results suggest that the color signals involved in color discrimination and STCD tasks are controlled by separate mechanisms with different characteristic properties.

  7. Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate

    Science.gov (United States)

    Geng, Guoqing; Myers, Rupert J.; Li, Jiaqi; Maboudian, Roya; Carraro, Carlo; Shapiro, David A.; Monteiro, Paulo J. M.

    2017-03-01

    The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is more deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca2+ of the interlayer. Dreierketten chain cross-links act as ‘columns’ to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a ‘bottom-up’ approach.

  8. Theoretical investigation of the first-shell mechanism of acetylene hydration catalyzed by a biomimetic tungsten complex.

    Science.gov (United States)

    Liu, Yan-Fang; Liao, Rong-Zhen; Ding, Wan-Jian; Yu, Jian-Guo; Liu, Ruo-Zhuang

    2011-06-01

    The reaction mechanism of the hydration of acetylene to acetaldehyde catalyzed by [W(IV)O(mnt)(2)](2-) (where mnt(2-) is 1,2-dicyanoethylenedithiolate) is studied using density functional theory. Both the uncatalyzed and the catalyzed reaction are considered to find out the origin of the catalysis. Three different models are investigated, in which an aquo, a hydroxo, or an oxo coordinates to the tungsten center. A first-shell mechanism is suggested, similarly to recent calculations on tungsten-dependent acetylene hydratase. The acetylene substrate first coordinates to the tungsten center in an η(2) fashion. Then, the tungsten-bound hydroxide activates a water molecule to perform a nucleophilic attack on the acetylene, resulting in the formation of a vinyl anion and a tungsten-bound water molecule. This is followed by proton transfer from the tungsten-bound water molecule to the newly formed vinyl anion intermediate. Tungsten is directly involved in the reaction by binding and activating acetylene and providing electrostatic stabilization to the transition states and intermediates. Three other mechanisms are also considered, but the associated energetic barriers were found to be very high, ruling out those possibilities.

  9. Flow assurance intervention, hydrates remediation

    Energy Technology Data Exchange (ETDEWEB)

    Mancini, Christopher S. [Oceaneering International Inc., Houston, TX (United States)

    2012-07-01

    This paper addresses the issues of removing hydrates in sub sea flow lines and associated equipment with an Remotely Operated Vehicle (ROV) of opportunity and a multi-service-vessel (MSV). The paper is split into three topics: the equipment used with the ROV, assessing the interface points and handling fluids produced from drawing down the pressure. Each section is explained thoroughly and backed up with real world experience. The equipment section details information from actual jobs performed and why the particular components were utilized. The system is generally contained in an ROV mounted skid. Pumps are utilized to draw down the pressure inside the hydrated section of equipment, removing one of the three necessary components for hydrates formation. Once the section is pumped down, several options exist for handling the fluids pumped out of the system: pumping to surface, re-injection into the well, or injection into an operating flow line. This method of hydrates remediation is both economical and timely. Hydrate blockages form in low temperatures and high pressures. Reducing the pressure or increasing the temperature so the conditions lie to the right of the hydrate dissociation curve will slowly decompose the blockage. Depressurization and the use of MEG or methanol will give favorable conditions to remove the hydrate plug. Oceaneering has the capabilities to remove hydrates using the FRS in conjunction with an installation vessel to dispose of the gas and fluid removed from the flow line. Hydrate remediation techniques should be implemented into the initial design to reduce costs later. The cost of stopped production combined with the day rate for equipment needed for hydrate removal outweighs the costs if no technique is utilized. (author)

  10. Are major dissociative disorders characterized by a qualitatively different kind of dissociation?

    Science.gov (United States)

    Rodewald, Frauke; Dell, Paul F; Wilhelm-Gossling, Claudia; Gast, Ursula

    2011-01-01

    A total of 66 patients with a major dissociative disorder, 54 patients with nondissociative disorders, and 30 nonclinical controls were administered the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised, the Dissociative Experiences Scale, the Multidimensional Inventory of Dissociation, and the Symptom Checklist 90-Revised. Dissociative patients reported significantly more dissociative and nondissociative symptoms than did nondissociative patients and nonclinical controls. When general psychopathology was controlled, the dissociation scores of dissociative patients were still significantly higher than those of both other groups, whereas the dissociation scores of nondissociative patients and nonclinical controls no longer differed. These findings appear to be congruent with a typological model of dissociation that distinguishes between 2 qualitatively different kinds of dissociation. Specifically, the results of this study suggest that the dissociation that occurs in major dissociative disorders (i.e., dissociative identity disorder [DID] and dissociative disorder not otherwise specified, Type 1 [DDNOS-1]) is qualitatively different from the dissociation that occurs in persons who do not have a dissociative disorder. In contrast to previous research, the dissociation of persons who do not have a dissociative disorder is not limited to absorption; it covers a much wider range of phenomena. The authors hypothesize that different mechanisms produce the dissociation of persons with DID and DDNOS-1 as opposed to the dissociation of persons who do not have a dissociative disorder.

  11. Evaluation of long-term gas hydrate production testing locations on the Alaska North Slope

    Science.gov (United States)

    Collett, Timothy S.; Boswell, Ray; Lee, Myung W.; Anderson, Brian J.; Rose, Kelly K.; Lewis, Kristen A.

    2012-01-01

    The results of short-duration formation tests in northern Alaska and Canada have further documented the energy-resource potential of gas hydrates and have justified the need for long-term gas-hydrate-production testing. Additional data acquisition and long-term production testing could improve the understanding of the response of naturally occurring gas hydrate to depressurization-induced or thermal-, chemical-, or mechanical-stimulated dissociation of gas hydrate into producible gas. The Eileen gashydrate accumulation located in the Greater Prudhoe Bay area in northern Alaska has become a focal point for gas-hydrate geologic and production studies. BP Exploration (Alaska) Incorporated and ConocoPhillips have each established research partnerships with the US Department of Energy to assess the production potential of gas hydrates in northern Alaska. A critical goal of these efforts is to identify the most suitable site for production testing. A total of seven potential locations in the Prudhoe Bay, Kuparuk River, and Milne Point production units were identified and assessed relative to their suitability as a long-term gas-hydrate-production test sites. The test-site-assessment criteria included the analysis of the geologic risk associated with encountering reservoirs for gas-hydrate testing. The site-selection process also dealt with the assessment of the operational/logistical risk associated with each of the potential test sites. From this review, a site in the Prudhoe Bay production unit was determined to be the best location for extended gas-hydrate-production testing. The work presented in this report identifies the key features of the potential test site in the Greater Prudhoe Bay area and provides new information on the nature of gas-hydrate occurrence and the potential impact of production testing on existing infrastructure at the most favorable sites. These data were obtained from well-log analysis, geological correlation and mapping, and numerical

  12. Dissociative amnesia.

    Science.gov (United States)

    Staniloiu, Angelica; Markowitsch, Hans J

    2014-08-01

    Dissociative amnesia is one of the most enigmatic and controversial psychiatric disorders. In the past two decades, interest in the understanding of its pathophysiology has surged. In this report, we review new data about the epidemiology, neurobiology, and neuroimaging of dissociative amnesia and show how advances in memory research and neurobiology of dissociation inform proposed pathogenetic models of the disorder. Dissociative amnesia is characterised by functional impairment. Additionally, preliminary data suggest that affected people have an increased and possibly underestimated suicide risk. The prevalence of dissociative amnesia differs substantially across countries and populations. Symptoms and disease course also vary, indicating a possibly heterogeneous disorder. The accompanying clinical features differ across cultural groups. Most dissociative amnesias are retrograde, with memory impairments mainly involving the episodic-autobiographical memory domain. Anterograde dissociative amnesia occurring without significant retrograde memory impairments is rare. Functional neuroimaging studies of dissociative amnesia with prevailing retrograde memory impairments show changes in the network that subserves autobiographical memory. At present, no evidence-based treatments are available for dissociative amnesia and no broad framework exists for its rehabilitation. Further research is needed into its neurobiology, course, treatment options, and strategies to improve differential diagnoses. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Effects of Fluid Saturation on Gas Recovery from Class-3 Hydrate Accumulations Using Depressurization: Case Study of Yuan-An Ridge Site in Southwestern Offshore Taiwan

    Science.gov (United States)

    Huang, Yi-Jyun; Wu, Cheng-Yueh; Hsieh, Bieng-Zih

    2016-04-01

    Gas hydrates are crystalline compounds in which guest gas molecules are trapped in host lattices of ice crystals. In Taiwan, the significant efforts have recently begun to evaluate the reserves of hydrate because the vast accumulations of gas hydrates had been recognized in southwestern offshore Taiwan. Class-3 type hydrate accumulations are referred to an isolated hydrate layer without an underlying zone of mobile fluids, and the entire hydrate layer may be well within the hydrate stability zone. The depressurization method is a useful dissociation method for gas production from Class-3 hydrate accumulations. The dissociation efficiency is controlled by the responses of hydrate to the propagating pressure disturbance, and the pressure propagation is relating to the amount (or saturation) of the mobile fluid in pore space of the hydrate layer. The purpose of this study is to study the effects of fluid saturation on the gas recovery from a class-3 hydrate accumulation using depressurization method. The case of a class-3 hydrate deposit of Yuan-An Ridge in southwestern offshore Taiwan is studied. The numerical method was used in this study. The reservoir simulator we used to study the dissociation of hydrate and the production of gas was the STARS simulator developed by CMG, which coupled heat transfer, geo-chemical, geo-mechanical, and multiphase fluid flow mechanisms. The study case of Yuan-An Ridge is located in southwestern offshore Taiwan. The hydrate deposit was found by the bottom simulating reflectors (BSRs). The geological structure of the studied hydrate deposit was digitized to build the geological model (grids) of the case. The formation parameters, phase behavior data, rock and fluid properties, and formation's initial conditions were assigned sequentially to grid blocks, and the completion and operation conditions were designed to wellbore blocks to finish the numerical model. The changes of reservoir pressure, temperature, saturation due to the hydrate

  14. Dissociative Ionization Mechanism and Appearance Energies in Adipic Acid Revealed by Imaging Photoelectron Photoion Coincidence, Selective Deuteration, and Calculations.

    Science.gov (United States)

    Heringa, Maarten F; Slowik, Jay G; Prévôt, André S H; Baltensperger, Urs; Hemberger, Patrick; Bodi, Andras

    2016-05-26

    Adipic acid, a model compound for oxygenated organic aerosol, has been studied at the VUV beamline of the Swiss Light Source. Internal energy selected cations were prepared by threshold photoionization using vacuum ultraviolet synchrotron radiation and imaging photoelectron photoion coincidence spectroscopy (iPEPICO). The threshold photoelectron spectrum yields a vertical ionization energy (IE) of 10.5 eV, significantly above the calculated adiabatic IE of 8.6 eV. The cationic minimum is accessible after vertical ionization by H-transfer from one of the γ-carbons to a carbonyl oxygen and is sufficiently energetic to decay by water loss at the ionization onset. The slope of the breakdown curves, quantum chemical calculations, and selective deuteration of the carboxylic hydrogens establish the dissociative photoionization mechanism. After ionization, one γ-methylene hydrogen and the two carboxylic hydrogens are randomized prior to H2O loss. On the basis of the deuteration degree in the H2O + CO-loss product at higher energies, a direct water-loss channel without complete randomization also exists. The breakdown diagram and center of gravity of the H2O + CO-loss peak were modeled to obtain 0 K appearance energies of 10.77, 10.32, and 11.53 eV for H2O + CO loss, CH2COOH loss, and H2O + CH2COOH loss from adipic acid. These agree well with the CBS-QB3 calculated values of 10.68, 10.45, and 11.57 eV, respectively, which shows that threshold photoionization can yield energetics data as long as the dissociation is statistical, even when the parent ion cannot be observed. The results can be used as a starting point for a deeper understanding of the ionization and low-energy fragmentation of organic aerosol components.

  15. Unexpected linear ion trap collision-induced dissociation and Fourier transform ion cyclotron resonance infrared multi-photon dissociation fragmentation of a hydrated C-glycoside of 5-fluorouridine formed by the action of the pseudouridine synthases RluA and TruB.

    Science.gov (United States)

    Miracco, Edward J; Bogdanov, Bogdan; Mueller, Eugene G

    2011-09-30

    As part of the investigation of the pseudouridine synthases, 5-fluorouridine in RNA was employed as a mechanistic probe. The hydrated, rearranged product of 5-fluorouridine was isolated as part of a dinucleotide and found to undergo unusual fragmentation during mass spectrometry, with the facile loss of HNCO from the product pyrimidine ring favored over phosphodiester bond rupture. Although the loss of HNCO from uridine and pseudouridine is well established, the pericyclic process leading to their fragmentation cannot operate with the saturated pyrimidine ring in the product of 5-fluorouridine. Based on the MS(n) results and calculations reported here, a new mechanism relying on the peculiar disposition of the functional groups of the product pyrimidine ring is proposed to account for the unusually facile fragmentation.

  16. On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation

    Energy Technology Data Exchange (ETDEWEB)

    Weck, Philippe F.; Kim, Eunja; Buck, Edgar C.

    2015-09-11

    The mechanical properties and stability of studtite, (UO2)(O2)(H2O)2·2H2O, and metastudtite, (UO2)(O2)(H2O)2, two important corrosion phases observed on spent nuclear fuel exposed to water, have been investigated using density functional perturbation theory. While (UO2)(O2)(H2O)2 satisfies the necessary and sufficient Born criteria for mechanical stability, (UO2)(O2)(H2O)2·2H2O is found to be mechanically metastable, which might be the underlying cause of the irreversibility of the studtite to metastudtite transformation. According to Pugh’s and Poisson’s ratios and the Cauchy pressure, both phases are considered ductile and shear modulus is the parameter limiting their mechanical stability. Debye temperatures of 294 and 271 K are predicted for polycrystalline (UO2)(O2)(H2O)2·2H2O and (UO2)(O2)(H2O)2, suggesting a lower micro-hardness of metastudtite.

  17. Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate

    Science.gov (United States)

    Geng, Guoqing; Myers, Rupert J.; Li, Jiaqi; Maboudian, Roya; Carraro, Carlo; Shapiro, David A.; Monteiro, Paulo J. M.

    2017-01-01

    The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is more deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca2+ of the interlayer. Dreierketten chain cross-links act as ‘columns’ to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a ‘bottom-up’ approach. PMID:28281635

  18. Differential Salt-Induced Dissociation of the p53 Protein Complexes with Circular and Linear Plasmid DNA Substrates Suggest Involvement of a Sliding Mechanism

    Directory of Open Access Journals (Sweden)

    Peter Šebest

    2015-01-01

    Full Text Available A study of the effects of salt conditions on the association and dissociation of wild type p53 with different ~3 kbp long plasmid DNA substrates (supercoiled, relaxed circular and linear, containing or lacking a specific p53 binding site, p53CON using immunoprecipitation at magnetic beads is presented. Salt concentrations above 200 mM strongly affected association of the p53 protein to any plasmid DNA substrate. Strikingly different behavior was observed when dissociation of pre-formed p53-DNA complexes in increased salt concentrations was studied. While contribution from the p53CON to the stability of the p53-DNA complexes was detected between 100 and 170 mM KCl, p53 complexes with circular DNAs (but not linear exhibited considerable resistance towards salt treatment for KCl concentrations as high as 2 M provided that the p53 basic C-terminal DNA binding site (CTDBS was available for DNA binding. On the contrary, when the CTDBS was blocked by antibody used for immunoprecipitation, all p53-DNA complexes were completely dissociated from the p53 protein in KCl concentrations ≥200 mM under the same conditions. These observations suggest: (a different ways for association and dissociation of the p53-DNA complexes in the presence of the CTDBS; and (b a critical role for a sliding mechanism, mediated by the C-terminal domain, in the dissociation process.

  19. The Sense of Agency in Autism Spectrum Disorders: a Dissociation between Prospective and Retrospective Mechanisms?

    Directory of Open Access Journals (Sweden)

    Tiziana eZalla

    2015-09-01

    Full Text Available While a large number of studies have reported impairments in social and interpersonal abilities in individuals with autism spectrum disorder (ASD, relatively few studies have focused on self-related knowledge in this population. One of the processes implicated in the physical dimension of the Self is the sense of agency (SoA, i.e., the experience of initiating and controlling one’s own actions and producing desired changes in the world via these actions. So far, the few studies investigating SoA in ASD have reported contrasting results, with some showing spared, others impaired SoA. Here, we review the existing literature and suggest that the distinction between prospective and retrospective mechanisms of the SoA might help reconcile the existing findings. In the light of a multi-componential model of SoA, we propose the view that a specific impairment at the level of prospective mechanisms acting on internal agency signals (i.e., the intention, action selection, or command produced to achieve the goal may be responsible for the reduced SoA in ASD, along with spared retrospective mechanisms. Future research should shed light on the impact of abnormal SoA on social and self-related dysfunctions in ASD.

  20. Dissociable neural mechanisms underlying the modulation of pain and anxiety? An FMRI pilot study.

    Science.gov (United States)

    Wiech, Katja; Edwards, Robert; Moseley, Graham Lorimer; Berna, Chantal; Ploner, Markus; Tracey, Irene

    2014-01-01

    The down-regulation of pain through beliefs is commonly discussed as a form of emotion regulation. In line with this interpretation, the analgesic effect has been shown to co-occur with reduced anxiety and increased activity in the ventrolateral prefrontal cortex (VLPFC), which is a key region of emotion regulation. This link between pain and anxiety modulation raises the question whether the two effects are rooted in the same neural mechanism. In this pilot fMRI study, we compared the neural basis of the analgesic and anxiolytic effect of two types of threat modulation: a "behavioral control" paradigm, which involves the ability to terminate a noxious stimulus, and a "safety signaling" paradigm, which involves visual cues that signal the threat (or absence of threat) that a subsequent noxious stimulus might be of unusually high intensity. Analgesia was paralleled by VLPFC activity during behavioral control. Safety signaling engaged elements of the descending pain control system, including the rostral anterior cingulate cortex that showed increased functional connectivity with the periaqueductal gray and VLPFC. Anxiety reduction, in contrast, scaled with dorsolateral prefrontal cortex activation during behavioral control but had no distinct neural signature during safety signaling. Our pilot data therefore suggest that analgesic and anxiolytic effects are instantiated in distinguishable neural mechanisms and differ between distinct stress- and pain-modulatory approaches, supporting the recent notion of multiple pathways subserving top-down modulation of the pain experience. Additional studies in larger cohorts are needed to follow up on these preliminary findings.

  1. Dissociable neural mechanisms underlying the modulation of pain and anxiety? An FMRI pilot study.

    Directory of Open Access Journals (Sweden)

    Katja Wiech

    Full Text Available The down-regulation of pain through beliefs is commonly discussed as a form of emotion regulation. In line with this interpretation, the analgesic effect has been shown to co-occur with reduced anxiety and increased activity in the ventrolateral prefrontal cortex (VLPFC, which is a key region of emotion regulation. This link between pain and anxiety modulation raises the question whether the two effects are rooted in the same neural mechanism. In this pilot fMRI study, we compared the neural basis of the analgesic and anxiolytic effect of two types of threat modulation: a "behavioral control" paradigm, which involves the ability to terminate a noxious stimulus, and a "safety signaling" paradigm, which involves visual cues that signal the threat (or absence of threat that a subsequent noxious stimulus might be of unusually high intensity. Analgesia was paralleled by VLPFC activity during behavioral control. Safety signaling engaged elements of the descending pain control system, including the rostral anterior cingulate cortex that showed increased functional connectivity with the periaqueductal gray and VLPFC. Anxiety reduction, in contrast, scaled with dorsolateral prefrontal cortex activation during behavioral control but had no distinct neural signature during safety signaling. Our pilot data therefore suggest that analgesic and anxiolytic effects are instantiated in distinguishable neural mechanisms and differ between distinct stress- and pain-modulatory approaches, supporting the recent notion of multiple pathways subserving top-down modulation of the pain experience. Additional studies in larger cohorts are needed to follow up on these preliminary findings.

  2. The interaction of climate change and methane hydrates

    Science.gov (United States)

    Ruppel, Carolyn D.; Kessler, John D.

    2017-01-01

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

  3. Dissociation in decision bias mechanism between probabilistic information and previous decision

    Directory of Open Access Journals (Sweden)

    Yoshiyuki eKaneko

    2015-05-01

    Full Text Available Target detection performance is known to be influenced by events in the previous trials. It has not been clear, however, whether this bias effect is due to the previous sensory stimulus, motor response, or decision. Also it remains open whether or not the previous trial effect emerges via the same mechanism as the effect of knowledge about the target probability. In the present study, we asked normal human subjects to make a decision about the presence or absence of a visual target. We presented a pre-cue indicating the target probability before the stimulus, and also a decision-response mapping cue after the stimulus so as to tease apart the effect of decision from that of motor response. We found that the target detection performance was significantly affected by the probability cue in the current trial and also by the decision in the previous trial. While the information about the target probability modulated the decision criteria, the previous decision modulated the sensitivity to target-relevant sensory signals (d-prime. Using functional magnetic resonance imaging, we also found that activation in the left intraparietal sulcus was decreased when the probability cue indicated a high probability of the target. By contrast, activation in the right inferior frontal gyrus was increased when the subjects made a target-present decision in the previous trial, but this change was observed specifically when the target was present in the current trial. Activation in these regions was associated with individual-difference in the decision computation parameters. We argue that the previous decision biases the target detection performance by modulating the processing of target-selective information, and this mechanism is distinct from modulation of decision criteria due to expectation of a target.

  4. Investigating syn- vs. post-eruption hydration mechanisms of the 2012 Havre submarine explosive eruption: Water speciation analysis of pumiceous rhyolitic glass

    Science.gov (United States)

    Mitchell, S. J.; McIntosh, I. M.; Houghton, B. F.; Shea, T.; Carey, R.

    2016-12-01

    Volatiles preserved in volcanic glass can record the quenching, fragmentation and solubility conditions during an explosive eruption. The VEI-5 2012 eruption of Havre volcano, which produced >1.5 km3 of rhyolite, provides exciting new insight into deep-submarine explosive eruptions. With no direct observations of the eruption at the 900 mbsl vent, the analysis and interpretation of volatile concentrations and speciation within pyroclasts is essential to constraining the eruption style and quenching mechanisms in this understudied environment. We present here the first detailed water speciation data for a large submarine explosive eruption. Water concentrations were measured in pyroclasts from known deposit localities across the Havre stratigraphic succession after ROV collection in 2015. Variations in total water concentration (H2OT) within pyroclasts were determined using high spatial resolution (1 - 2 µm) micro-Raman spectroscopy and water speciation (molecular water (H2Om) and OH) concentrations were measured using Fourier-transform infrared spectroscopy. H2OT concentrations are consistent between Raman and FTIR analysis, ranging from 0.1 - 1.5 wt % H2OT over different stratigraphic units. Comparison of water speciation data with speciation models suggests the Havre pyroclasts experienced secondary, non-magmatic hydration. Since OH is unaltered by secondary hydration, OH concentrations aid in the interpretation of quench depths and inferring of eruption mechanisms. The variability of excess H2Om across units suggests a more complex glass-hydration mechanism during the eruption instead of exclusively post-eruption, low-temperature secondary rehydration. The young sample ages are inconsistent with our current understanding of low-temperature H2O-diffusivity timescales, implying faster secondary rehydration in a higher-temperature submarine setting. We here explore potentially novel syn-eruptive, higher-temperature hydration mechanisms for deep-submarine pumice.

  5. Mechanism and kinetics of H{sub 2}S-CO{sub 2} mixture dissociation in plasma of a microwave-discharge

    Energy Technology Data Exchange (ETDEWEB)

    Potapkin, B.V.; Strelkova, M.I.; Fridman, A.A. [RRC Kurchatov Institute, Moscow (Russian Federation)] [and others

    1995-08-01

    Several experimental and theoretical investigations of plasma-chemical H{sub 2}S dissociation have addressed the effects of different gas compositions and various types of discharges (such as microwave, radio-frequency, arc, and glidarc discharges). There are two primary reasons for these investigations: (1) the plasma-chemical process recovers both hydrogen (a valuable chemical reagent) and sulfur from H{sub 2}S (as in the conventional Claus process), and (2) plasmas can be used for selectively decomposing H{sub 2}S in air and other exhaust gases for environmental-control purposes. These studies have shown that, in plasmas with strong centrifugal force fields, H{sub 2}S can be dissociated with high specific rates and low specific energies of dissociation (0.8-1.0 eV/molecule). Furthermore, acid gases from both natural deposits and those produced in industrial processes often contain significant amounts of CO{sub 2} in addition to H{sub 2}S. Unfortunately, CO{sub 2}can have substantial, negative impacts on H{sub 2}S dissociation. In particular, CO{sub 2} can significantly increase the process energy consumption and affect by-product composition. However, until this study, the influence of CO{sub 2} on the plasma-chemical dissociation of H{sub 2}S has not been studied in detail. This study presents the results of a theoretical analysis of an experimental determination of the CO{sub 2} effects over a wide range of CO{sub 2} concentrations. This analysis identified the primary chemical reaction mechanism and the kinetics for the plasma-chemical dissociation of H{sub 2}S, including the generation of two undesirable by-products, SO{sub 2} and COS.

  6. Enhancing mung bean hydration using the ultrasound technology: description of mechanisms and impact on its germination and main components

    Science.gov (United States)

    Miano, Alberto Claudio; Pereira, Jessica Da Costa; Castanha, Nanci; Júnior, Manoel Divino Da Matta; Augusto, Pedro Esteves Duarte

    2016-12-01

    The ultrasound technology was successfully used to improve the mass transfer processes on food. However, the study of this technology on the grain hydration and on its main components properties was still not appropriately described. This work studied the application of the ultrasound technology on the hydration process of mung beans (Vigna radiata). This grain showed sigmoidal hydration behavior with a specific water entrance pathway. The ultrasound reduced ~25% of the hydration process time. In addition, this technology caused acceleration of the seed germination – and some hypothesis for this enhancement were proposed. Moreover, it was demonstrated that the ultrasound did not change both structure and pasting properties of the bean starch. Finally, the flour rheological properties proved that the ultrasound increased its apparent viscosity, and as the starch was not modified, this alteration was attributed to the proteins. All these results are very desirable for industry since the ultrasound technology improves the hydration process without altering the starch properties, accelerates the germination process (that is important for the malting and sprouting process) and increases the flour apparent viscosity, which is desirable to produce bean-based products that need higher consistency.

  7. Enhancing mung bean hydration using the ultrasound technology: description of mechanisms and impact on its germination and main components.

    Science.gov (United States)

    Miano, Alberto Claudio; Pereira, Jessica da Costa; Castanha, Nanci; Júnior, Manoel Divino da Matta; Augusto, Pedro Esteves Duarte

    2016-12-19

    The ultrasound technology was successfully used to improve the mass transfer processes on food. However, the study of this technology on the grain hydration and on its main components properties was still not appropriately described. This work studied the application of the ultrasound technology on the hydration process of mung beans (Vigna radiata). This grain showed sigmoidal hydration behavior with a specific water entrance pathway. The ultrasound reduced ~25% of the hydration process time. In addition, this technology caused acceleration of the seed germination - and some hypothesis for this enhancement were proposed. Moreover, it was demonstrated that the ultrasound did not change both structure and pasting properties of the bean starch. Finally, the flour rheological properties proved that the ultrasound increased its apparent viscosity, and as the starch was not modified, this alteration was attributed to the proteins. All these results are very desirable for industry since the ultrasound technology improves the hydration process without altering the starch properties, accelerates the germination process (that is important for the malting and sprouting process) and increases the flour apparent viscosity, which is desirable to produce bean-based products that need higher consistency.

  8. Drilling Gas Hydrates on hydrate Ridge, Oregon continental margin

    Science.gov (United States)

    Trehu, A. M.; Bohrmann, G.; Leg 204 Science Party

    2002-12-01

    During Leg 204, we cored and logged 9 sites on the Oregon continental margin to determine the distribution and concentration of gas hydrates in an accretionary ridge and adjacent slope basin, investigate the mechanisms that transport methane and other gases into the gas hydrate stability zone (GHSZ), and obtain constraints on physical properties of hydrates in situ. A 3D seismic survey conducted in 2000 provided images of potential subsurface fluid conduits and indicated the position of the GHSZ throughout the survey region. After coring the first site, we acquired Logging-While-Drilling (LWD) data at all but one site to provide an overview of downhole physical properties. The LWD data confirmed the general position of key seismic stratigraphic horizons and yielded an initial estimate of hydrate concentration through the proxy of in situ electrical resistivity. These records proved to be of great value in planning subsequent coring. The second new hydrate proxy to be tested was infrared thermal imaging of cores on the catwalk as rapidly as possible after retrieval. The thermal images were used to identify hydrate samples and to estimate the distribution and texture of hydrate within the cores. Geochemical analyses of interstitial waters and of headspace and void gases provide additional information on the distribution and concentration of hydrate within the stability zone, the origin and pathway of fluids into and through the GHSZ, and the rates at which gas hydrate is forming. Bio- and lithostratigraphic description of cores, measurement of physical properties, and in situ pressure core sampling and thermal measurements complement the data set, providing ground-truth tests of inferred physical and sedimentological properties. Among the most interesting preliminary results are: 1) that gas hydrates are distributed through a broad depth range within the GHSZ and that different physical and chemical proxies for hydrate distribution and concentration give generally

  9. Development of Alaskan gas hydrate resources. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Kamath, V.A.; Sharma, G.D.; Patil, S.L.

    1991-06-01

    The research undertaken in this project pertains to study of various techniques for production of natural gas from Alaskan gas hydrates such as, depressurization, injection of hot water, steam, brine, methanol and ethylene glycol solutions through experimental investigation of decomposition characteristics of hydrate cores. An experimental study has been conducted to measure the effective gas permeability changes as hydrates form in the sandpack and the results have been used to determine the reduction in the effective gas permeability of the sandpack as a function of hydrate saturation. A user friendly, interactive, menu-driven, numerical difference simulator has been developed to model the dissociation of natural gas hydrates in porous media with variable thermal properties. A numerical, finite element simulator has been developed to model the dissociation of hydrates during hot water injection process.

  10. Elucidating collision induced dissociation products and reaction mechanisms of protonated uracil by coupling chemical dynamics simulations with tandem mass spectrometry experiments.

    Science.gov (United States)

    Molina, Estefanía Rossich; Ortiz, Daniel; Salpin, Jean-Yves; Spezia, Riccardo

    2015-12-01

    In this study we have coupled mixed quantum-classical (quantum mechanics/molecular mechanics) direct chemical dynamics simulations with electrospray ionization/tandem mass spectrometry experiments in order to achieve a deeper understanding of the fragmentation mechanisms occurring during the collision induced dissociation of gaseous protonated uracil. Using this approach, we were able to successfully characterize the fragmentation pathways corresponding to ammonia loss (m/z 96), water loss (m/z 95) and cyanic or isocyanic acid loss (m/z 70). Furthermore, we also performed experiments with isotopic labeling completing the fragmentation picture. Remarkably, fragmentation mechanisms obtained from chemical dynamics simulations are consistent with those deduced from isotopic labeling.

  11. Experimental Investigations into the Production Behavior of Methane Hydrate in Porous Sediment under Ethylene Glycol Injection and Hot Brine Stimulation

    OpenAIRE

    Li, Xiaosen; Li, Gang

    2010-01-01

    1 2 3 The flowing of hot water or hot brine injected in the vessel can be regarded as the moving of a piston from the inlet to the outlet. The hydrate dissociation process is divided into three stages: free gas production, hydrate dissociation and residual gas production. The process of the hydrate dissociation is a process of the temperature decrease in the presence of the brine solution. The duration of the hydrate dissociation is shortened and the degree of the depth of the temperature dro...

  12. Gas hydrates

    Digital Repository Service at National Institute of Oceanography (India)

    Ramprasad, T.

    and the role it plays in the global climate and the future of fuels. Russia, Japan, Nigeria, Peru, Chile, Pakistan, Indonesia, Korea, etc are various countries who are perusing the gas hydrates studies as a future resource for fuel. Indian Initiative..., 1993, Free gas at the base of the gas hydrate zone in the vicinity of the Chile Triple junction: Geology, v. 21, pp. 905-908. Borowski, W.S., C.K. Paull, and U. William, III, 1999, Global and local variations of interstitial sulfate gradients...

  13. Gas hydrate formation in deep-sea sediments - on the role of sediment-mechanical process determination; Gashydratbildung in Tiefseesedimenten - zur Rolle der sedimentmechanischen Prozesssteuerung

    Energy Technology Data Exchange (ETDEWEB)

    Feeser, V. [Kiel Univ. (Germany). Geologisch-Palaeontologisches Inst.

    1997-12-31

    Slope failures in gas hydrate regions are encountered throughout the oceans. The stability of seafloor slopes can be assessed and predicted by means of calculation methods based on mechanical laws and parameters which describe the deformation behaviour and/or mechanical strength of the slope-forming sediments. Thermodynamic conditions conducive to the formation of gas hydrates in marine sediments differ from conditions prevailing in exclusively water-filled systems. The present contribution describes the relevant energetic conditions on the basis of a simple spherical model giving due consideration to petrographic parameters. Depending on pore size distribution, lithological stress conditions, pore water pressure, and sediment strength gas hydrates will either develop as a cementing phase or as segregated lenses. (MSK) [Deutsch] In den Weltmeeren ereignen sich immer wieder Hangrutschungen in Gashydratgebieten. Die zur Beurteilung und Prognonse von Hangstabilitaeten zu verwendenden Berechnungsverfahren erfordern Stoffgesetze und Parameter, welche das Deformations-und/oder Festigkeitsverhalten der hangbildenden Sedimente beschreiben. Die thermodynamischen Bildungsbedingungen von Gashydraten in marinen Sedimenten unterscheiden sich von den Bedingungen in ausschliesslich wassergefuellten Systemen. Unter Einbeziehung petrographischer Eigenschaften werden die energetischen Bedingungen beschrieben. Dazu dient ein einfaches Kugelmodell. Je nach vorhandenem Porenraumspektrum, lithostatischen Spannungsverhaeltnissen, Porenwasserdruck und Sedimentfestigkeit wachsen Gashydrate als Porenraumzement oder als segregierte Linsen.

  14. Are seafloor pockmarks on the Chatham Rise, New Zealand, linked to CO2 hydrates? Gas hydrate stability considerations.

    Science.gov (United States)

    Pecher, I. A.; Davy, B. W.; Rose, P. S.; Coffin, R. B.

    2015-12-01

    Vast areas of the Chatham Rise east of New Zealand are covered by seafloor pockmarks. Pockmark occurrence appears to be bathymetrically controlled with a band of smaller pockmarks covering areas between 500 and 700 m and large seafloor depressions beneath 800 m water depth. The current depth of the top of methane gas hydrate stability in the ocean is about 500 m and thus, we had proposed that pockmark formation may be linked to methane gas hydrate dissociation during sealevel lowering. However, while seismic profiles show strong indications of fluid flow, geochemical analyses of piston cores do not show any evidence for current or past methane flux. The discovery of Dawsonite, indicative of significant CO2 flux, in a recent petroleum exploration well, together with other circumstantial evidence, has led us to propose that instead of methane hydrate, CO2 hydrate may be linked to pockmark formation. We here present results from CO2 hydrate stability calculations. Assuming water temperature profiles remain unchanged, we predict the upper limit of pockmark occurrence to coincide with the top of CO2 gas hydrate stability during glacial-stage sealevel lowstands. CO2 hydrates may therefore have dissociated during sealevel lowering leading to gas escape and pockmark formation. In contrast to our previous model linking methane hydrate dissociation to pockmark formation, gas hydrates would dissociate beneath a shallow base of CO2 hydrate stability, rather than on the seafloor following upward "grazing" of the top of methane hydrate stability. Intriguingly, at the water depths of the larger seafloor depressions, the base of gas hydrate stability delineates the phase boundary between CO2 hydrates and super-saturated CO2. We caution that because of the high solubility of CO2, dissociation from hydrate to free gas or super-saturated CO2 would imply high concentrations of CO2 and speculate that pockmark formation may be linked to CO2 hydrate dissolution rather than dissociation

  15. Unimolecular reaction mechanism of an imidazolin-2-ylidene: an iPEPICO study on the complex dissociation of an Arduengo-type carbene.

    Science.gov (United States)

    Hemberger, Patrick; Bodi, Andras; Gerber, Thomas; Würtemberger, Max; Radius, Udo

    2013-05-27

    The photoionization and dissociative photoionization of Im(iPr)2, 1,3-diisopropylimidazolin-2-ylidene, was investigated by imaging photoelectron photoion coincidence (iPEPICO) with vacuum ultraviolet (VUV) synchrotron radiation. A lone-pair electron of the carbene carbon atom is removed upon ionization and the molecular geometry changes significantly. Only 0.5 eV above the adiabatic ionization energy, IEad =7.52±0.1 eV, the carbene cation fragments, yielding propene or a methyl radical in parallel dissociation reactions with appearance energies of 8.22 and 8.17 eV, respectively. Both reaction channels appear at almost the same photon energy, suggesting a shared transition state. This is confirmed by calculations, which reveal the rate-determining step as hydrogen-atom migration from the isopropyl group to the carbene carbon center forming a resonance-stabilized imidazolium ion. Above 10.5 eV, analogous sequential dissociation channels open up. The first propene-loss fragment ion dissociates further and another methyl or propene is abstracted. Again, a resonance-stabilized imidazolium ion acts as intermediate. The aromaticity of the system is enhanced even in vertical ionization. Indeed, the coincidence technique confirms that a real imidazolium ion is produced by hydrogen transfer over a small barrier. The simple analysis of the breakdown diagram yields all the clues to disentangle the complex dissociative photoionization mechanism of this intermediate-sized molecule. Photoelectron photoion coincidence is a promising tool to unveil the fragmentation mechanism of larger molecules in mass spectrometry.

  16. Effects of Salinity and Sea Level Change on Permafrost-Hosted Methane Hydrate Reservoirs

    Science.gov (United States)

    Elwood-Madden, M.

    2010-12-01

    Recent observations of methane release from sediments on the circum-arctic continental shelf indicate that arctic warming is likely leading to increased fluxes of methane . Thermodynamics predicts that 2-4 degree increases in global temperature will lead to massive marine hydrate decomposition; however, the rate of warming deep ocean waters and sediments is fairly slow, resulting in modest fluxes of methane over hundreds to thousands of years. In contrast, increasing arctic temperatures and rising sea level may have immediate effects on permafrost-hosted hydrate deposits. Rising sea level affects both the geothermal gradient of the region and the salinity of pore waters, leading to hydrate destabilization (Figure 1). Seawater infiltration of permafrost may be currently dissociating permafrost-hosted methane hydrate through a combination of mechanisms: shifting geothermal gradients to higher temperatures, addition of salts due to seawater encroachment, and the transition from solid state diffusion of methane through overlying ice cemented permafrost to mass transfer through seawater-saturated sediments via aqueous diffusion, advection, or ebullition. Effects of seawater erosion of permafrost have been observed in arctic coastal areas, and degradation of arctic permafrost is predicted to continue, especially in coastal areas. However, the rate at which these processes proceed and their effects on permafrost-hosted methane hydrates have been largely uninvestigated. Changes in geothermal gradient alone take hundreds to thousands of years to affect relatively deep hydrate reservoirs. However, warmer temperatures combined with freezing point depression effects of seawater may lead to rapid melting of permafrost ice, thus accelerating the transfer of heat to the hydrate reservoirs and changing the mass transfer mechanism of methane release from slow solid state diffusion through ice to more rapid aqueous diffusion, advection, or ebullition. Therefore, we hypothesize that

  17. HCl dissociating on a rigid Au(111) surface: A six-dimensional quantum mechanical study on a new potential energy surface based on the RPBE functional

    Science.gov (United States)

    Liu, Tianhui; Fu, Bina; Zhang, Dong H.

    2017-04-01

    The dissociative chemisorption of HCl on the Au(111) surface has recently been an interesting and important subject, regarding the discrepancy between the theoretical dissociation probabilities and the experimental sticking probabilities. We here constructed an accurate full-dimensional (six-dimensional (6D)) potential energy surface (PES) based on the density functional theory (DFT) with the revised Perdew-Burke-Ernzerhof (RPBE) functional, and performed 6D quantum mechanical (QM) calculations for HCl dissociating on a rigid Au(111) surface. The effects of vibrational excitations, rotational orientations, and site-averaging approximation on the present RPBE PES are investigated. Due to the much higher barrier height obtained on the RPBE PES than on the PW91 PES, the agreement between the present theoretical and experimental results is greatly improved. In particular, at the very low kinetic energy, the QM-RPBE dissociation probability agrees well with the experimental data. However, the computed QM-RPBE reaction probabilities are still markedly different from the experimental values at most of the energy regions. In addition, the QM-RPBE results achieve good agreement with the recent ab initio molecular dynamics calculations based on the RPBE functional at high kinetic energies.

  18. Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane

    Science.gov (United States)

    Lee, Ming-Tsung; Vishnyakov, Aleksey; Neimark, Alexander V.

    2016-01-01

    Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. The DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments.

  19. Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ming-Tsung; Vishnyakov, Aleksey; Neimark, Alexander V., E-mail: aneimark@rutgers.edu [Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854-8058 (United States)

    2016-01-07

    Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. The DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments.

  20. Transport Mechanisms for CO2-CH4 Exchange and Safe CO2 Storage in Hydrate-Bearing Sandstone

    Directory of Open Access Journals (Sweden)

    Knut Arne Birkedal

    2015-05-01

    Full Text Available CO2 injection in hydrate-bearing sediments induces methane (CH4 production while benefitting from CO2 storage, as demonstrated in both core and field scale studies. CH4 hydrates have been formed repeatedly in partially water saturated Bentheim sandstones. Magnetic Resonance Imaging (MRI and CH4 consumption from pump logs have been used to verify final CH4 hydrate saturation. Gas Chromatography (GC in combination with a Mass Flow Meter was used to quantify CH4 recovery during CO2 injection. The overall aim has been to study the impact of CO2 in fractured and non-fractured samples to determine the performance of CO2-induced CH4 hydrate production. Previous efforts focused on diffusion-driven exchange from a fracture volume. This approach was limited by gas dilution, where free and produced CH4 reduced the CO2 concentration and subsequent driving force for both diffusion and exchange. This limitation was targeted by performing experiments where CO2 was injected continuously into the spacer volume to maintain a high driving force. To evaluate the effect of diffusion length multi-fractured core samples were used, which demonstrated that length was not the dominating effect on core scale. An additional set of experiments is presented on non-fractured samples, where diffusion-limited transportation was assisted by continuous CO2 injection and CH4 displacement. Loss of permeability was addressed through binary gas (N2/CO2 injection, which regained injectivity and sustained CO2-CH4 exchange.

  1. Computational Material Modeling of Hydrated Cement Paste Calcium Silicate Hydrate (C-S-H) Chemistry Structure - Influence of Magnesium Exchange on Mechanical Stiffness: C-S-H Jennite

    Science.gov (United States)

    2015-04-27

    material chemistry structure are studied following a molecular dynamics (MD) computational modeling methodology. Calcium ions are replaced with... chemistry structure. Conference Name: 1st Pan-American Conference on Computational Mechanics Conference Date: April 27, 2015 1st Pan-American Congress on...MODELING OF C-S-H Material chemistry level modeling following the principles and techniques commonly grouped under Computational Material Science is

  2. Hyperglycemia associated dissociative fugue (organic dissociative disorder in an elderly

    Directory of Open Access Journals (Sweden)

    Dushad Ram

    2015-01-01

    Full Text Available Inadequate glycemic control in patients with diabetes is known to be associated with psychiatric disorders such as depression, anxiety disorder, and cognitive impairment. However, dissociative syndrome has not been reported so far. Here we are reporting a case of repeated dissociative fugue associated with hyperglycemia, in an elderly with type II diabetes. Possible neurobiological mechanism has been discussed.

  3. Hyperglycemia associated dissociative fugue (organic dissociative disorder) in an elderly

    OpenAIRE

    Dushad Ram; Ashoka, H.G.; Basavnna Gowdappa

    2015-01-01

    Inadequate glycemic control in patients with diabetes is known to be associated with psychiatric disorders such as depression, anxiety disorder, and cognitive impairment. However, dissociative syndrome has not been reported so far. Here we are reporting a case of repeated dissociative fugue associated with hyperglycemia, in an elderly with type II diabetes. Possible neurobiological mechanism has been discussed.

  4. A DFT study of temperature dependent dissociation mechanism of HF in HF(H2O)7 cluster

    Indian Academy of Sciences (India)

    Swatantra K Yadav; Hirdyesh Mishra; Ashwani K Tiwari

    2015-10-01

    We report a Density Functional Theoretical (DFT) study of dissociation of Hydrogen Fluoride (HF) in HF(H2O)7 cluster, using B3LYP functional and empirical exchange correlation functional M06-2X along with 6-31+G(d,p) basis set. Dissociation constant, KRP, of HF dissociation and pKa values of HF in cluster at various temperatures have been reported. It has been found that both KRP and pKa are highly dependent on temperature. The variation of pKa with temperature suggests that HF is strong acid at lower temperatures. Our study also reveals that HF is a stronger acid in water cluster than in bulk water. Further, the results obtained by DFT calculations have been compared with the earlier reported results obtained from Monte Carlo (MC) simulation. It is found that DFT results are qualitatively consistent with the results of MC simulation but quantitatively different.

  5. Ductile flow of methane hydrate

    Science.gov (United States)

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

    2003-01-01

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

  6. Quantum chemical study of mechanisms of dissociation and isomerization reactions in some molecules and radicals of astrophysical significance: Cyanides and related molecules

    Indian Academy of Sciences (India)

    V P Gupta; Archina Sharma

    2006-09-01

    A theoretical study of the mechanism of photodecomposition in carbonyl cyanide, diethynyl ketone, acetyl cyanide and formyl cyanide has been conducted using density functional and MP2 theories. A complete analysis of the electronic spectra of these molecules in terms of nature, energy and intensity of electronic transitions has been provided by time-dependent density functional theory. Mixing coefficients and main configurations of the electronic states have been used to identify the states leading to the photodecomposition process. While the Rydberg state 1(n,3s) is involved in the dissociation of formyl cyanide and acetyl cyanide, the $^{*}_{CC} / ^{*}_{CN}$ states are involved in the case of carbonyl cyanide and diethynyl ketone. In all cases, however, stepwise decomposition process is preferred over the concerted reaction process. Based on potential energy curves for bond dissociation and the transition state and IRC studies, it is found that besides the direct dissociation of carbonyl cyanide, a photoisomerization process through a non-planar transition state may also occur resulting in the formation of a stable and planar isomer CNC(O)CN. A complete vibrational analysis of the higher energy isomer has been conducted and several new fundamental bands are predicted. Some of the earlier experimental results on the photodecomposition mechanism and energies of photofragments in carbonyl cyanide and acetyl cyanide have also been rationalized.

  7. Naltrexone attenuates cue- but not drug-induced methamphetamine seeking: a possible mechanism for the dissociation of primary and secondary reward.

    Science.gov (United States)

    Anggadiredja, Kusnandar; Sakimura, Katsuya; Hiranita, Takato; Yamamoto, Tsuneyuki

    2004-09-24

    The present study was aimed to clarify the role of the opioid system in the reinstatement of methamphetamine (METH)-seeking behavior in METH self-administering rats. Following 12 days of self-administration of METH, the replacement of METH with saline resulted in a gradual decrease in lever press responses (extinction). Under extinction conditions, METH-priming or re-exposure to cues previously paired with METH infusion markedly increased the responses (reinstatement of drug-seeking). Naltrexone administered 30 min before re-exposure to METH-associated cues attenuated reinstatement of drug-seeking behavior. On the other hand, administration of this antagonist had no effect on the reinstatement induced by METH-priming. We discussed these findings in relation with the dissociation of primary and secondary reward, suggesting that an opioid mechanism is responsible for this dissociation. Further, these results indicate the possibility of using naltrexone as an anti-relapse agent.

  8. Gas hydrate inhibition of drilling fluid additives

    Energy Technology Data Exchange (ETDEWEB)

    Xiaolan, L.; Baojiang, S.; Shaoran, R. [China Univ. of Petroleum, Dongying (China). Inst. of Petroleum Engineering

    2008-07-01

    Gas hydrates that form during offshore well drilling can have adverse impacts on well operational safety. The hydrates typically form in the risers and the annulus between the casing and the drillstring, and can stop the circulation of drilling fluids. In this study, experiments were conducted to measure the effect of drilling fluid additives on hydrate inhibition. Polyalcohols, well-stability control agents, lubricating agents, and polymeric materials were investigated in a stirred tank reactor at temperatures ranging from -10 degree C to 60 degrees C. Pressure, temperature, and torque were used to detect onset points of hydrate formation and dissociation. The inhibitive effect of the additives on hydrate formation was quantified. Phase boundary shifts were measured in terms of temperature difference or sub-cooling gained when chemicals were added to pure water. Results showed that the multiple hydroxyl groups in polyalcohol chemicals significantly inhibited hydrate formation. Polymeric and polyacrylamide materials had only a small impact on hydrate formation, while sulfonated methyl tannins were found to increase hydrate formation. 6 refs., 1 tab., 4 figs.

  9. Gas-hydrate occurrence on the W-Svalbard margin at the gateway to the Arctic Ocean

    Science.gov (United States)

    Bünz, Stefan; Mienert, Jürgen

    2010-05-01

    Gas hydrates contain more carbon than does any other global reservoir and are abundant on continental margins worldwide. These two facts make gas hydrates important as a possible future energy resource, in submarine landsliding and in global climate change. With the ongoing global warming, there is a need for a better understanding of the distribution of gas hydrates and their sensitivity to environmental changes. Gas hydrate systems in polar latitudes may be of particular importance due to the fact that environmental changes will be felt here first and most likely are more extreme than elsewhere. The gas-hydrate systems offshore western Svalbard are far more extensive (~4000km^2) than previously assumed and include the whole Vestnesa Ridge, an elongated sediment drift north of the Molloy Transform and just east of the Molloy Ridge, one of the shortest segments of the slow spreading North-Atlantic Ridge system. However, in this peculiar setting gas hydrates also occur within few km of a mid-oceanic ridge and transform fault, which makes this gas hydrate system unique on Earth. The close proximity to the spreading centre and its hydrothermal circulation system affects the dynamics of the gas hydrate system. A strong cross-cutting BSR is visible, especially in areas of dipping seafloor. Other places show a weak almost subtle BSR. The base of gas-hydrate stability varies with distance from the ridge system, suggesting a strong temperature-controlled subsurface depth as the underlying young oceanic crust cools off eastward. High amplitude reflections over a depth range of up to 150m underneath the BSR indicate the presence of a considerable amount of free gas. The free gas is focused laterally upwards by the less-permeable hydrated sediments as the only fluid-escape features occur at the crest of the Vestnesa Ridge. The fluid migration system and its active plumbing system at the crest provide an efficient mechanism for gas escape from the base of the hydrate stability

  10. Water retention curve for hydrate-bearing sediments

    Science.gov (United States)

    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.

  11. Natural Gas Hydrate as a Storage Mechanism for Safe, Sustainable and Economical Production from Offshore Petroleum Reserves

    Directory of Open Access Journals (Sweden)

    Michael T. Kezirian

    2017-06-01

    Full Text Available Century Fathom presents an innovative process to utilize clathrate hydrates for the production, storage and transportation of natural gas from off-shore energy reserves in deep ocean environments. The production scheme was developed by considering the preferred state of natural gas in the deep ocean and addressing the hazards associated with conventional techniques to transport natural gas. It also is designed to mitigate the significant shipping cost inherent with all methods. The resulting proposed scheme restrains transport in the hydrate form to the ocean and does not attempt to supply energy to the residential consumer. Instead; the target recipients are industrial operations. The resulting operational concept is intrinsically safer by design; environmentally sustainable and significantly cost-effective compared with currently proposed schemes for the use of natural gas hydrates and has the potential to be the optimal solution for new production of reserves; depending on the distance to shore and capacity of the petroleum reserve. A potential additional benefit is the byproduct of desalinated water.

  12. The scientific objectives and program of the Japanese offshore methane hydrate production test

    Science.gov (United States)

    Yamamoto, K.; Fujii, T.; Noguchi, S.; Nagao, J.

    2012-12-01

    A gas production attempt from deepwater marine methane hydrate deposits is planned in early 2013 in the AT1 site in the north slope Daini-Atsumi Knoll in the Eastern Nankai Trough. The scientific goal of this production test is to understand the behavior of methane hydrate dissociation under an in-situ condition. The program includes one to several weeks of gas flow by applying depressurization technique. Drilling operations for the production test started in February 2012 at the test location, and two monitoring boreholes and part of production well have been drilled and completed. Reservoir characterization study is an essential part of the science program. For this purpose, intensive geophysical logging and coring programs are included in the drilling program. The logging data were mainly obtained from a hole named AT1-MC. The well was drilled with LWD tools, wireline logging suits were run subsequently. Also pressure-preserved cores were recovered from methane hydrate-concentrated and overburden sections in a dedicated borehole (AT1-C). To keep the pressure and temperature of cores under gas hydrate stability condition all the time, pressure core analysis and transfer system (PCATS) was used. Also the PCATS-triaxial device that can make mechanical and physical property measurements possible under tri-axial effective stress conditions was utilized. The physical, hydraulic and mechanical properties obtained from core and log data will be used for modeling works, and given to the numerical simulator MH21-HYDRES for methane hydrate production modeling as input parameters for forward analysis and inversion (history matching) to understand the in-situ processes. The monitoring of the methane hydrate dissociation processes is another important subject. The two monitoring holes have temperature sensors to detect temperature drop and recovery due to gas hydrate dissociation and heat transfer. Also, one of the monitoring holes is kept re-accessible to allow cased

  13. Textural and mechanical characterization of C-S-H gels from hydration of synthetic T1-C3S, β-C2S and their blends

    Directory of Open Access Journals (Sweden)

    Dolado, J. S.

    2011-06-01

    Full Text Available The textural and mechanical characterization of C-S-H gels formed from the hydration of pure T1-C3S, β-C2S and their blends are studied by Nitrogen sorption and nanoindentation experiments. The surface area and nanoporosity of C-S-H gels formed from the hydration of β-C2S and the 30-70 (T1-C3S and β-C2S mixture are higher than those from hydration of T1-C3S, and 70-30, with the difference decreasing with hydration age. Such changes are well supported by findings of nanoindentation study, which shows the greater relative volume of C-S-H phases with lower densities in the β-C2S and the 30-70 pastes. With the increase in hydration age, the relative volume of C-S-H phases with higher densities increased at the expenses of those with lower density. Important quantitative correlations were found among these textural characteristics and the mean chain length, determined from 29Si magic-angle-spinning (MAS NMR, of the C-S-H gels.La caracterización textural y mecánica de geles C-S-H formados a partir de la hidratación de muestras puras de T1-C3S, ß-C2S y sus mezclas ha sido estudiada por medio de adsorción de nitrógeno y nanoindentación. El área superficial y la nano-porosidad de los geles formados durante la hidratación del ß-C2S y la mezcla 30-70 (T1-C3S- ß-C2S son mayores que los correspondientes a los geles del T1-C3S, y la mezcla 70-30; esta diferencia disminuye con el tiempo de hidratación. Estos cambios coinciden con los resultados de nanoindentación que indican un aumento de volumen relativo de las fases C-S-H con una densidad menor en el caso del ß-C2S y la mezcla 30-70. Al aumentar el tiempo de hidratación, el volumen relativo de fases C-S-H de mayor densidad aumenta a expensas de aquellas de menor densidad. Importantes correlaciones cuantitativas se establecen entre las características texturales y la longitud de cadena media del gel C-S-H, determinada mediante RMN-MAS de 29Si.

  14. Calorimetric Determination of Enthalpy of Formation of Natural Gas Hydrates

    Institute of Scientific and Technical Information of China (English)

    高军; KennethN.Marsh

    2003-01-01

    This paper reports the measurements of enthalpies of natural gas hydrates in typical natural gas mixture containing methane, ethane, propane and iso-butane at pressure in the vicinity of 2000 kPa (300 psi) and 6900 kPa(1000psi). The measurements were made in a multi-cell differential scanning calorimeter using modified high pressure cells. The enthalpy of water and the enthalpy of dissociation of the gas hydrate were determined from the calorimeter response during slow temperature scanning at constant pressure. The amount of gas released from the dissociation of hydrate was determined from the pumped volume of the high pressure pump. The occupation ratio (mole ratio) of the water to gas and the enthalpy of hydrate formation are subject to uncertainty of 1.5%.The results show that the enthalpy of hydrate formation and the occupation ratio are essentially independent of pressure.

  15. Fundamental challenges to methane recovery from gas hydrates

    Science.gov (United States)

    Servio, P.; Eaton, M.W.; Mahajan, D.; Winters, W.J.

    2005-01-01

    The fundamental challenges, the location, magnitude, and feasibility of recovery, which must be addressed to recover methane from dispersed hydrate sources, are presented. To induce dissociation of gas hydrate prior to methane recovery, two potential methods are typically considered. Because thermal stimulation requires a large energy input, it is less economically feasible than depressurization. The new data will allow the study of the effect of pressure, temperature, diffusion, porosity, tortuosity, composition of gas and water, and porous media on gas-hydrate production. These data also will allow one to improve existing models related to the stability and dissociation of sea floor hydrates. The reproducible kinetic data from the planned runs together with sediment properties will aid in developing a process to economically recover methane from a potential untapped hydrate source. The availability of plentiful methane will allow economical and large-scale production of methane-derived clean fuels to help avert future energy crises.

  16. Hydrate Equilibrium Data for CO2+N-2 System in the Presence of Tetra-n-butylammonium Fluoride (TBAF) and Mixture of TBAF and Cyclopentane (CP)

    DEFF Research Database (Denmark)

    Tzirakis, Fragkiskos; Stringari, Paolo; Coquelet, Christophe;

    2016-01-01

    Hydrates can be used for CO2 capture from flue gases (hydrate crystallization). In this work, hydrate equilibrium data were measured and compared with literature data. The isochoric method was used to determine the gas hydrate dissociation points. Different CO2+N2 gas mixtures were used in the pr...

  17. Hydrate Equilibrium Data for CO2+N-2 System in the Presence of Tetra-n-butylammonium Fluoride (TBAF) and Mixture of TBAF and Cyclopentane (CP)

    DEFF Research Database (Denmark)

    Tzirakis, Fragkiskos; Stringari, Paolo; Coquelet, Christophe

    2016-01-01

    Hydrates can be used for CO2 capture from flue gases (hydrate crystallization). In this work, hydrate equilibrium data were measured and compared with literature data. The isochoric method was used to determine the gas hydrate dissociation points. Different CO2+N2 gas mixtures were used...

  18. Methane Recovery from Hydrate-bearing Sediments

    Energy Technology Data Exchange (ETDEWEB)

    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, 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

  19. Quantifying hydrate formation and kinetic inhibition

    Energy Technology Data Exchange (ETDEWEB)

    Sloan, E.D.; Subramanian, S.; Matthews, P.N.; Lederhos, J.P.; Khokhar, A.A. [Colorado School of Mines, Golden, CO (United States). Center for Hydrate Research

    1998-08-01

    In the Prausnitz tradition, molecular and macroscopic evidence of hydrate formation and kinetic inhibition is presented. On the microscopic level, the first Raman spectra are presented for the formation of both uninhibited and inhibited methane hydrates with time. This method has the potential to provide a microscopic-based kinetics model. Three macroscopic aspects of natural gas hydrate kinetic inhibition are also reported: (1) The effect of hydrate dissociation residual structures was measured, which has application in decreasing the time required for subsequent formation. (2) The performance of a kinetic inhibitor (poly(N-vinylcaprolactam) or PVCap) was measured and correlated as a function of PVCap molecular weight and concentrations of PVCap, methanol, and salt in the aqueous phase. (3) Long-duration test results indicated that the use of PVCap can prevent pipeline blockage for a time exceeding the aqueous phase residence time in some gas pipelines.

  20. Mechanical dissociation of human embryonic stem cell colonies by manual scraping after collagenase treatment is much more detrimental to cellular viability than is trypsinization with gentle pipetting.

    Science.gov (United States)

    Heng, Boon Chin; Liu, Hua; Ge, Zigang; Cao, Tong

    2007-05-01

    Because hESC (human embryonic stem cells) are 'social cells' that require co-operative interactions and intimate physical contact with each other, it is absolutely essential to dissociate hESC colonies into cellular clumps rather than into a single-cell suspension during serial passage. The present study compared two commonly used protocols for dissociating hESC colonies. The first protocol involved mild enzymatic treatment with collagenase type IV (1 mg/ml) for approx. 5-10 min, prior to mechanical dissociation into cellular clumps through manual scraping with a plastic pipette tip. The second protocol involved a short duration of exposure (2-3 min) to low concentrations of trypsin (0.05%), followed by gentle pipetting. The MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide] assay was used to compare the recovery of viable cells after dissociating hESC colonies with these two protocols, before and after conventional freeze-thawing with 10% (v/v) DMSO. Besides undifferentiated hESC, the randomly differentiated fibroblastic progenies of hESC at various passages (P0-P4), together with an immortalized cell line (CRL-1486), were also utilized to compare the two protocols. The results demonstrated that the second protocol (trypsinization with gentle pipetting) is much less detrimental to cellular viability than is the first protocol (collagenase treatment with scratching). This in turn translated to higher freeze-thaw survival rates. It is hypothesized that scratching after collagenase treatment (first protocol) somehow induces physical damage to the cells, thereby leading to a lower recovery of viable cells, both before and after freeze-thawing.

  1. Mechanism studies on thermal dissociation of tri-n-octylamine hydrochloride with FTIR, TG, DSC and quantum chemical methods

    Indian Academy of Sciences (India)

    CHUNHUA DONG; XINGFU SONG; EVERT JAN MEIJER; GUILAN CHEN; YANXIA XU; JIANGUO YU

    2017-09-01

    The thermal dissociation of tri-n-octylamine hydrochloride (TOAHCl) was investigated using both the quantum chemical simulation and experimental methods. The pathway through which a mixture of trin-octylamine (TOA) and hydrogen chloride (HCl), rather than di-n-octylamine (DOA) and 1-chlorooctane,are produced has been determined through transition state (TS) search with Intrinsic Reaction Coordinate (IRC) calculations. Particularly, strong agreement between the experimental FTIR spectra and that of TOA demonstrates the same result for the first time. Moreover, the thermal dissociation of TOAHCl proceeds intwo continuous steps, which is different from the low molecular mass amine hydrochlorides. The experimental enthalpy of the dissociation was 70.793 kJ mol⁻¹ with DSC measurement which is very close to the density functional theory (DFT) calculation result 69.395 kJ mol⁻¹. Furthermore, with the aid of DFT calculations, some other important thermochemical characteristics such as crystal lattice energy with the value of 510.597 kJ mol⁻¹ were evaluated by means of Born–Fajans–Haber cycle.

  2. Laser-induced dissociation dynamics of triatomic molecule in electronic excited states: A full-dimensional quantum mechanics study.

    Science.gov (United States)

    Sun, Zhaopeng; Yang, Chuanlu; Zheng, Yujun

    2015-12-14

    We present a detailed theoretical approach to investigate the laser-induced dissociation dynamics of a triatomic molecule on its electronic excited state in full dimensional case. In this method, the time evolution of the time-dependent system is propagated via combined the split operator method and the expansion of Chebyshev polynomials (or short-time Chebyshev propagation) and the system wave functions are expanded in terms of molecular rotational bases. As an example of the application of this formalism, the dissociation dynamics of H3(+)→H2(+)+H induced by ultrashort UV laser pulses are investigated on new Born-Oppenheimer potential energy surfaces. Our numerical results show that the signals of dissociation products will be easier to observe as the increasing of field strength. Driving by a 266 nm laser beam, the calculated central value of kinetic-energy-release is 2.04 eV which shows excellent agreement with the experimental estimation of 2.1 eV. When the H3(+) ion is rotationally excited, the spatial distribution of product fragments will become well converged.

  3. Controls on evolution of gas-hydrate system in the Krishna-Godavari basin, offshore India

    Digital Repository Service at National Institute of Oceanography (India)

    Badesab, F.K.; Dewangan, P.; Usapkar, A.; Kocherla, M.; Peketi, A.; Mohite, K.; Sangode, S.J.; Deenadayalan, K.

    magnetic minerals in the studied samples. 5.5. Can magnetic record be used as a potential tracer to identify the fossil gas hydrate zone in the K-G basin? In marine settings, the dissociation of gas hydrates takes place whenever P-T condition changes..., whenever the suitable P-T conditions prevail, hydrate nucleation takes place leaving the former boundary of gas hydrate stability zone (GHSZ) as a fossil gas hydrate horizon. In K-G basin, the present base of GHSZ calculated using hydrate stability...

  4. Study on gas hydrate as a new energy resource in the twenty first century

    Energy Technology Data Exchange (ETDEWEB)

    Ryu, Byung Jae; Kim, Won Sik; Oh, Jae Ho [Korea Institute of Geology Mining and Materials, Taejon (Korea)] [and others

    1998-12-01

    Methane hydrate, a special type of clathrate hydrates, is a metastable solid compound mainly consisted of methane and water and generally called as gas hydrate. It is stable in the specific low- temperature/high-pressure conditions. Very large amount of methane that is the main component of natural gas, is accumulated in the form of methane hydrate subaquatic areas. Methane hydrate are the major reservoir of methane on the earth. On the other hand, the development and transmission through pipeline of oil and natural gas in the permafrost and deep subaquatic regions are significantly complicated by formation and dissociation of methane hydrate. The dissociation of natural methane hydrates caused by increasing temperature and decreasing pressure could cause the atmospheric pollution and geohazard. The formation, stable existence and dissociation of natural methane hydrates depend on the temperature, pressure, and composition of gas and characteristics of the interstitial waters. For the study on geophysical and geological conditions for the methane hydrate accumulation and to find BSR in the East Sea, Korea, the geophysical surveys using air-gun system, multibeam echo sounder, SBP were implemented in last September. The water temperature data vs. depth were obtained to determine the methane hydrate stability zone in the study area. The experimental equilibrium condition of methane hydrate was also measured in 3 wt.% sodium chloride solution. The relationship between Methane hydrate formation time and overpressure was analyzed through the laboratory work. (author). 49 refs., 6 tabs., 26 figs.

  5. Application of a Multi-Scale form of Terzaghi’s Effective Stress Principle for Unsaturated Expansive Clays to Simulate Hydro-Mechanical Behavior During Hydration

    Directory of Open Access Journals (Sweden)

    Mainka Julia

    2016-01-01

    Full Text Available Our recently developed multi-scale form of Terzaghi’s effective stress principle for unsaturated swelling clays that was rigorously derived by periodic homogenization starting from micro- and nano-mechanical analyses is applied to numerically simulate one-dimensional swelling pressure tests of compacted bentonites during hydration. The total macroscopic stress captures the coupling between disjoining forces at the nanoscopic scale of clay platelets and capillary effects at the microscopic scale of clay aggregates over the entire water content range. The numerical results allow to draw conclusions on the water transfer mechanism between inter- and intra-aggregate pores during hydration and consequently on the evolution of the external swelling pressure resulting from the competition between capillary and disjoining forces. In addition, such application highlights the abilities and the limits of the electrical double-layer theory to compute the disjoining pressure in the nano-pores. For large platelet distances, in the range of osmotic swelling, the nature of the disjoining pressure is electro-chemical and can be computed from Poisson-Boltzmann theory. Conversely, at small distances, in the crystalline swelling, a solvation component has to be added to account for the molecular nature of the solvent. As a first improvement of the nano-scale description the solvent is treated as a hard sphere fluid using Density Functional Theory.

  6. Seepage from an arctic shallow marine gas hydrate reservoir is insensitive to momentary ocean warming

    Science.gov (United States)

    Hong, Wei-Li; Torres, Marta E.; Carroll, Jolynn; Crémière, Antoine; Panieri, Giuliana; Yao, Haoyi; Serov, Pavel

    2017-06-01

    Arctic gas hydrate reservoirs located in shallow water and proximal to the sediment-water interface are thought to be sensitive to bottom water warming that may trigger gas hydrate dissociation and the release of methane. Here, we evaluate bottom water temperature as a potential driver for hydrate dissociation and methane release from a recently discovered, gas-hydrate-bearing system south of Spitsbergen (Storfjordrenna, ~380 m water depth). Modelling of the non-steady-state porewater profiles and observations of distinct layers of methane-derived authigenic carbonate nodules in the sediments indicate centurial to millennial methane emissions in the region. Results of temperature modelling suggest limited impact of short-term warming on gas hydrates deeper than a few metres in the sediments. We conclude that the ongoing and past methane emission episodes at the investigated sites are likely due to the episodic ventilation of deep reservoirs rather than warming-induced gas hydrate dissociation in this shallow water seep site.

  7. Latest progress in numerical simulations on multiphase flow and thermodynamics in production of natural gas from gas hydrate reservoir

    Institute of Scientific and Technical Information of China (English)

    Lin ZUO; Lixia SUN; Changfu YOU

    2009-01-01

    Natural gas hydrates are promising potential alternative energy resources. Some studies on the multiphase flow and thermodynamics have been conducted to investigate the feasibility of gas production from hydrate dissociation. The methods for natural gas production are analyzed and several models describing the dissociation process are listed and compared. Two prevailing models, one for depressurization and the other for thermal stimulation, are discussed in detail. A comprehensive numerical method considering the multiphase flow and thermodynamics of gas production from various hydrate-bearing reservoirs is required to better understand the dissociation process of natural gas hydrate, which would be of great benefit to its future exploration and exploitation.

  8. Why can water cages adsorb aqueous methane? A potential of mean force calculation on hydrate nucleation mechanisms.

    Science.gov (United States)

    Guo, Guang-Jun; Li, Meng; Zhang, Yi-Gang; Wu, Chang-Hua

    2009-11-28

    By performing constrained molecular dynamics simulations in the methane-water system, we successfully calculated the potential of mean force (PMF) between a dodecahedral water cage (DWC) and dissolved methane for the first time. As a function of the distance between DWC and methane, this is characterized by a deep well at approximately 6.2 A and a shallow well at approximately 10.2 A, separated by a potential barrier at approximately 8.8 A. We investigated how the guest molecule, cage rigidity and the cage orientation affected the PMF. The most important finding is that the DWC itself strongly adsorbs methane and the adsorption interaction is independent of the guests. Moreover, the activation energy of the DWC adsorbing methane is comparable to that of hydrogen bonds, despite differing by a factor of approximately 10% when considering different water-methane interaction potentials. We explain that the cage-methane adsorption interaction is a special case of the hydrophobic interaction between methane molecules. The strong net attraction in the DWC shell with radii between 6.2 and 8.8 A may act as the inherent driving force that controls hydrate formation. A cage adsorption hypothesis for hydrate nucleation is thus proposed and discussed.

  9. Gas Hydrates Research Programs: An International Review

    Energy Technology Data Exchange (ETDEWEB)

    Jorge Gabitto; Maria Barrufet

    2009-12-09

    Gas hydrates sediments have the potential of providing a huge amount of natural gas for human use. Hydrate sediments have been found in many different regions where the required temperature and pressure conditions have been satisfied. Resource exploitation is related to the safe dissociation of the gas hydrate sediments. Basic depressurization techniques and thermal stimulation processes have been tried in pilot efforts to exploit the resource. There is a growing interest in gas hydrates all over the world due to the inevitable decline of oil and gas reserves. Many different countries are interested in this valuable resource. Unsurprisingly, developed countries with limited energy resources have taken the lead in worldwide gas hydrates research and exploration. The goal of this research project is to collect information in order to record and evaluate the relative strengths and goals of the different gas hydrates programs throughout the world. A thorough literature search about gas hydrates research activities has been conducted. The main participants in the research effort have been identified and summaries of their past and present activities reported. An evaluation section discussing present and future research activities has also been included.

  10. PM6 study of free radical scavenging mechanisms of flavonoids: why does O-H bond dissociation enthalpy effectively represent free radical scavenging activity?

    Science.gov (United States)

    Amić, Dragan; Stepanić, Višnja; Lučić, Bono; Marković, Zoran; Dimitrić Marković, Jasmina M

    2013-06-01

    It is well known that the bond dissociation enthalpy (BDE) of the O-H group is related to the hydrogen atom transfer (HAT) mechanism of free radical scavenging that is preferred in gas-phase and non-polar solvents. The present work shows that the BDE may also be related to radical scavenging processes taking place in polar solvents, i.e., single electron transfer followed by proton transfer (SET-PT) and sequential proton loss electron transfer (SPLET). This is so because the total energy requirements related to the SET-PT [sum of the ionization potential (IP) and proton dissociation enthalpy (PDE)] and the SPLET [sum of the proton affinity (PA) and electron transfer enthalpy (ETE)] are perfectly correlated with the BDE. This could explain why the published data for polyphenolic antioxidant activity measured by various assays are better correlated with the BDE than with other reaction enthalpies involved in radical scavenging mechanisms, i.e., the IP, PDE, PA and ETE. The BDE is fairly well able to rank flavonoids as antioxidants in any medium, but to conclude which radical scavenging mechanism represents the most probable reaction pathway from the thermodynamic point of view, the IP and PA (ETE) should also be considered. This is exemplified in the case of the radical scavenging activity of 25 flavonoids.

  11. A Novel Robot System Integrating Biological and Mechanical Intelligence Based on Dissociated Neural Network-Controlled Closed-Loop Environment

    Science.gov (United States)

    Wang, Yuechao; Li, Hongyi; Zheng, Xiongfei

    2016-01-01

    We propose the architecture of a novel robot system merging biological and artificial intelligence based on a neural controller connected to an external agent. We initially built a framework that connected the dissociated neural network to a mobile robot system to implement a realistic vehicle. The mobile robot system characterized by a camera and two-wheeled robot was designed to execute the target-searching task. We modified a software architecture and developed a home-made stimulation generator to build a bi-directional connection between the biological and the artificial components via simple binomial coding/decoding schemes. In this paper, we utilized a specific hierarchical dissociated neural network for the first time as the neural controller. Based on our work, neural cultures were successfully employed to control an artificial agent resulting in high performance. Surprisingly, under the tetanus stimulus training, the robot performed better and better with the increasement of training cycle because of the short-term plasticity of neural network (a kind of reinforced learning). Comparing to the work previously reported, we adopted an effective experimental proposal (i.e. increasing the training cycle) to make sure of the occurrence of the short-term plasticity, and preliminarily demonstrated that the improvement of the robot’s performance could be caused independently by the plasticity development of dissociated neural network. This new framework may provide some possible solutions for the learning abilities of intelligent robots by the engineering application of the plasticity processing of neural networks, also for the development of theoretical inspiration for the next generation neuro-prostheses on the basis of the bi-directional exchange of information within the hierarchical neural networks. PMID:27806074

  12. Well log characterization of natural gas hydrates

    Science.gov (United States)

    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

  13. Thermal conductivity of hydrate-bearing sediments

    Science.gov (United States)

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

    2009-11-01

    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.

  14. Thermal conductivity of hydrate-bearing sediments

    Science.gov (United States)

    Cortes, D.D.; Martin, A.I.; Yun, T.S.; Francisca, F.M.; Santamarina, J.C.; Ruppel, C.

    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. Copyright 2009 by the American Geophysical Union.

  15. Production behaviour of gas hydrate under hot sea water injection : laboratory case study

    Energy Technology Data Exchange (ETDEWEB)

    Nengkoda, A. [Schlumberger, Calgary, AB (Canada); Budhijanto, B.; Supranto, S.; Prasetyo, I.; Purwono, S.; Sutijan, S. [Gadjah Mada Univ., Yogyakarta (Indonesia)

    2010-07-01

    The gas hydrate potential in Indonesia was discussed, with particular reference to offshore production of gas from deep-water gas-hydrates by injection of hot seawater. In 2004, the Indonesian National Agency for Assessment and Application Technology estimated the gas hydrate resource potential to be 850 trillion cubic feet (tcf). To date, the 3 most reliable scenarios for gas hydrate production are thermal stimulation which involves increasing the temperature until the hydrates break into water and gas; depressurization which involves lowering the pressure by pumping out gas at the base of the hydrate to cause dissociation of hydrates into gas; and injection of a chemical inhibitor such as methanol into the hydrated sediments to cause destabilization, thus releasing gas from hydrates. This study investigated the effect of hot seawater injection on the gas hydrate production under laboratory conditions. The temperature profile distribution was examined along with operational parameters and flow characteristics of the dissociated gas and water from hydrates in porous systems under a synthetic hydrate setup. The study showed that gas production increases with time until a maximum is reached, at which time it begins to decrease. The energy ratio of thermal stimulation production was found to be influenced by the injection water temperature and rate as well as the hydrate content in the synthetic sediment. Scale problems were found to be associated with high temperature seawater injection. 8 refs., 3 tabs., 7 figs.

  16. New Methods for Gas Hydrate Energy and Climate Studies

    Science.gov (United States)

    Ruppel, C. D.; Pohlman, J.; Waite, W. F.; Hunt, A. G.; Stern, L. A.; Casso, M.

    2015-12-01

    Over the past few years, the USGS Gas Hydrates Project has focused on advancements designed to enhance both energy resource and climate-hydrate interaction studies. On the energy side, the USGS now manages the Pressure Core Characterization Tools (PCCTs), which includes the Instrumented Pressure Testing Chamber (IPTC) that we have long maintained. These tools, originally built at Georgia Tech, are being used to analyze hydrate-bearing sediments recovered in pressure cores during gas hydrate drilling programs (e.g., Nankai 2012; India 2015). The USGS is now modifying the PCCTs for use on high-hydrate-saturation and sand-rich sediments and hopes to catalyze third-party tool development (e.g., visualization). The IPTC is also being used for experiments on sediments hosting synthetic methane hydrate, and our scanning electron microscope has recently been enhanced with a new cryo-stage for imaging hydrates. To support climate-hydrate interaction studies, the USGS has been re-assessing the amount of methane hydrate in permafrost-associated settings at high northern latitudes and examined the links between methane carbon emissions and gas hydrate dissociation. One approach relies on the noble gas signature of methane emissions. Hydrate dissociation uniquely releases noble gases partitioned by molecular weight, providing a potential fingerprint for hydrate-sourced methane emissions. In addition, we have linked a DOC analyzer with an IRMS at Woods Hole Oceanographic Institution, allowing rapid and precise measurement of DOC and DIC concentrations and carbon isotopic signatures. The USGS has also refined methods to measure real-time sea-air flux of methane and CO2 using cavity ring-down spectroscopy measurements coupled with other data. Acquiring ~8000 km of data on the Western Arctic, US Atlantic, and Svalbard margins, we have tested the Arctic methane catastrophe hypothesis and the link between seafloor methane emissions and sea-air methane flux.

  17. Experimental study of enhanced gas recovery from gas hydrate bearing sediments by inhibitor and steam injection methods

    Energy Technology Data Exchange (ETDEWEB)

    Kawamura, T.; Ohtake, M.; Sakamoto, Y.; Yamamoto, Y.; Haneda, H. [National Inst. of Advanced Industrial Science and Technology, Tsukuba (Japan). Methane Hydrate Research Laboratory; Komai, T. [National Inst. of Advanced Industrial Science and Technoloyg, Tsukuba (Japan). Inst. for Geo-Resource and Environment; Higuchi, S. [Nihon Axis Co. Ltd., Mito (Japan)

    2008-07-01

    Inhibitor and steam injection methods for recovering methane hydrate-bearing sediments were investigated. New apparatus designs were used to inject steam into artificial methane hydrate-bearing sediments. Aqueous methanol was injected into a silica-based hydrate-bearing sediment in order to examine the dissociation behaviour of the methane hydrates. Experiments were conducted to examine the effects of steam injection using pure water; an aqueous methyl alcohol (MeOh) solution at 10 wt per cent; and an aqueous sodium chloride (NaC1) solution at 3 wt per cent. Temperatures for the injected fluids were set at 40 degrees C. Total gas production behaviour was divided into 3 stages: (1) the replacement of the remaining gas with the injected solution in the pore space; (2) gas production by hydrate dissociation; and (3) steady state and gas release. Results showed that cumulative gas production using the inhibitor solutions of MeOH and NaC1 proceeded more rapidly than the pure water samples. Downstream temperatures were not maintained at initial temperatures but decreased following the initiation of hydrate dissociation. Temperature changes were attributed to the coupling effect of the dissociation temperature and changes in inhibitor concentrations at the methane hydrate's surface. The use of inhibitors resulted in higher levels of cumulative gas production and more rapid hydrate dissociation rates. It was concluded that depressurization and steam injection induced hydrate dissociation from both upstream and downstream to the center of the sediment sample. 18 refs., 9 figs.

  18. MOLECULAR DYNAMICS SIMULATIONS OF FILLED AND EMPTY CAGE-LIKE WATER CLUSTERS IN LIQUID WATER AND THEIR SIGNIFICANCE TO GAS HYDRATE FORMATION MECHANISMS

    Institute of Scientific and Technical Information of China (English)

    GUO Guangjun; ZHANG Yigang; ZHAO Yajuan

    2003-01-01

    Molecular dynamics simulations are performed to observe the evolutions of 512 and 51262 cage-like water clusters filled with or without a methane molecule immersed in bulk liquid water at 250 K and 230 K. The lifetimes of these clusters are calculated according to their Lindemann index δ (t) using the criteria of δ≥0.07. For both the filled and empty clusters, we find the dynamics of bulk water determines the lifetimes of cage-like water clusters, and that the lifetime of 512 62 cage-like cluster is the same as that of 512 cage-like cluster. Although the methane molecule indeed makes the filled cage-like cluster more stable than the empty one, the empty cage-like cluster still has chance to be long-lived compared with the filled clusters. These observations support the labile cluster hypothesis on the formation mechanisms of gas hydrates.

  19. Atrioventricular Dissociation after Electroconvulsive Therapy

    Directory of Open Access Journals (Sweden)

    Siegfried William Yu

    2011-01-01

    Full Text Available Electroconvulsive therapy (ECT is increasingly used as a treatment for psychiatric disorders. Cardiac effects are the principal cause of medical complications in these patients. We report a case of atrioventricular (AV dissociation that occurred after ECT that was treated with pacemaker implantation. The mechanisms contributing to the onset of AV dissociation in this patient, and the management and rationale for device therapy, in light of the most recent guidelines, are reviewed.

  20. Evaluation of Heat Induced Methane Release from Methane Hydrates

    Science.gov (United States)

    Leeman, J.; Elwood-Madden, M.; Phelps, T. J.; Rawn, C. J.

    2010-12-01

    Clathrates, or gas hydrates, structurally are guest gas molecules populating a cavity in a cage of water molecules. Gas hydrates naturally occur on Earth under low temperature and moderate pressure environments including continental shelf, deep ocean, and permafrost sediments. Large quantities of methane are trapped in hydrates, providing significant near-surface reserves of carbon and energy. Thermodynamics predicts that hydrate deposits may be destabilized by reducing the pressure in the system or raising the temperature. However, the rate of methane release due to varying environmental conditions remains relatively unconstrained and complicated by natural feedback effects of clathrate dissociation. In this study, hydrate dissociation in sediment due to localized increases in temperature was monitored and observed at the mesoscale (>20L) in a laboratory environment. Experiments were conducted in the Seafloor Process Simulator (SPS) at Oak Ridge National Laboratory (ORNL) to simulate heat induced dissociation. The SPS, containing a column of Ottawa sand saturated with water containing 25mg/L Sno-Max to aid nucleation, was pressurized and cooled well into the hydrate stability field. A fiber optic distributed sensing system (DSS) was embedded at four depths in the sediment column. This allowed the temperature strain value (a proxy for temperature) of the system to be measured with high spatial resolution to monitor the clathrate formation/dissociation processes. A heat exchanger embedded in the sediment was heated using hot recirculated ethylene glycol and the temperature drop across the exchanger was measured. These experiments indicate a significant and sustained amount of heat is required to release methane gas from hydrate-bearing sediments. Heat was consumed by hydrate dissociated in a growing sphere around the heat exchanger until steady state was reached. At steady state all heat energy entering the system was consumed in maintaining the temperature profile

  1. Hydration of highly charged ions.

    Science.gov (United States)

    Hofer, Thomas S; Weiss, Alexander K H; Randolf, Bernhard R; Rode, Bernd M

    2011-08-01

    Based on a series of ab initio quantum mechanical charge field molecular dynamics (QMCF MD) simulations, the broad spectrum of structural and dynamical properties of hydrates of trivalent and tetravalent ions is presented, ranging from extreme inertness to immediate hydrolysis. Main group and transition metal ions representative for different parts of the periodic system are treated, as are 2 threefold negatively charged anions. The results show that simple predictions of the properties of the hydrates appear impossible and that an accurate quantum mechanical simulation in cooperation with sophisticated experimental investigations seems the only way to obtain conclusive results.

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

    Science.gov (United States)

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

    2004-12-01

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

  3. Modeling the Injection of Carbon Dioxide and Nitrogen into a Methane Hydrate Reservoir and the Subsequent Production of Methane Gas on the North Slope of Alaska

    Science.gov (United States)

    Garapati, N.; McGuire, P. C.; Liu, Y.; Anderson, B. J.

    2012-12-01

    HydrateResSim (HRS) is an open-source finite-difference reservoir simulation code capable of simulating the behavior of gas hydrate in porous media. The original version of HRS was developed to simulate pure methane hydrates, and the relationship between equilibrium temperature and pressure is given by a simple, 1-D regression expression. In this work, we have modified HydrateResSim to allow for the formation and dissociation of gas hydrates made from gas mixtures. This modification allows one to model the ConocoPhillips Ignik Sikumi #1 field test performed in early 2012 on the Alaska North Slope. The Ignik Sikumi #1 test is the first field-based demonstration of gas production through the injection of a mixture of carbon dioxide and nitrogen gases into a methane hydrate reservoir and thereby sequestering the greenhouse gas CO2 into hydrate form. The primary change to the HRS software is the added capability of modeling a ternary mixture consisting of CH4 + CO2 + N2 instead of only one hydrate guest molecule (CH4), therefore the new software is called Mix3HydrateResSim. This Mix3HydrateResSim upgrade to the software was accomplished by adding primary variables (for the concentrations of CO2 and N2), governing equations (for the mass balances of CO2 and N2), and phase equilibrium data. The phase equilibrium data in Mix3HydrateResSim is given as an input table obtained using a statistical mechanical method developed in our research group called the cell potential method. An additional phase state describing a two-phase Gas-Hydrate (GsH) system was added to consider the possibility of converting all available free water to form hydrate with injected gas. Using Mix3HydrateResSim, a methane hydrate reservoir with coexisting pure-CH4-hydrate and aqueous phases at 7.0 MPa and 5.5°C was modeled after the conditions of the Ignik Sikumi #1 test: (i) 14-day injection of CO2 and N2 followed by (ii) 30-day production of CH4 (by depressurization of the well). During the

  4. Petrophysical Characterization and Reservoir Simulator for Methane Gas Production from Gulf of Mexico Hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Kishore Mohanty; Bill Cook; Mustafa Hakimuddin; Ramanan Pitchumani; Damiola Ogunlana; Jon Burger; John Shillinglaw

    2006-06-30

    Gas hydrates are crystalline, ice-like compounds of gas and water molecules that are formed under certain thermodynamic conditions. Hydrate deposits occur naturally within ocean sediments just below the sea floor at temperatures and pressures existing below about 500 meters water depth. Gas hydrate is also stable in conjunction with the permafrost in the Arctic. Most marine gas hydrate is formed of microbially generated gas. It binds huge amounts of methane into the sediments. Estimates of the amounts of methane sequestered in gas hydrates worldwide are speculative and range from about 100,000 to 270,000,000 trillion cubic feet (modified from Kvenvolden, 1993). Gas hydrate is one of the fossil fuel resources that is yet untapped, but may play a major role in meeting the energy challenge of this century. In this project novel techniques were developed to form and dissociate methane hydrates in porous media, to measure acoustic properties and CT properties during hydrate dissociation in the presence of a porous medium. Hydrate depressurization experiments in cores were simulated with the use of TOUGHFx/HYDRATE simulator. Input/output software was developed to simulate variable pressure boundary condition and improve the ease of use of the simulator. A series of simulations needed to be run to mimic the variable pressure condition at the production well. The experiments can be matched qualitatively by the hydrate simulator. The temperature of the core falls during hydrate dissociation; the temperature drop is higher if the fluid withdrawal rate is higher. The pressure and temperature gradients are small within the core. The sodium iodide concentration affects the dissociation pressure and rate. This procedure and data will be useful in designing future hydrate studies.

  5. Anomalous preservation of pure methane hydrate at 1 atm

    Science.gov (United States)

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

    2001-01-01

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

  6. Characterizing electrical properties and permeability changes of hydrate bearing sediments using ERT data

    Science.gov (United States)

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

    2015-09-01

    A LArge Reservoir Simulator (LARS) was equipped with an electrical resistivity tomography (ERT) array to monitor hydrate formation and dissociation experiments. During two hydrate formation experiments reaching 90 per cent bulk hydrate saturation, frequent measurements of the electrical properties within the sediment sample were performed. Subsequently, several common mixing rules, including two different interpretations of Archie's law, were tested to convert the obtained distribution of the electrical resistivity into the spatial distribution of local hydrate saturation. It turned out that the best results estimating values of local hydrate saturation were obtained using the Archievar-phi approach where the increasing hydrate phase is interpreted as part of the sediment grain framework reducing the sample's porosity. These values of local hydrate saturation were used to determine local permeabilities by applying the Carman-Kozeny relation. The formed hydrates were dissociated via depressurization. The decomposition onset as well as areas featuring hydrates and free gas were inferred from the ERT results. Supplemental consideration of temperature and pressure data granted information on discrete areas of hydrate dissociation.

  7. Apparatus investigates geological aspects of gas hydrates

    Science.gov (United States)

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

    1999-01-01

    The US Geological Survey has developed a laboratory research system which allows the study of the creation and dissociation of gas hydrates under deepwater conditions and with different sediment types and pore fluids. The system called GHASTLI (gas hydrate and sediment test laboratory instrument) comprises a pressure chamber which holds a sediment specimen, and which can simulate water depths to 2,500m and different sediment overburden. Seawater and gas flow through a sediment specimen can be precisely controlled and monitored. It can simulate a wide range of geology and processes and help to improve understanding of gas hydrate processes and aid prediction of geohazards, their control and potential use as an energy source. This article describes GHASTLI and how it is able to simulate natural conditions, focusing on fluid volume, acoustic velocity-compressional and shear wave, electric resistance, temperature, pore pressure, shear strength, and permeability.

  8. In silico approach to investigating the adsorption mechanisms of short chain perfluorinated sulfonic acids and perfluorooctane sulfonic acid on hydrated hematite surface.

    Science.gov (United States)

    Feng, Hongru; Lin, Yuan; Sun, Yuzhen; Cao, Huiming; Fu, Jianjie; Gao, Ke; Zhang, Aiqian

    2017-05-01

    Short chain perfluorinated sulfonic acids (PFSAs) that were introduced as alternatives for perfluorooctane sulfonic acid (PFOS) have been widely produced and used. However, few studies have investigated the environmental process of short chain PFSAs, and the related adsorption mechanisms still need to be uncovered. The water-oxide interface is one of the major environmental interfaces that plays an important role in affecting the adsorption behaviour and transport potential of the environmental pollutant. In this study, we performed molecular dynamics simulations and quantum chemistry calculations to investigate the adsorption mechanisms of five PFSAs and their adsorption on hydrated hematite surface as well. Different to the vertical configuration reported for PFOS on titanium oxide, all PFSAs share the same adsorption configuration as the long carbon chains parallel to the surface. The formation of hydrogen bonds between F and inter-surface H helps to stabilize the unique configuration. As a result, the sorption capacity increases with increasing C-F chain length. Moreover, both calculated adsorption energy and partial density of states (PDOS) analysis demonstrate a PFSAs adsorption mechanism in between physical and chemical adsorption because the hydrogen bonds formed by the overlap of F (p) orbital and H (s) orbital are weak intermolecular interactions while the physical adsorption are mainly ascribed to the electrostatic interactions. This massive calculation provides a new insight into the pollutant adsorption behaviour, and in particular, may help to evaluate the environmental influence of pollutants. Copyright © 2017. Published by Elsevier Ltd.

  9. Charmonium dissociation cross sections and charmonium dissociation rates in hadronic matter

    CERN Document Server

    Liu, Feng-Rong; Xu, Xiao-Ming

    2016-01-01

    K*-charmonium dissociation reactions in hadronic matter are studied in the Born approximation, in the quark-interchange mechanism, and with a temperature-dependent quark potential. We obtain the temperature dependence of unpolarized cross sections for K*-charmonium dissociation reactions which produce charmed mesons and charmed strange mesons. We use the cross sections for charmonium dissociation in collisions with pion, rho meson, kaon, vector kaon, and eta meson to calculate dissociation rates of charmonium with the five types of mesons. Because of the temperature dependence of the meson masses, dissociation cross sections, and meson distribution functions, the charmonium dissociation rates generally increase with the increase of temperature and decrease with the increase of charmonium momentum from 2.2 GeV/c. We find that the first derivative of the dissociation rate with respect to the charmonium momentum is zero when the charmonium is at rest. While the eta + psi' and eta + chi_c dissociation reactions c...

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

    Science.gov (United States)

    Winters, W.J.

    1999-01-01

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

  11. Dissociative recombination of HCl+

    Science.gov (United States)

    Larson, Åsa; Fonseca dos Santos, Samantha; E. Orel, Ann

    2017-08-01

    The dissociative recombination of HCl+, including both the direct and indirect mechanisms, is studied. For the direct process, the relevant electronic states are calculated ab initio by combining electron scattering calculations to obtain resonance positions and autoionization widths with multi-reference configuration interaction calculations of the ion and Rydberg states. The cross section for the direct dissociation along electronic resonant states is computed by solution of the time-dependent Schrödinger equation. For the indirect process, an upper bound value for the cross section is obtained using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Vibrational excitations of the ionic core from the ground vibrational state, v = 0 , to the first three excited vibrational states, v = 1 , v = 2 , and v = 3 , are considered. Autoionization is neglected and the effect of the spin-orbit splitting of the ionic potential energy upon the indirect dissociative recombination cross section is considered. The calculated cross sections are compared to measurements.

  12. P-T stability conditions of methane hydrate in sediment from South China Sea

    Institute of Scientific and Technical Information of China (English)

    Shicai Sun; Yuguang Ye; Changling Liu; Fengkui Xiang; Yah Ma

    2011-01-01

    For reasonable assessment and safe exploitation of marine gas hydrate resource,it is important to determine the stability conditions of gas hydrates in marine sediment.In this paper,the seafloor water sample and sediment sample (saturated with pore water) from Shenhu Area of South China Sea were used to synthesize methane hydrates,and the stability conditions of methane hydrates were investigated by multi-step heating dissociation method.Preliminary experimental results show that the dissociation temperature of methane hydrate both in seafloor water and marine sediment,under any given pressure,is depressed by approximately -1.4 K relative to the pure water system.This phenomenon indicates that hydrate stability in marine sediment is mainly affected by pore water ions.

  13. Large-scale simulation of methane dissociation along the West Spitzbergen Margin

    Energy Technology Data Exchange (ETDEWEB)

    Reagan, M.T.; Moridis, G.J.

    2009-07-15

    Vast quantities of methane are trapped in oceanic hydrate deposits, and there is concern that a rise in the ocean temperature will induce dissociation of these hydrate accumulations, potentially releasing large amounts of methane into the atmosphere. The recent discovery of active methane gas venting along the landward limit of the gas hydrate stability zone (GHSZ) on the shallow continental slope west of Spitsbergen could be an indication of this process, if the source of the methane can be confidently attributed to dissociating hydrates. In the first large-scale simulation study of its kind, we simulate shallow hydrate dissociation in conditions representative of the West Spitsbergen margin to test the hypothesis that the observed gas release originated from hydrates. The simulation results are consistent with this hypothesis, and are in remarkable agreement with the recently published observations. They show that shallow, low-saturation hydrate deposits, when subjected to temperature increases at the seafloor, can release significant quantities of methane, and that the releases will be localized near the landward limit of the top of the GHSZ. These results indicate the possibility that hydrate dissociation and methane release may be both a consequence and a cause of climate change.

  14. Physical, mechanical and hydration kinetics of particleboards manufactured with woody biomass (Cupressus lusitanica, Gmelina arborea, Tectona grandis), agricultural resources, and Tetra Pak packages.

    Science.gov (United States)

    Moya, Róger; Camacho, Diego; Oporto, Gloria S; Soto, Roy F; Mata, Julio S

    2014-02-01

    Lignocellulosic wastes resulting from agricultural activities as well as Tetra Pak residues from urban centres can cause significant levels of pollution. A possible action to minimize this problem is to use them in the production of particleboards. The purpose of this study was to evaluate the physical, mechanical, and hydration properties of particleboards manufactured with the mixture of woody biomass (Cupressus lusitanica, Gmelina arborea, and Tectona grandis) and either agricultural wastes [pineapple leaves (Ananas comosus) and palm residues (Elaeis guineensis)] or Tetra Pak residues (TP). The results show that the particleboards prepared with TP and woody biomass can reduce the swelling and water absorption in up to 40% and 50% compared with particleboards without TP. Also, these particleboards had increased flexure resistance and shear stress (up to 100%) compared with those without TP. On the contrary, particleboards prepared with pineapple leaves in combination with woody biomass showed the lowest mechanical properties, particularly for tensile strength, hardness, glue-line shear, and nail and screw evaluation.

  15. First-principles investigation of methanethiol adsorption and dissociation mechanisms on the high-Miller-index vicinal surface Cu(4 1 0).

    Science.gov (United States)

    Raouafi, Faycal; Seydou, Mahamadou; Lassoued, Karima; Taleb, Abdelhafed; Diawara, Boubakar

    2016-05-05

    In this work, we present detailed investigations of methanethiol adsorption on a Cu(4 1 0) surface within the framework of the self-consistent first-principles calculations as implemented in the Vienna ab initio simulation package (VASP). In particular, the adsorption sites, the surface coverage rate and electronic properties have been determined and compared to experimental values. The results indicate that the favorable adsorption site in the case of low coverage rate is a bridge on the step followed by the hollow site on the terrace. The adsorption significantly affects the outermost layer of the surface mainly for a higher coverage rate in a (2 × 2) supercell. The nature of the chemisorption process on the surface is analyzed by means of the density of states which, combined with charge density difference and atomic charge calculations, confirms the ionic character of the S-Cu bond. The specific effect of the presence of steps is highlighted by comparing the adsorption on the (1 0 0) terrace to the adsorption on the extended Cu(1 0 0) surface. Compared to the flat Cu(1 0 0), it is found here that while the stability is almost the same at p(2 × 2) coverage, the CH3S/Cu(4 1 0) becomes more stable than CH3S/Cu(1 0 0) at c(2 × 2) coverage with 0.30 eV per molecule. The mechanism of methanethiol dissociation is explored by the nudged elastic band method and demonstrates that the most favorable path is dissociation followed by migration of hydrogen from the step to its most stable position (hollow on the terrace) with energy barriers less than 0.5 eV.

  16. Ab Initio QM/MM Study Shows a Highly Dissociated SN2 Hydrolysis Mechanism for the cGMP-Specific Phosphodiesterase-5.

    Science.gov (United States)

    Li, Zhe; Wu, Yinuo; Feng, Ling-Jun; Wu, Ruibo; Luo, Hai-Bin

    2014-12-09

    Phosphodiesterases (PDEs) are the sole enzymes hydrolyzing the important second messengers cGMP and cAMP and have been identified as therapeutic targets for several diseases. The most successful examples are PDE5 inhibitors (i.e., sildenafil and tadalafil), which have been approved for the treatment of male erectile dysfunction and pulmonary hypertension. However, the side effects mostly due to nonselective inhibition toward other PDE isoforms, set back the clinical usage of PDE5 inhibitors. Until now, the exact catalytic mechanism of the substrate cGMP by PDE5 is still unclear. Herein, the first computational study on the catalytic hydrolysis mechanism of cGMP for PDE5 (catalytic domain) is performed by employing the state-of-the-art ab initio quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations. Our simulations show a SN2 type reaction procedure via a highly dissociated transition state with a reaction barrier of 8.88 kcal/mol, which is quite different from the previously suggested hydrolysis mechanism of cAMP for PDE4. Furthermore, the subsequent ligand exchange and the release of the product GMP have also been investigated by binding energy analysis and MD simulations. It is deduced that ligand exchange would be the rate-determining step of the whole reaction, which is consistent with many previous experimental results. The obtained mechanistic insights should be valuable for not only the rational design of more specific inhibitors toward PDE5 but also understanding the general hydrolysis mechanism of cGMP-specific PDEs.

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

    Science.gov (United States)

    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.

  18. Studies of Reaction Kinetics of Methane Hydrate Dissocation in Porous Media

    Energy Technology Data Exchange (ETDEWEB)

    Moridis, George J.; Seol, Yongkoo; Kneafsey, Timothy J.

    2005-03-10

    The objective of this study is the description of the kinetic dissociation of CH4-hydrates in porous media, and the determination of the corresponding kinetic parameters. Knowledge of the kinetic dissociation behavior of hydrates can play a critical role in the evaluation of gas production potential of gas hydrate accumulations in geologic media. We analyzed data from a sequence of tests of CH4-hydrate dissociation by means of thermal stimulation. These tests had been conducted on sand cores partially saturated with water, hydrate and CH4 gas, and contained in an x-ray-transparent aluminum pressure vessel. The pressure, volume of released gas, and temperature (at several locations within the cores) were measured. To avoid misinterpreting local changes as global processes, x-ray computed tomography scans provided accurate images of the location and movement of the reaction interface during the course of the experiments. Analysis of the data by means of inverse modeling (history matching ) provided estimates of the thermal properties and of the kinetic parameters of the hydration reaction in porous media. Comparison of the results from the hydrate-bearing porous media cores to those from pure CH4-hydrate samples provided a measure of the effect of the porous medium on the kinetic reaction. A tentative model of composite thermal conductivity of hydrate-bearing media was also developed.

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

    Science.gov (United States)

    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.

  20. Investigation of the Abstraction and Dissociation Mechanism in the Nitrogen Trifluoride Channels: Combined Post-Hartree-Fock and Transition State Theory Approaches.

    Science.gov (United States)

    Claudino, D; Gargano, R; Carvalho-Silva, Valter H; E Silva, Geraldo M; da Cunha, W F

    2016-07-21

    The present paper concludes our series of kinetics studies on the reactions involved in the complex mechanism of nitrogen trifluoride decomposition. Two other related reactions that, along with this mechanism, take part in an efficient boron nitride growth process are also investigated. We report results concerning two abstraction reactions, namely NF2 + N ⇄ 2NF and NF3 + NF ⇄ 2NF2, and two dissociations, N2F4 ⇄ 2NF2 and N2F3 ⇄ NF2 + NF. State-of-the-art electronic structure calculations at the CCSD(T)/cc-pVTZ level of theory were considered to determine geometries and frequencies of reactants, products, and transition states. Extrapolation of the energies to the complete basis set limit was used to obtain energies of all the species. We applied transition state theory to compute thermal rate constants including Wigner, Eckart, Bell, and deformed theory corrections in order to take tunneling effects into account. The obtained results are in good agreement with the experimental data available in the literature and are expected to provide a better phenomenological understanding of the NF3 decomposition role in the boron nitride growth for a wide range of temperature values.

  1. Double-gating mechanism and diversity of an adenosine triphosphate (ATP)-sensitive K~+ channel in neurons acutely dissociated from rat neocortex

    Institute of Scientific and Technical Information of China (English)

    佟振清; 唐向东; 杨文俊

    1997-01-01

    Classically, ion channels are classified into 2 groups: chemical-sensitive (ligand-gated) and voltage-sensitive channels. Single ATP-sensitive K+ (K-ATP) channel currents were recorded in acutely dissociated rat neo-cortical neurons using patch clamp technique. A type of K-ATP channel has been found to be gated not only by intra-cellular ATP, but also by membrane potential ( Vm) , and proved to be a novel mechanism underlying the gating of ion channels, namely bi-gating mechanism. The results also show that the K-ATP channels possess heterogeneity and di-versity. These types of K-ATP channels have been identified in 40.12% of all patches, which are different in activa-tion-threshold and voltage-sensitivity. The present experiment studied the type-3 K-ATP channel with a unitary con-ductance of about 80 pS in detail ( n = 15). Taking account of all the available data, a variety of K-ATP channels are suggested to exist in body, and one type of them is bi-gated by both chemical substances and membrane poten

  2. Investigations into surfactant/gas hydrate relationship

    Energy Technology Data Exchange (ETDEWEB)

    Rogers, Rudy; Zhang, Guochang; Dearman, Jennifer; Woods, Charles [Swalm School of Chemical Engineering, Mississippi State University, Mississippi State, MS 39762 (United States)

    2007-03-15

    Gas hydrates have unique physical properties portending useful industrial applications of gas storage, gas separation, or water desalination. When gas hydrates were found in the early 1990s to occur naturally and abundantly in seafloors, three other primary interests and concerns emerged: potential new energy source, climate threat from their greenhouse gases, and seafloor instabilities. This paper presents research showing how anionic synthetic surfactants helped develop an industrial gas hydrate storage process for natural gas and how naturally-occurring in-situ anionic biosurfactants influence the formation and placement of gas hydrates in ocean sediments. The catalytic effects, mechanisms, and surface specificities imparted by synthetic surfactants in the gas storage process and imparted by biosurfactants in porous media are discussed. The Bacillus subtilis bacterium that is indigenous to gas hydrate mounds in the Gulf of Mexico was cultured in the laboratory. Its biosurfactant was separated and found to catalyze gas hydrates in porous media. The experiments indicate that seafloor-biosurfactants can be produced rapidly in-situ to achieve threshold concentrations whereby hydrates are promoted. The biosurfactants accumulate and promote hydrate formation on specific mineral surfaces such as sodium montmorillonite. (author)

  3. The Water Retention Curves in THF Hydrate-Bearing Sediments - Experimental Measurement and Pore Scale Simulation

    Science.gov (United States)

    Mahabadi, N.; Zheng, X.; Dai, S.; Seol, Y.; Zapata, C.; Yun, T.; Jang, J.

    2015-12-01

    The water retention curve (WRC) of hydrate-bearing sediments is critically important to understand the behaviour of hydrate dissociation for gas production. Most gas hydrates in marine environment have been formed from an aqueous phase (gas-dissolved water). However, the gas hydrate formation from an aqueous phase in a laboratory requires long period due to low gas solubility in water and is also associated with many experimental difficulties such as hydrate dissolution, difficult hydrate saturation control, and dynamic hydrate dissolution and formation. In this study, tetrahydrofuran (THF) is chosen to form THF hydrate because the formation process is faster than gas hydrate formation and hydrate saturation is easy to control. THF hydrate is formed at water-excess condition. Therefore, there is only water in the pore space after a target THF hydrate saturation is obtained. The pore habit of THF hydrate is investigated by visual observation in a transparent micromodel and X-ray computed tomography images; and the water retention curves are obtained under different THF hydrate saturation conditions. Targeted THF hydrate saturations are Sh=0, 0.2, 0.4, 0.6 and 0.8. Results shown that at a given water saturation the capillary pressure increases as THF hydrate saturation increases. And the gas entry pressure increases with increasing hydrate saturation. The WRC obtained by experiments is also compared with the results of a pore-network model simulation and Lattice Boltzmann Method. The fitting parameters of van Genuchten equation for different hydrate saturation conditions are suggested for the use as input parameters of reservoir simulators.

  4. Simulation of natural gas production from submarine gas hydrate deposits combined with carbon dioxide storage

    Science.gov (United States)

    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

  5. Study of the mechanism of a kinetic inhibitor on the crystallization of methane hydrate; Etude du mecanisme d'action d'un inhibiteur cinetique sur la cristallisation de l'hydrate de methane

    Energy Technology Data Exchange (ETDEWEB)

    Pic, J.St.

    2000-01-14

    In the offshore exploitation of liquid fuels, problems of line plugging often occur, especially due to gas hydrates crystallization. At the present time, operators resort to antifreeze additives, which efficiency is defeated either by harder operating conditions or by a more severe environmental legislation. So research recently shifted towards a new class of 'low dosage inhibitors'. In order to understand the influence of such additives, we designed a high pressure reactor, fitted with a liquid injection device and an in situ turbidimetric sensor. Access to both the particle size distribution of the suspension during the first stages of crystallization, and the total gas consumption, allows us to characterize the kinetics of methane hydration formation. First, we developed an original experimental procedure, which generates an initial 'breeding' of the solution, and thus improves the mastering of nucleation. The induction time then becomes one of the relevant parameters to investigate the performance of inhibitors. Afterwards, we performed a first series of experiments which allowed us to determine the influence of the operating conditions (pressure and stirring) on the evolution of the particle size distribution, in the absence of additives. Then, we pointed out the inhibiting effect of a model kinetic inhibitor, polyvinylpyrrolidone. When dissolved in the solution before crystallization occurs, it increases the induction delay, decreases the gas consumption rate and also slows down the birth of new particles for several hours. On the contrary, when injected in the medium during crystallization, this polymer no more affects the reaction kinetics. At last, we raise the bases for a modelling, taking into account the elementary crystallization processes of nucleation, growth and particles agglomeration. A parametric study has been confronted to the experimental data. It enables us to suggest hypotheses regarding the effect of gas hydrates kinetic

  6. Dissociation dynamics of methylal

    Energy Technology Data Exchange (ETDEWEB)

    Beaud, P.; Frey, H.-M.; Gerber, T.; Mischler, B.; Radi, P.P.; Tzannis, A.-P. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    The dissociation of methylal is investigated using mass spectrometry, combined with a pyrolytic radical source and femtosecond pump probe experiments. Based on preliminary results two reaction paths of methylal dissociation are proposed and discussed. (author) 4 fig., 3 refs.

  7. Dissociated Vertical Deviation

    Science.gov (United States)

    ... Frequently Asked Questions Español Condiciones Chinese Conditions Dissociated Vertical Deviation En Español Read in Chinese What is Dissociated Vertical Deviation (DVD)? DVD is a condition in which ...

  8. Spectroscopic determination of optimal hydration time of zircon surface

    Energy Technology Data Exchange (ETDEWEB)

    Ordonez R, E. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Garcia R, G. [Instituto Tecnologico de Toluca, Division de Estudios del Posgrado, Av. Tecnologico s/n, Ex-Rancho La Virgen, 52140 Metepec, Estado de Mexico (Mexico); Garcia G, N., E-mail: eduardo.ordonez@inin.gob.m [Universidad Autonoma del Estado de Mexico, Facultad de Quimica, Av. Colon y Av. Tollocan, 50180 Toluca, Estado de Mexico (Mexico)

    2010-07-01

    When a mineral surface is immersed in an aqueous solution, it develops and electric charge produced by the amphoteric dissociation of hydroxyl groups created by the hydration of the solid surface. This is one influential surface property. The complete hydration process takes a time which is specific for each mineral species. The knowledge of the aqueous solution contact time for complete surface hydration is mandatory for further surface phenomena studies. This study deals with the optimal hydration time of the raw zircon (ZrSiO{sub 4}) surface comparing the classical potentiometric titrations with a fluorescence spectroscopy technique. The latter is easy and rea liable as it demands only one sample batch to determine the optimal time to ensure a total hydration of the zircon surface. The analytical results of neutron activation analysis showed the presence of trace quantities of Dy{sup 3+}, Eu{sup 3+} and Er{sup 3} in the bulk of zircon. The Dy{sup 3+} is structured in the zircon crystalline lattice and undergoes the same chemical reactions as zircon. Furthermore, the Dy{sup 3+} has a good fluorescent response whose intensity is enhanced by hydration molecules. The results show that, according to the potentiometric analysis, the hydration process for each batch (at least 8 sample batches) takes around 2 h, while the spectrometric method indicates only 5 minutes from only one batch. Both methods showed that the zircon surface have a 16 h optimal hydration time. (Author)

  9. Postglacial response of Arctic Ocean gas hydrates to climatic amelioration

    Science.gov (United States)

    Serov, Pavel; Vadakkepuliyambatta, Sunil; Mienert, Jürgen; Patton, Henry; Portnov, Alexey; Silyakova, Anna; Panieri, Giuliana; Carroll, Michael L.; Carroll, JoLynn; Andreassen, Karin; Hubbard, Alun

    2017-06-01

    Seafloor methane release due to the thermal dissociation of gas hydrates is pervasive across the continental margins of the Arctic Ocean. Furthermore, there is increasing awareness that shallow hydrate-related methane seeps have appeared due to enhanced warming of Arctic Ocean bottom water during the last century. Although it has been argued that a gas hydrate gun could trigger abrupt climate change, the processes and rates of subsurface/atmospheric natural gas exchange remain uncertain. Here we investigate the dynamics between gas hydrate stability and environmental changes from the height of the last glaciation through to the present day. Using geophysical observations from offshore Svalbard to constrain a coupled ice sheet/gas hydrate model, we identify distinct phases of subglacial methane sequestration and subsequent release on ice sheet retreat that led to the formation of a suite of seafloor domes. Reconstructing the evolution of this dome field, we find that incursions of warm Atlantic bottom water forced rapid gas hydrate dissociation and enhanced methane emissions during the penultimate Heinrich event, the Bølling and Allerød interstadials, and the Holocene optimum. Our results highlight the complex interplay between the cryosphere, geosphere, and atmosphere over the last 30,000 y that led to extensive changes in subseafloor carbon storage that forced distinct episodes of methane release due to natural climate variability well before recent anthropogenic warming.

  10. Temperature dependence of the hydrated electron's excited-state relaxation. II. Elucidating the relaxation mechanism through ultrafast transient absorption and stimulated emission spectroscopy

    Science.gov (United States)

    Farr, Erik P.; Zho, Chen-Chen; Challa, Jagannadha R.; Schwartz, Benjamin J.

    2017-08-01

    The structure of the hydrated electron, particularly whether it exists primarily within a cavity or encompasses interior water molecules, has been the subject of much recent debate. In Paper I [C.-C. Zho et al., J. Chem. Phys. 147, 074503 (2017)], we found that mixed quantum/classical simulations with cavity and non-cavity pseudopotentials gave different predictions for the temperature dependence of the rate of the photoexcited hydrated electron's relaxation back to the ground state. In this paper, we measure the ultrafast transient absorption spectroscopy of the photoexcited hydrated electron as a function of temperature to confront the predictions of our simulations. The ultrafast spectroscopy clearly shows faster relaxation dynamics at higher temperatures. In particular, the transient absorption data show a clear excess bleach beyond that of the equilibrium hydrated electron's ground-state absorption that can only be explained by stimulated emission. This stimulated emission component, which is consistent with the experimentally known fluorescence spectrum of the hydrated electron, decreases in both amplitude and lifetime as the temperature is increased. We use a kinetic model to globally fit the temperature-dependent transient absorption data at multiple temperatures ranging from 0 to 45 °C. We find the room-temperature lifetime of the excited-state hydrated electron to be 137 ±40 fs, in close agreement with recent time-resolved photoelectron spectroscopy (TRPES) experiments and in strong support of the "non-adiabatic" picture of the hydrated electron's excited-state relaxation. Moreover, we find that the excited-state lifetime is strongly temperature dependent, changing by slightly more than a factor of two over the 45 °C temperature range explored. This temperature dependence of the lifetime, along with a faster rate of ground-state cooling with increasing bulk temperature, should be directly observable by future TRPES experiments. Our data also suggest

  11. Mechanisms of the reactions of 1,3-dicarbonyl compounds with nucleophilic reagents. IV. Kinetics of the hydration of 4-aroyl-5-methoxycarbonyl-1-phenyl-2,3-dihydropyrrole-2,3-diones in toluene

    Energy Technology Data Exchange (ETDEWEB)

    Kozlov, A.P.; Perevozchikov, L.A.; Maslivets, A.N.; Smirnova, L.I.; Andreichikov, Yu.S.

    1988-03-20

    The kinetics of the hydration of 4-aroyl-5-methoxycarbonyl-1-phenyl-2,3-dihydropyrrole-2,3-diones in toluene, uncatalyzed and catalyzed by carboxylic acids, was studied. With decrease in the pK/sub a/ values of the catalysts the mechanism of catalysis changes from bifunctional to general-acid, and this leads to reversal of the reactivity of the substrates.

  12. Mecanismos de hidratação do óxido de magnésio Mechanisms of magnesium oxide hydration

    Directory of Open Access Journals (Sweden)

    L. F. Amaral

    2007-12-01

    Full Text Available O óxido de magnésio, MgO, é uma importante matéria-prima para a indústria de refratários por ser um material de elevada refratariedade (ponto de fusão próximo a 2800 °C, resistente a escórias básicas, e de custo competitivo. No entanto, em presença de água, o MgO rapidamente se hidrata formando hidróxido de magnésio, Mg(OH2. Essa reação leva a uma expansão volumétrica de até três vezes, limitando sua aplicação em concretos refratários. Para desenvolver soluções que minimizem este problema, torna-se necessário um melhor entendimento do mecanismo pelo qual o MgO se hidrata e quais as principais variáveis envolvidas. Dois mecanismos distintos para esta reação foram propostos: a dissolução seguida de precipitação e b reação em uma única etapa ocorrendo diretamente na superfície das partículas. Este trabalho apresenta uma revisão crítica com relação aos mecanismos propostos e sua potencial aplicação em concretos refratários contendo MgO. Suspensões aquosas de MgO e diferentes técnicas de caracterização (ensaios reológicos oscilatórios, medidas de expansão volumétrica aparente e condutividade iônica permitiram correlacionar os mecanismos apresentados, principalmente com respeito à cinética da reação de hidratação.Magnesium oxide, MgO, is an important raw material for refractories industry due to its high refractoriness (melting point of approximately 2800 ºC, corrosion resistance in basic environment and competitive cost. Nevertheless, MgO presents a great tendency to react with water producing magnesium hydroxide, Mg(OH2. This reaction generates a threefold volumetric expansion and could lead to material breakdown inhibiting its application in refractory castables. In order to develop solutions to minimize this effect, a further understanding of the magnesia hydration mechanism and the main variables involved in this reaction is required. Two different mechanisms were proposed: a

  13. Investigation of the Mechanism of Electron Capture and Electron Transfer Dissociation of Peptides with a Covalently Attached Free Radical Hydrogen Atom Scavenger.

    Science.gov (United States)

    Sohn, Chang Ho; Yin, Sheng; Peng, Ivory; Loo, Joseph A; Beauchamp, J L

    2015-11-15

    The mechanisms of electron capture and electron transfer dissociation (ECD and ETD) are investigated by covalently attaching a free-radical hydrogen atom scavenger to a peptide. The 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) radical was chosen as the scavenger due to its high hydrogen atom affinity (ca. 280 kJ/mol) and low electron affinity (ca. 0.45 ev), and was derivatized to the model peptide, FQX(TEMPO)EEQQQTEDELQDK. The X(TEMPO) residue represents a cysteinyl residue derivatized with an acetamido-TEMPO group. The acetamide group without TEMPO was also examined as a control. The gas phase proton affinity (882 kJ/mol) of TEMPO is similar to backbone amide carbonyls (889 kJ/mol), minimizing perturbation to internal solvation and sites of protonation of the derivatized peptides. Collision induced dissociation (CID) of the TEMPO tagged peptide dication generated stable odd-electron b and y type ions without indication of any TEMPO radical induced fragmentation initiated by hydrogen abstraction. The type and abundance of fragment ions observed in the CID spectra of the TEMPO and acetamide tagged peptides are very similar. However, ECD of the TEMPO labeled peptide dication yielded no backbone cleavage. We propose that a labile hydrogen atom in the charge reduced radical ions is scavenged by the TEMPO radical moiety, resulting in inhibition of N-Cα backbone cleavage processes. Supplemental activation after electron attachment (ETcaD) and CID of the charge-reduced precursor ion generated by electron transfer of the TEMPO tagged peptide dication produced a series of b + H (b(H)) and y + H (y(H)) ions along with some c ions having suppressed intensities, consistent with stable O-H bond formation at the TEMPO group. In summary, the results indicate that ECD and ETD backbone cleavage processes are inhibited by scavenging of a labile hydrogen atom by the localized TEMPO radical moiety. This observation supports the conjecture that ECD and ETD processes involve long

  14. Improvement of Mechanical, Thermal and Optical Properties of Barium Mixed Cobalt Tartrate Hydrate Crystals Grown by Gel Method

    Directory of Open Access Journals (Sweden)

    S. Vanaja

    2015-10-01

    Full Text Available In this present work, CTH and BCTH crystals have been prepared by gel technique by using single diffusion method at room temperature. The as grown crystals were characterized by using XRD, FT-IR, UV, TG / DTA and Micro hardness studies. X-ray powder diffraction results analyzed by using suitable software suggest that a CTH and BCTH crystals belong to cubic crystal system. The unit cell volume is observed to increase with increase in the concentration of barium in cobalt tartrate due to the lattice distortion. The band gap and optical properties have analyzed by UV-Visible spectrum. The functional groups and compound formation of the crystals have been studied by FT-IR spectrum. The mechanical properties of the grown crystals were tested by using Vicker’s microhardness studies. The work hardening coefficient (n was determined to be 3.7 for CTH, 5.3 for BCTH (1 : 1 and 6.4 for BCTH (2 : 1 and the stiffness constants for different loads were calculated and reported. Thermal analysis suggests that pure cobalt tartrate starts decomposing at 73.2 °C whereas the barium mixed cobalt tartrate brings about better thermal stability which increases with an increase in barium concentration.

  15. Investigations on structural and photoluminescence mechanism of cerium doped L-Histidine hydrochloride mono hydrate single crystals for optical applications

    Science.gov (United States)

    Rajyalakshmi, S.; Ramachandra Rao, K.; Brahmaji, B.; Samatha, K.; Visweswara Rao, T. K.; Ramakrishna, Y.

    2017-02-01

    Semi organic nonlinear optical material of Ce3+ ion added L-Histidine hydrochloride monohydrate (LHHC) crystals have been grown successfully by the slow evaporation solution technique (SEST) as well as Sankaranarayanan-Ramasamy (SR) technique. Unit cell data have been measured from the single crystal X-ray diffraction analysis and High resolution X-ray diffraction analysis (HRXRD) study shows relatively a good crystalline perfection. Fourier transform infra-red spectroscopy (FTIR) spectra indicates that the Ce3+ ion is coordinated with carboxylate group of grown crystal. The lower UV-cutoff wavelength of the incorporation of Ce3+ ion in LHHC is 240 nm. The incorporation of Ce3+ ion in the crystal lattice was observed by energy dispersive X-ray analysis (EDAX). The nonlinear optical (NLO) efficiency of SR-grown crystal is 3.7 times greater with respect to potassium dihydrogen phosphate (KDP). We report first-time the photoluminescence (PL) mechanism of emission spectrum, which shows broad band located at 350 nm corresponding to 5d → 4f transition of Ce3+ ion and excited by 250 nm wavelength. The excitation spectrum shows a band at 258 nm due to the 4f → 5d transition of Ce3+ ion. The nature of decay curve of the grown crystal is bi-exponential with a long life time of τ2 is 8.8270 μs.

  16. Terahertz sensing of corneal hydration.

    Science.gov (United States)

    Singh, Rahul S; Tewari, Priyamvada; Bourges, Jean Louis; Hubschman, Jean Pierre; Bennett, David B; Taylor, Zachary D; Lee, H; Brown, Elliott R; Grundfest, Warren S; Culjat, Martin O

    2010-01-01

    An indicator of ocular health is the hydrodyanmics of the cornea. Many corneal disorders deteriorate sight as they upset the normal hydrodynamics of the cornea. The mechanisms include the loss of endothelial pump function of corneal dystophies, swelling and immune response of corneal graft rejection, and inflammation and edema, which accompany trauma, burn, and irritation events. Due to high sensitivity to changes of water content in materials, a reflective terahertz (300 GHz and 3 THz) imaging system could be an ideal tool to measure the hydration level of the cornea. This paper presents the application of THz technology to visualize the hydration content across ex vivo porcine corneas. The corneas, with a thickness variation from 470 - 940 µm, were successfully imaged using a reflective pulsed THz imaging system, with a maximum SNR of 50 dB. To our knowledge, no prior studies have reported on the use of THz in measuring hydration in corneal tissues or other ocular tissues. These preliminary findings indicate that THz can be used to accurately sense hydration levels in the cornea using a pulsed, reflective THz imaging system.

  17. Experimental study on steam and inhibitor injection into methane hydrate bearing sediments

    Science.gov (United States)

    Kawamura, T.; Sakamoto, Y.; Temma, N.; Yamamoto, Y.; Komai, T.

    2007-12-01

    Natural gas hydrate that exists in the ocean sediment is thought to constitute a large methane gas reservoir and is expected to be an energy resource in the future. In order to make recovery of natural gas from hydrates commercially viable, hydrates must be dissociated in-situ. Inhibitor injection method is thought to be one of the effective dissociation method as well as depressurization and thermal stimulation. Meanwhile, steam injection method is practically used for oil sand to recover heavy oil and recognized as a means that is commercially successful. In this study, the inhibitor injection method and the steam injection method for methane hydrate bearing sediments have been examined and discussed on an experimental basis. New experimental apparatuses have been designed and constructed. Using these apparatuses, inhibitor and steam were successfully injected into artificial methane hydrate bearing sediments that were simulated in laboratory scale. In the case of inhibitor injection, characteristic temperature drop during dissociation was observed. And decreases of permeability that is caused by the reformation of methane hydrate were prevented effectively. In the case of steam injection, the phase transition from vapor water to liquid water in methane hydrate bearing sediments was observed. It can be concluded that roughly 44 % of total hydrate origin gas was produced after steam injection. From these approaches, the applicability of these methods as enhanced gas recovery methods are discussed.

  18. Modelling of tetrahydrofuran promoted gas hydrate systems for carbon dioxide capture processes

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen; Thomsen, Kaj; Abildskov, Jens

    2014-01-01

    accurate descriptions of both fluid- and hydrate phase equilibria in the studied system and its subsystems. The developed model is applied to simulate two simplified, gas hydrate-based processes for post-combustion carbon dioxide capture from power station flue gases. The first process, an unpromoted...... hydrate process, operates isothermally at a temperature of 280. K. Applying three consecutive hydrate formation/dissociation stages (three-stage capture process), a carbon dioxide-rich product (97. mol%) is finally delivered at a temperature of 280. K and a pressure of 3.65. MPa. The minimum pressure...... requirement of the first stage is estimated to be 24.9. MPa, corresponding to the incipient hydrate dissociation pressure at 280. K for the considered flue gas. A second simulated carbon dioxide capture process uses tetrahydrofuran as a thermodynamic promoter to reduce the pressure requirements. By doing so...

  19. Numerical simulation on gas production from a hydrate reservoir underlain by a free gas zone

    Institute of Scientific and Technical Information of China (English)

    BAI YuHu; LI QingPing; LI XiangFang; DU Yan

    2009-01-01

    Physical and mathematical models of gas production by depressurization from a hydrate reservoir underlain by a free gas zone are established. The mathematical model can interpret the effects of the flow of multiphase fluids, the process of hydrate dissociation, ice-water phase transition, the variation of permeability, the convection and conduction on hydrate dissociation and gas and water production. The evolutions of temperature, pressure, and saturations in the hydrate and free gas zones are eluci-dated during gas production. The variation of some parameters, such as gas and water rates, with time is presented. The results show that the overlying hydrate zone can supply a certain amount of gas to improve the output of a production well and evidently prolong the lifespan of a gas reservoir.

  20. Origins of hydration lubrication.

    Science.gov (United States)

    Ma, Liran; Gaisinskaya-Kipnis, Anastasia; Kampf, Nir; Klein, Jacob

    2015-01-14

    Why is friction in healthy hips and knees so low? Hydration lubrication, according to which hydration shells surrounding charges act as lubricating elements in boundary layers (including those coating cartilage in joints), has been invoked to account for the extremely low sliding friction between surfaces in aqueous media, but not well understood. Here we report the direct determination of energy dissipation within such sheared hydration shells. By trapping hydrated ions in a 0.4-1 nm gap between atomically smooth charged surfaces as they slide past each other, we are able to separate the dissipation modes of the friction and, in particular, identify the viscous losses in the subnanometre hydration shells. Our results shed light on the origins of hydration lubrication, with potential implications both for aqueous boundary lubricants and for biolubrication.

  1. The influence of SO2 and NO2 impurities on CO2 gas hydrate formation and stability.

    Science.gov (United States)

    Beeskow-Strauch, Bettina; Schicks, Judith M; Spangenberg, Erik; Erzinger, Jörg

    2011-04-11

    The sequestration of industrially emitted CO(2) in gas hydrate reservoirs has been recently discussed as an option to reduce atmospheric greenhouse gas. This CO(2) contains, despite much effort to clean it, traces of impurities such as SO(2) and NO(2) . Here, we present results of a pilot study on CO(2) hydrates contaminated with 1% SO(2) or 1% NO(2) and show the impact on hydrate formation and stability. Microscopic observations show similar hydrate formation rates, but an increase in hydrate stability in the presence of SO(2). Laser Raman spectroscopy indicates a strong enrichment of SO(2) in the liquid and hydrate phase and its incorporation in both large and small cages of the hydrate lattice. NO(2) is not verifiable by laser Raman spectroscopy, only the presence of nitrate ions could be confirmed. Differential scanning calorimetry analyses show that hydrate stability and dissociation enthalpy of mixed CO(2)-SO(2) hydrates increase, but that only negligible changes arise in the presence of NO(2) impurities. X-ray diffraction data reveal the formation of sI hydrate in all experiments. The conversion rates of ice+gas to hydrate increase in the presence of SO(2), but decrease in the presence of NO(2). After hydrate dissociation, SO(2) and NO(2) dissolved in water and form strong acids.

  2. Thermodynamic promotion of carbon dioxide-clathrate hydrate formation by tetrahydrofuran, cyclopentane and their mixtures

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen; Thomsen, Kaj; Abildskov, Jens

    2013-01-01

    Gas clathrate hydrate dissociation pressures are reported for mixtures of carbon dioxide, water and thermodynamic promoters forming structure II hydrates.Hydrate (H)-aqueous liquid (Lw)-vapour (V) equilibrium pressures for the ternary system composed of water, tetrahydrofuran (THF), and carbon....... It is shown that upon adding THF to the pure aqueous phase to form a 4mass percent solution, the equilibrium pressure of the formed hydrates may be lowered compared to the ternary system of water, cyclopentane and carbon dioxide. © 2013 Elsevier Ltd....

  3. Measuring and modelling of the combined thermodynamic promoting effect of tetrahydrofuran and cyclopentane on carbon dioxide hydrates

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen; Daraboina, Nagu; Thomsen, Kaj

    2014-01-01

    promoters due to its significant pressure reducing effect in hydrate forming systems such as those related to carbon dioxide capture.The present work shows that hydrate dissociation pressures may be lowered by up to 22% compared to those of the cyclopentane promoted carbon dioxide hydrate system by addition......This work documents both experimental data, and by thermodynamic modelling, the synergistic effect occurring in promoted carbon dioxide hydrate systems at the simultaneous presence of tetrahydrofuran and cyclopentane.Cyclopentane has previously been considered a reference among gas hydrate...

  4. Preservation of methane hydrate at 1 atm

    Science.gov (United States)

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

    2001-01-01

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

  5. Infrared spectroscopy for monitoring gas hydrates in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Dobbs, G.T.; Luzinova, Y.; Mizaikoff, B. [Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemistry and Biochemistry; Raichlin, Y.; Katzir, A. [Tel-Aviv Univ., Tel-Aviv (Israel). Shool of Physics and Astronomy

    2008-07-01

    This paper introduced the first principles for monitoring gas hydrate formation and dissociation in aqueous solution by evaluating state-responsive infrared (IR) absorption features of water with fiberoptic evanescent field spectroscopy. A first order linear functional relationship was also derived according to Lambert Beer's law in order to quantify the percentage gas hydrate within the volume of water probed via the evanescent field. In addition, spectroscopic studies evaluating seafloor sediments collected from a gas hydrate site in the Gulf of Mexico revealed minimal spectral interferences from sediment matrix components. As such, evanescent field sensing strategies were established as a promising perspective for monitoring the dynamics of gas hydrates in oceanic environments. 21 refs., 5 figs.

  6. Thermodynamics of clathrate hydrate at low and high pressures with application to the outer solar system

    Science.gov (United States)

    Lunine, J. I.; Stevenson, D. J.

    1985-01-01

    The thermodynamic stability of clathrate hydrate is calculated to predict the formation conditions corresponding to a range of solar system parameters. The calculations were performed using the statistical mechanical theory developed by van der Waals and Platteeuw (1959) and existing experimental data concerning clathrate hydrate and its components. Dissociation pressures and partition functions (Langmuir constants) are predicted at low pressure for CO clathrate (hydrate) using the properties of chemicals similar to CO. It is argued that nonsolar but well constrained noble gas abundances may be measurable by the Galileo spacecraft in the Jovian atmosphere if the observed carbon enhancement is due to bombardment of the atmosphere by clathrate-bearing planetesimals sometime after planetary formation. The noble gas abundances of the Jovian satellite Titan are predicted, assuming that most of the methane in Titan is accreted as clathrate. It is suggested that under thermodynamically appropriate conditions, complete clathration of water ice could have occurred in high-pressure nebulas around giant planets, but probably not in the outer solar nebula. The stability of clathrate in other pressure ranges is also discussed.

  7. Methane hydrates and contemporary climate change

    Science.gov (United States)

    Ruppel, Carolyn D.

    2011-01-01

    As the evidence for warming climate became better established in the latter part of the 20th century (IPCC 2001), some scientists raised the alarm that large quantities of methane (CH4) might be liberated by widespread destabilization of climate-sensitive gas hydrate deposits trapped in marine and permafrost-associated sediments (Bohannon 2008, Krey et al. 2009, Mascarelli 2009). Even if only a fraction of the liberated CH4 were to reach the atmosphere, the potency of CH4 as a greenhouse gas (GHG) and the persistence of its oxidative product (CO2) heightened concerns that gas hydrate dissociation could represent a slow tipping point (Archer et al. 2009) for Earth's contemporary period of climate change.

  8. Hydro-bio-geomechanical properties of hydrate-bearing sediments from Nankai Trough

    Science.gov (United States)

    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

  9. X-ray computed-tomography observations of water flow through anisotropic methane hydrate-bearing sand

    Energy Technology Data Exchange (ETDEWEB)

    Seol, Yongkoo; Kneafsey, Timothy J.

    2009-06-01

    We used X-ray computed tomography (CT) to image and quantify the effect of a heterogeneous sand grain-size distribution on the formation and dissociation of methane hydrate, as well as the effect on water flow through the heterogeneous hydrate-bearing sand. A 28 cm long sand column was packed with several segments having vertical and horizontal layers with sands of different grain-size distributions. During the hydrate formation, water redistribution occurred. Observations of water flow through the hydrate-bearing sands showed that water was imbibed more readily into the fine sand, and that higher hydrate saturation increased water imbibition in the coarse sand due to increased capillary strength. Hydrate dissociation induced by depressurization resulted in different flow patterns with the different grain sizes and hydrate saturations, but the relationships between dissociation rates and the grain sizes could not be identified using the CT images. The formation, presence, and dissociation of hydrate in the pore space dramatically impact water saturation and flow in the system.

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

    Science.gov (United States)

    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.

  11. Mechanical property and hydration mechanism of slag blended magnesium phosphate cement%矿渣磷酸镁水泥的力学性能和水化机理

    Institute of Scientific and Technical Information of China (English)

    侯磊; 李金洪; 王浩林

    2011-01-01

    以高炉矿渣作为磷酸镁水泥(MPC)的活性混合材料,研究了MPC的凝固时间、力学性能、物相组成和显微结构,并探讨了矿渣MPC的作用机理.实验固定磷镁比为25%,硼镁比为7.5%,矿渣掺量分别为磷镁总质量的0%、10%、20%、30%和40%.结果表明,矿渣参与了水化反应并提高了MPC的胶凝性能,随着矿渣掺量增大,矿渣MPC的抗压强度提高,但矿渣水化产生的膨胀应力会破坏MPC的内部结构,因此其抗折强度随矿渣掺量增大而降低.矿渣MPC的主要水化产物为六水合磷酸镁铵(MgNH4PO4·6 H2O),矿渣的掺入使凝胶相增加,并有部分Ca2+进入MgNH4PO4·6 H2O品格,使水化产物的形貌、大小发生变化.样品中剩余较多死烧镁和矿渣颗粒,可起骨料作用.%Blast-furnace slag was used as an active addition of magnesium phosphate cement. The influence of blast-furnace slag on the setting time, mechanical property, mineral phase and microstucture of slag blended magnesium phosphate cement (MPC) was studied. The prescription was designed as follows: the ratio of monoammonium phosphate to magnesia was 25% in mass, the borax additive amount to magnesia was 7.5% , the additive amount of blast-furnace slag was 0% , 10%, 20%, 30% and 40% separately in the ratio of total amount of dead burned magnesia and monoammonium phosphate to MPC. The results show that slag might participate the hydration, which improves the bonding of MPC, and the compressive strength of slag-blended MPC is improved with the increasing additive amount of slag. However, slag might results in expansion stress during hydration process, which causes lattice disturbance in hardened MPC, so the flexual strength decreases with the increasing additive amount of slag at the same time. The main hydration product of slag blended MPC is struvite (MgNH4PO4·6 H2O), the content of amorphous phase might increase after being mixed with slag in MPC, and Ca2+ ions in slag can result

  12. Hydration Assessment of Athletes

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    @@ KEY POINTS · Although there is no scientific consensus for 1 ) howbest to assess the hydration status of athletes, 2)what criteria to use as acceptable outcome measurements, or 3) the best time to apply practical assessment methods, there are methods that can be used toprovide athletes with useful feedback about their hydration status

  13. Kinetic studies of gas hydrate formation with low-dosage hydrate inhibitors

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Pipeline blockage by gas hydrates is a serious problem in the petroleum industry.Low-dosage inhibitors have been developed for its cost-effective and environmentally acceptable characteristics.In a 1.072-L reactor with methane,ethane and propane gas mixture under the pressure of about 8.5 MPa at 4 °C,hydrate formation was investigated with low-dosage hydrate inhibitors PVP and GHI1,the change of the compressibility factor and gas composition in the gas phase was analyzed,the gas contents in hydrates were compared with PVP and GHI1 added,and the inhibition mechanism of GHI1 was discussed.The results show that PVP and GHI1 could effectively inhibit the growth of gas hydrates but not nucleation.Under the experimental condition with PVP added,methane and ethane occupied the small cavities of the hydrate crystal unit and the ability of ethane entering into hydrate cavities was weaker than that of methane.GHI1 could effectively inhibit molecules which could more readily form hydrates.The ether and hydroxy group of diethylene glycol monobutyl ether have the responsibility for stronger inhibition ability of GHI1 than PVP.

  14. 水泥基材料极早期水化机理及微观结构分析%Early Hydration Mechanism and Microstructural Analysis of Cement-based Materials

    Institute of Scientific and Technical Information of China (English)

    张文强; 李海玉; 陈帅

    2014-01-01

    The issue about the study of ion concentration of pore solution in hydration of cement will try to explain the very early hydration process and its mechanism of hydration.In addition,the issue uses the method of corrupting fly ash by alkaline solution to simulate the impact of pore solution alkalinity reacting hydration and hydration products. The results show that the basic trend of the ion concentration is consistent,which mixed 0,10%,20% of ash respec-tively.Its change is different to the ion concentration of pore solution,because in the beginning stages of hydration,it is mainly controlled by the alkaline soluble substances.Additionally to AFM observation,the change of microstructure of fly ash is closely related to the concentration of alkali ions.%测试了水泥浆体中孔溶液离子浓度在水化极早期的演变规律;运用原子力显微镜(AFM),采用碱性模拟溶液腐蚀粉煤灰的方法来研究了水化过程中孔溶液碱度对粉煤灰化学反应活性以及水化反应和水化产物生成的影响。研究结果表明:粉煤灰掺量分别为0、10%、20%的三种水泥水化孔溶液各离子浓度随水化时间的推移,其变化趋势基本是相同的。水化最开始的阶段孔溶液离子浓度主要是由碱性物溶解控制,其变化呈现差异性。AFM观察结果表明,碱性溶液可以侵蚀粉煤灰颗粒表面,改变其微观结构,改变的程度与侵蚀溶液碱离子浓度密切相关。经侵蚀的粉煤灰颗粒表面有纤维状水化产物形成。

  15. Hydrate Evolution in Response to Ongoing Environmental Shifts

    Energy Technology Data Exchange (ETDEWEB)

    Rempel, Alan [Univ. of Oregon, Eugene, OR (United States)

    2015-12-31

    Natural gas hydrates have the potential to become a vital domestic clean-burning energy source. However, past changes in environmental conditions have caused hydrates to become unstable and trigger both massive submarine landslides and the development of crater-like pockmarks, thereby releasing methane into the overlying seawater and atmosphere, where it acts as a powerful greenhouse gas. This project was designed to fill critical gaps in our understanding of domestic hydrate resources and improve forecasts for their response to environmental shifts. Project work can be separated into three interrelated components, each involving the development of predictive mathematical models. The first project component concerns the role of sediment properties on the development and dissociation of concentrated hydrate anomalies. To this end, we developed numerical models to predict equilibrium solubility of methane in twophase equilibrium with hydrate as a function of measureable porous medium characteristics. The second project component concerned the evolution of hydrate distribution in heterogeneous reservoirs. To this end, we developed numerical models to predict the growth and decay of anomalies in representative physical environments. The third project component concerned the stability of hydrate-bearing slopes under changing environmental conditions. To this end, we developed numerical treatments of pore pressure evolution and consolidation, then used "infinite-slope" analysis to approximate the landslide potential in representative physical environments, and developed a "rate-and-state" frictional formulation to assess the stability of finite slip patches that are hypothesized to develop in response to the dissociation of hydrate anomalies. The increased predictive capabilities that result from this work provide a framework for interpreting field observations of hydrate anomalies in terms of the history of environmental forcing that led to their development. Moreover

  16. Methane hydrate stability in the presence of water-soluble hydroxyalkyl cellulose

    Institute of Scientific and Technical Information of China (English)

    M. Mohammad-Taheri; A. Zarringhalam Moghaddam; K. Nazari; N. Gholipour Zanjani

    2012-01-01

    The effect of low-dosage water-soluble hydroxyethyl cellulose (approximate Mw~90,000 and 250,000) as a member ofhydroxyalkyl cellulosic polymer group on methane hydrate stability was investigated by monitoring hydrate dissociation at pressures greater than atmospheric pressure in a closed vessel.In particular,the influence of molecular weight and mass concentration of hydroxyethyl cellulose (HEC) was studied with respect to hydrate formation and dissociation.Methane hydrate formation was performed at 2 ℃ and at a pressure greater than 100 bar.Afterwards,hydrate dissociation was initiated by step heating from - 10 ℃ at a mild pressure of 13 bar to -3 ℃,0 ℃ and 2 ℃.With respect to the results obtained for methane hydrate formation/dissociation and the amount of gas uptake,we concluded that HEC 90,000 at 5000 ppm is suitable for long-term gas storage and transportation under a mild pressure of 13 bar and at temperatures below the freezing point.

  17. Energy from gas hydrates - assessing the opportunities and challenges for Canada: report of the expert panel on gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2008-09-15

    Gas hydrates form when water and natural gas combine at low temperatures and high pressures in regions of permafrost and in marine subseafloor sediments. Estimates suggest that the total amount of natural gas bound in hydrate form may exceed all conventional gas resources, or even the amount of all combined hydrocarbon energy. Gas from gas hydrate could provide a potentially vast new source of energy to offset declining supplies of conventional natural gas in North America and to provide greater energy security for countries such as Japan and India that have limited domestic sources. However, complex issues would need to be addressed if gas hydrate were to become a large part of the energy future of Canada. Natural Resources Canada asked the Council of Canadian Academies to assemble a panel of experts to examine the challenges for an acceptable operational extraction of gas hydrates in Canada. This report presented an overview of relevant contextual background, including some basic science; the medium-term outlook for supply and demand in markets for natural gas; broad environmental issues related to gas hydrate in its natural state and as a fuel; and an overview of Canada's contribution to knowledge about gas hydrate in the context of ongoing international research activity. The report also presented current information on the subject and what would be required to delineate and quantify the resource. Techniques for extracting gas from gas hydrate were also outlined. The report also addressed safety issues related to gas hydrate dissociation during drilling operations or release into the atmosphere; the environmental issues associated with potential leakage of methane into the atmosphere and with the large volumes of water produced during gas hydrate dissociation; and jurisdictional and local community issues that would need to be resolved in order to proceed with the commercial exploitation of gas hydrate. It was concluded that there does not appear to be

  18. Octa-coordination and the hydrated Ba2+(aq) ion

    CERN Document Server

    Chaudhari, Mangesh I; Rempe, Susan B

    2014-01-01

    The hydration structure of Ba^{2+} ion is important for understanding blocking mechanisms in potassium ion channels. Here, we combine statistical mechanical theory, ab initio molecular dynamics simulations, and electronic structure methods to calculate the hydration free energy and local hydration structure of Ba^{2+}(aq). The predicted hydration free energy (-302.9$\\pm$0.7 kcal/mol) matches the experimental value (-302.56 kcal/mol) when the fully occupied and exclusive inner solvation shell is treated. In the local environment defined by the inner and first shell of hydrating waters, Ba^{2+} is directly coordinated by eight (8) waters. Octa-coordination resembles the structure of Ba^{2+} and K^+ bound in potassium ion channels, but differs from the local hydration structure of K^+(aq) determined earlier.

  19. Hydrate equilibrium data for the CO2 + N2 system with the use of tetra-n-butylammonium bromide (TBAB), cyclopentane (CP) and their mixture

    DEFF Research Database (Denmark)

    Tzirakis, Fragkiskos; Stringari, Paolo; von Solms, Nicolas

    2016-01-01

    Carbon Dioxide capture and sequestration (CCS) is nowadays an important area of research for decreasing CO2 emissions worldwide. Hydrates can become of great importance in the future as they form the basis for a new technology that can be used for CO2 capture from flue gases (hydrate crystallizat......Carbon Dioxide capture and sequestration (CCS) is nowadays an important area of research for decreasing CO2 emissions worldwide. Hydrates can become of great importance in the future as they form the basis for a new technology that can be used for CO2 capture from flue gases (hydrate...... crystallization). In this work hydrate equilibrium data are measured and compared with literature data. In particular, experimental results for hydrate dissociation with several promoters are presented. The isochoric method is used to determine the gas hydrate dissociation points. Different CO2 + N2 gas mixtures...

  20. Hydration rate of obsidian.

    Science.gov (United States)

    Friedman, I; Long, W

    1976-01-30

    The hydration rates of 12 obsidian samples of different chemical compositions were measured at temperatures from 95 degrees to 245 degrees C. An expression relating hydration rate to temperature was derived for each sample. The SiO(2) content and refractive index are related to the hydration rate, as are the CaO, MgO, and original water contents. With this information it is possible to calculate the hydration rate of a sample from its silica content, refractive index, or chemical index and a knowledge of the effective temperature at which the hydration occurred. The effective hydration temperature can be either measured or approximated from weather records. Rates have been calculated by both methods, and the results show that weather records can give a good approximation to the true EHT, particularly in tropical and subtropical climates. If one determines the EHT by any of the methods suggested, and also measures or knows the rate of hydration of the particular obsidian used, it should be possible to carry out absolute dating to +/- 10 percent of the true age over periods as short as several years and as long as millions of years.

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

    Science.gov (United States)

    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

  2. Psychiatric symptoms and dissociation in conversion, somatization and dissociative disorders.

    Science.gov (United States)

    Espirito-Santo, Helena; Pio-Abreu, Jose Luis

    2009-03-01

    Conversion, dissociation and somatization are historically related in the long established concept of hysteria. Somewhere along the way they were separated due to the Cartesian dualistic view. The aim of the present study was to compare these pathologies and investigate whether symptoms of these pathologies overlap in their clinical appearance in a Portuguese sample. Twenty-six patients with conversion disorder, 38 with dissociative disorders, 40 with somatization disorder, and a comparison group of 46 patients having other psychiatric disorders answered questions about dissociation (Dissociative Experiences Scale), somatoform dissociation (Somatoform Dissociation Questionnaire), and psychopathological symptoms (Brief Symptom Inventory). Dissociative and somatoform symptoms were significantly more frequent in dissociative and conversion disorder than in somatization disorder and controls. There were no significant differences between dissociative and conversion patients. Conversion disorder is closely related to dissociative disorders. These results support the ICD-10 categorization of conversion disorder among dissociative disorders and the hypothesis of analogous psychopathological processes in conversion and dissociative disorders versus somatization disorder.

  3. Dissociation in mediation

    Directory of Open Access Journals (Sweden)

    Daniela Muraru

    2008-01-01

    Full Text Available This paper approaches several texts that are part of the so-called discourse of mediation, adopting a pragma-dialectical perspective of the theory of dissociation. It is an attempt to identify the uses of dissociative patterns, with special emphasis on the indicators of dissociation. The paper investigates the various uses of the concept of dissociation as a discursive technique in the argumentation on the different aspects that are involved in international conflict, such as the discussion of the notion of peace. The purpose is to identify the role of dissociation, as a device strategically used by the mediator to help the parties minimize the disagreement space, and come to a conflict resolution.

  4. Critical state soil constitutive model for methane hydrate soil

    National Research Council Canada - National Science Library

    S. Uchida; K. Soga; K. Yamamoto

    2012-01-01

      This paper presents a new constitutive model that simulates the mechanical behavior of methane hydrate-bearing soil based on the concept of critical state soil mechanics, referred to as the Methane...

  5. Effect of borax on the hydration process of FGD building gypsum and its mechanism analysis%硼砂对脱硫建筑石膏水化的影响及其机理分析

    Institute of Scientific and Technical Information of China (English)

    夏强; 蒋林华; 仲超; 圣兆兴; 李晓; 张飞军

    2011-01-01

    As FGD building gypsum has a character of fast solidity. The effect of borax on the hydration process and crystal morphology of dehydrate of FGD building gypsum and relationship between pH value and retarding effect were analyzed. Furthermore, by using the X-ray photoelectron spectroscopy technique, its retarding mechanism was also studied. The results indicate that the addition of borax retards the early hydration of FGD building gypsum, which leads to a delay in the hydration heat evolution. It can also prolong the setting time but has a little influence on strength development. Borax has a better retarding effect in alkaline hydration conditions and the setting time reaches the peak point when pH=10. The addition of borax will lead to the transformation of dihydrate crystal from needlelike to short prismatic. It could cause the large crystal sizes and few links between crystals, in that the strength will be lower. Borax interacts with the Ca element on the crystal nuclei surface of dehydrates and forms a chemical adsorption layer, inhibiting its growth, and consequently slowing down the hydration process.%针对脱硫建筑石膏凝结硬化快的特点,研究了硼砂对脱硫建筑石膏水化进程与二水石膏晶体形貌的影响,以及不同pH值时硼砂的缓凝效果,结合光电子能谱技术对其缓凝机理进行了分析.结果表明,硼砂可以抑制脱硫建筑石膏早期水化,使其水化放热减缓,凝结时间延长,但石膏硬化体强度有所降低;硼砂在碱性的水化条件下对脱硫石膏缓凝效果最佳,在pH值=10时凝结时间出现峰值;硼砂的掺入会改变二水石膏的晶体形貌,使二水石膏形貌由针状变成短柱状,晶体尺寸明显粗化,晶体之间搭接不良,引起强度损失;硼砂与脱硫石膏表面钙元素发生络合作用,在其表面形成化学吸附层,抑制晶核长大,延缓石膏水化进程.

  6. Hydrate morphology: Physical properties of sands with patchy hydrate saturation

    Science.gov (United States)

    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.

  7. Dissociation: Cognitive capacity or dysfunction?

    NARCIS (Netherlands)

    de Ruiter, M.B.; Bernet, M.; Phaf, R.H.

    2006-01-01

    Dissociative experiences are mostly studied as a risk factor for dissociative pathology. Nonpathological dissociation is quite common in the general population, however, and may reflect a constitutionally determined cognitive style rather than a pathological trait acquired through the experience of

  8. Wet hydrate dissolution plant

    OpenAIRE

    Stanković Mirjana S.; Kovačević Branimir T.; Pezo Lato L.

    2003-01-01

    The IGPC Engineering Department designed basic projects for a wet hydrate dissolution plant, using technology developed in the IGPC laboratories. Several projects were completed: technological, machine, electrical, automation. On the basis of these projects, a production plant with capacity of 50,000 t/y was manufactured, at "Zeolite Mira", Mira (VE), Italy, in 1997, for increasing detergent zeolite production from 50,000 to 100,000 t/y. Several goals were realized by designing a wet hydrate ...

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

    Science.gov (United States)

    Clennell, M.B.; Hovland, M.; Booth, J.S.; Henry, P.; Winters, W.J.

    1999-01-01

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

  10. Thermally induced evolution of phase transformations in gas hydrate sediment

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Thermally induced evolution of phase transformations is a basic physical-chemical process in the dissociation of gas hydrate in sediment (GHS). Heat transfer leads to the weakening of the bed soil and the simultaneous establishment of a time varying stress field accompanied by seepage of fluids and deformation of the soil. As a consequence, ground failure could occur causing engineering damage or/and environmental disaster. This paper presents a simplified analysis of the thermal process by assuming that thermal conduction can be decoupled from the flow and deformation process. It is further assumed that phase transformations take place instantaneously. Analytical and numerical results are given for several examples of simplified geometry. Experiments using Tetra-hydro-furan hydrate sediments were carried out in our laboratory to check the theory. By comparison, the theoretical, numerical and experimental results on the evolution of dissociation fronts and temperature in the sediment are found to be in good agreement.

  11. Gas hydrates: entrance to a methane age or climate threat?

    Energy Technology Data Exchange (ETDEWEB)

    Krey, Volker; Nakicenovic, Nebojsa; Grubler, Arnulf; O' Neill, Brian; Riahi, Keywan [International Institute for Applied Systems Analysis (IIASA), Schlossplatz 1, 2361 Laxenburg (Austria); Canadell, Josep G [Global Carbon Project, CSIRO Marine and Atmospheric Research, GPO Box 3023, Canberra, ACT 2601 (Australia); Abe, Yuichi [Social Science Consulting Unit, Japan Nus Co. Ltd, Loop-X Building 7F, 9-15 Kaigan 3-Chome, Minato-ku, Tokyo 108-0022 (Japan); Andruleit, Harald [Bundesanstalt fuer Geowissenschaften und Rohstoffe (BGR), Stilleweg 2, 30655 Hannover (Germany); Archer, David [Department of the Geophysical Sciences at the University of Chicago, 5734 South Ellis Avenue, Chicago, IL 60637 (United States); Hamilton, Neil T M [WWF International Arctic Programme, Kristian Augusts gate 7a, 0130 Oslo (Norway); Johnson, Arthur [Hydrate Energy International, 612 Petit Berdot Drive, Kenner, LA 70065 (United States); Kostov, Veselin [Department of Physics and Astronomy, Johns Hopkins University, 3400 N Charles Street Baltimore, MD 21218 (United States); Lamarque, Jean-Francois [Atmospheric Chemistry Division, National Center for Atmospheric Research (NCAR), PO Box 3000, Boulder, CO 80307 (United States); Langhorne, Nicholas [US Office of Naval Research Global, Edison House, 223 Old Marylebone Road, London (United Kingdom); Nisbet, Euan G [Department of Geology, Royal Holloway, University of London, Egham, Surrey TW20 0EX (United Kingdom); Riedel, Michael [Earth and Planetary Sciences, McGill University, 3450 University Street, Montreal, QC, H3A 2A7 (Canada); Wang Weihua [Computer Network Information Center, Chinese Academy of Sciences, No. 4, 4th South Street, ZhongGuanCun, PO Box 349, Haidian District, Beijing 100080 (China); Yakushev, Vladimir, E-mail: krey@iiasa.ac.a [Gazprom VNIIGAZ LLC, Razvilka, Leninsky District, Moscow Region, 142717 (Russian Federation)

    2009-09-15

    Methane hydrates, ice-like compounds in which methane is held in crystalline cages formed by water molecules, are widespread in areas of permafrost such as the Arctic and in sediments on the continental margins. They are a potentially vast fossil fuel energy source but, at the same time, could be destabilized by changing pressure-temperature conditions due to climate change, potentially leading to strong positive carbon-climate feedbacks. To enhance our understanding of both the vulnerability of and the opportunity provided by methane hydrates, it is necessary (i) to conduct basic research that improves the highly uncertain estimates of hydrate occurrences and their response to changing environmental conditions, and (ii) to integrate the agendas of energy security and climate change which can provide an opportunity for methane hydrates-in particular if combined with carbon capture and storage-to be used as a 'bridge fuel' between carbon-intensive fossil energies and zero-emission energies. Taken one step further, exploitation of dissociating methane hydrates could even mitigate against escape of methane to the atmosphere. Despite these opportunities, so far, methane hydrates have been largely absent from energy and climate discussions, including global hydrocarbon assessments and the Fourth Assessment Report of the Intergovernmental Panel on Climate Change.

  12. Three-phase flow of submarine gas hydrate pipe transport

    Institute of Scientific and Technical Information of China (English)

    李立; 徐海良; 杨放琼

    2015-01-01

    In the hydraulic transporting process of cutter-suction mining natural gas hydrate, when the temperature−pressure equilibrium of gas hydrate is broken, gas hydrates dissociate into gas. As a result, solid−liquid two-phase flow (hydrate and water) transforms into gas−solid−liquid three-phase flow (methane, hydrate and water) inside the pipeline. The Euler model and CFD-PBM model were used to simulate gas−solid−liquid three-phase flow. Numerical simulation results show that the gas and solid phase gradually accumulate to the center of the pipe. Flow velocity decreases from center to boundary of the pipe along the radial direction. Comparison of numerical simulation results of two models reveals that the flow state simulated by CFD-PBM model is more uniform than that simulated by Euler model, and the main behavior of the bubble is small bubbles coalescence to large one. Comparison of numerical simulation and experimental investigation shows that the values of flow velocity and gas fraction in CFD-PBM model agree with experimental data better than those in Euler model. The proposed PBM model provides a more accurate and effective way to estimate three-phase flow state of transporting gas hydrate within the submarine pipeline.

  13. Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition

    Science.gov (United States)

    Alavi, Saman; Ripmeester, J. A.

    2010-04-01

    Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

  14. Controls on gas hydrate stability in methane depleted sediments: Laboratory and field measurements

    Science.gov (United States)

    Lapham, L.; Chanton, J.; Martens, C. S.

    2009-12-01

    Gas hydrate deposits are the Earth’s largest reservoir of the powerful greenhouse gas methane and thus a key future energy resource. However, hydrate stability in sedimentary environments featuring highly variable methane concentrations needs to be understood to allow resource estimation and recovery. Hydrates are at chemical equilibrium and therefore stable where high pressures, low temperatures, and moderate salinities coexist with methane-saturated pore waters. When all of these conditions are not met, hydrates should dissociate or dissolve, releasing methane to the overlying water and possibly the atmosphere. In addition, other natural factors may control the kinetics of their degradation complicating models for hydrate stability and occurrence. Our measurements indicate that the pore-waters surrounding some shallow buried hydrates are not methane-saturated suggesting that dissolution should occur relatively rapidly. Yet, these hydrate deposits are known to persist relatively unchanged for years. We hypothesize that, once formed, hydrate deposits may be stabilized by natural factors inhibiting dissolution, including oil or microbial biofilm coatings. While most studies have focused on pressure and temperature changes where hydrates occur, relatively few have included measurements of in situ methane concentration gradients because of the difficulties inherent to making such measurements. Here we present recent measurements of methane concentration and stable carbon isotope gradients immediately adjacent to undisturbed hydrate surfaces obtained through deployments of novel seafloor instruments. Our results suggest that the hydrates studied are relatively stable when exposed to overlying and pore-waters that are undersaturated with methane. Concurrent laboratory measurements of methane concentration gradients next to artificial hydrate surfaces were utilized to test our protective coating hypothesis. After a stable dissolution rate for hydrate samples was

  15. The dissociative bond.

    Science.gov (United States)

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  16. Multiple-path dissociation mechanism for mono- and dinuclear tris(hydroxamato)iron(III) complexes with dihydroxamic acid ligands in aqueous solution.

    Science.gov (United States)

    Boukhalfa, H; Crumbliss, A L

    2000-09-18

    Linear synthetic dihydroxamic acids ([CH3N(OH)C=O)]2(CH2)n; H2Ln) with short (n = 2) and long (n = 8) hydrocarbon-connecting chains form mono- and dinuclear complexes with Fe(III) in aqueous solution. At conditions where the formation of Fe2(Ln)3 is favored, complexes with each of the two ligand systems undergo [H+]-induced ligand dissociation processes via multiple sequential and parallel paths, some of which are common and some of which are different for the two ligands. The pH jump induced ligand dissociation proceeds in two major stages (I and II) where each stage is shown to be comprised of multiple components (Ix, where x = 1-3 for L2 and L8, and IIy, where y = 1-3 for L2 and y = 1-4 for L8). A reaction scheme consistent with kinetic and independent ESI-MS data is proposed that includes the tris-chelated complexes (coordinated H2O omitted for clarity) (Fe2(Ln)3, Fe2(L2)2(L2H)2, Fe(LnH)3, Fe(L8)(L8H)), bis-chelated complexes (Fe2(Ln)2(2+), Fe(LnH)2+, Fe(L8)+), and monochelated complexes (Fe(LnH)2+). Analysis of kinetic data for ligand dissociation from Fe2(Ln)(LnH)3+ (n = 2, 4, 6, 8) allows us to estimate the dielectric constant at the reactive dinuclear Fe(III) site. The existence of multiple ligand dissociation paths for the dihydroxamic acid complexes of Fe(III) is a feature that distinguishes these systems from their bidentate monohydroxamic acid and hexadentate trihydroxamic acid counterparts and may be a reason for the biosynthesis of dihydroxamic acid siderophores, despite higher environmental molar concentrations necessary to completely chelate Fe(III).

  17. Kinetics and mechanisms for the adsorption, dissociation, and diffusion of hydrogen in Ni and Ni/YSZ slabs: a DFT study.

    Science.gov (United States)

    Weng, Meng Hsiung; Chen, Hsin-Tsung; Wang, Yao-Chun; Ju, Shin-Pon; Chang, Jee-Gong; Lin, M C

    2012-04-03

    The adsorption, dissociation, and diffusion of hydrogen in Ni(100) and Ni(100)/YSZ(100) slabs with two different interfaces (Ni/cation and Ni/O interface) have been studied by the density functional theory (DFT) with the Perdew-Wang functional. The H(2) molecule is found to preferentially absorb on a Top (T) site with side-on configuration on the Ni(100) surface, while the H-atom is strongly bound at a fcc Hollow (H) site. The barrier for the H(2) dissociation on both surfaces is calculated to be only ~0.1 eV. The potential energy pathways of H diffusion on pure Ni and Ni/YSZ with the two different interfaces are studied. Our calculated results show that the H-atom diffusion occurs via surface path rather than the bulk path. For the bulk path in Ni/YSZ, H-atom migration can occur more readily at the Ni/cation interface compared to the Ni/O interface. The existence of vacancy in the interface region is found to improve the mobility of H-atoms at the interface of Ni/YSZ slab. The rate constants for hydrogen dissociation and diffusion in pure Ni and Ni/YSZ are predicted.

  18. Dissociative recombination in aeronomy

    Science.gov (United States)

    Fox, J. L.

    1989-01-01

    The importance of dissociative recombination in planetary aeronomy is summarized, and two examples are discussed. The first is the role of dissociative recombination of N2(+) in the escape of nitrogen from Mars. A previous model is updated to reflect new experimental data on the electronic states of N produced in this process. Second, the intensity of the atomic oxygen green line on the nightside of Venus is modeled. Use is made of theoretical rate coefficients for production of O (1S) in dissociative recombination from different vibrational levels of O2(+).

  19. First-principles elasticity of monocarboaluminate hydrates

    KAUST Repository

    Moon, J.

    2014-07-01

    The elasticity of monocarboaluminate hydrates, 3CaO·Al2O3·CaCO3·xH2O (x = 11 or 8), has been investigated by first-principles calculations. Previous experimental study revealed that the fully hydrated monocarboaluminate (x = 11) exhibits exceptionally low compressibility compared to other reported calcium aluminate hydrates. This stiff hydration product can contribute to the strength of concrete made with Portland cements containing calcium carbonates. In this study, full elastic tensors and mechanical properties of the crystal structures with different water contents (x = 11 or 8) are computed by first-principles methods based on density functional theory. The results indicate that the compressibility of monocarboaluminate is highly dependent on the water content in the interlayer region. The structure also becomes more isotropic with the addition of water molecules in this region. Since the monocarboaluminate is a key hydration product of limestone added cement, elasticity of the crystal is important to understand its mechanical impact on concrete. Besides, it is put forth that this theoretical calculation will be useful in predicting the elastic properties of other complex cementitous materials and the influence of ion exchange on compressibility.

  20. Norwegian Research Strategies on gas Hydrates and Natural Seeps in the Nordic Seas Region (GANS)

    Science.gov (United States)

    Hjelstuen, B. O.; Sejrup, H. P.; Andreassen, K.; Boe, R.; Eldholm, O.; Hovland, M.; Knies, J.; Kvalstad, T.; Kvamme, B.; Mienert, J.; Pedersen, R. B.

    2004-12-01

    Continuous leakage of methane to the oceans from hydrate reservoirs that partially are exposed towards the seafloor is an increasing international concern, as the greenhouse gas methane is significantly more (c. 20 times) aggressive than CO2. In Norway we have research groups with interest and experience on natural seeps and gas hydrates. These features, and processes related to them, are challenging research targets which demands inputs from different fields if important research breakthroughs shall be made. In February 2004 deep sea researchers from the University of Tromso, Geological Survey of Norway, Norwegian Geotechnical Institute, Statoil and University of Bergen met to obtain an overview of the research effort in the fields of natural seeps and gas hydrates in Norway and to discuss national coordination, research strategies, research infrastructure and international co-operation. The following research strategies were agreed upon: i) Strengthen multidisciplinary research on deep sea systems, ii) develop a strategy for research on natural seeps and gas hydrates, iii) contribute in national coordination of research on natural seeps and gas hydrates, iv) Coordinate the use and development of research infrastructures important for research on natural seeps and gas hydrates, and v) contribute in the international evaluations of strategies for hydrate reservoir exploitation. Proposed research tasks for GANS include: i) Gas and gas hydrate formation processes and conditions for transport, accumulation, preservation and dissociation in sediments, ii) Effect of gas hydrate on physical properties of sediment, iii) Detection and quantification of in situ gas hydrate content and distribution pattern, iv) Effect of dissociation on soil properties, v) Gas hydrates as an energy resource, vi) Rapid methane release and climate change, and vii) Geohazard and environmental impact.

  1. Hydration of Portland cement with additions of calcium sulfoaluminates

    Energy Technology Data Exchange (ETDEWEB)

    Le Saout, Gwenn, E-mail: gwenn.le-saout@mines-ales.fr [Empa, Swiss Federal Laboratories for Materials Science and Technology, Concrete and Construction Chemistry Laboratory, Ueberlandstrasse 129, CH-8600 Duebendorf (Switzerland); Lothenbach, Barbara [Empa, Swiss Federal Laboratories for Materials Science and Technology, Concrete and Construction Chemistry Laboratory, Ueberlandstrasse 129, CH-8600 Duebendorf (Switzerland); Hori, Akihiro [DENKA Chemicals GmbH, Wehrhahn-Center, Cantadorstr. 3, D-40211 Duesseldorf (Germany); Higuchi, Takayuki [Denki Kagaku Kogyo Kabushiki Kaisha (DENKA), Omi, Itoigawa, Niigata, 949-0393 (Japan); Winnefeld, Frank [Empa, Swiss Federal Laboratories for Materials Science and Technology, Concrete and Construction Chemistry Laboratory, Ueberlandstrasse 129, CH-8600 Duebendorf (Switzerland)

    2013-01-15

    The effect of mineral additions based on calcium aluminates on the hydration mechanism of ordinary Portland cement (OPC) was investigated using isothermal calorimetry, thermal analysis, X-ray diffraction, scanning electron microscopy, solid state nuclear magnetic resonance and pore solution analysis. Results show that the addition of a calcium sulfoaluminate cement (CSA) to the OPC does not affect the hydration mechanism of alite but controls the aluminate dissolution. In the second blend investigated, a rapid setting cement, the amorphous calcium aluminate reacts very fast to ettringite. The release of aluminum ions strongly retards the hydration of alite but the C-S-H has a similar composition as in OPC with no additional Al to Si substitution. As in CSA-OPC, the aluminate hydration is controlled by the availability of sulfates. The coupling of thermodynamic modeling with the kinetic equations predicts the amount of hydrates and pore solution compositions as a function of time and validates the model in these systems.

  2. HFC-134a refrigerant gas hydrate formation process and RIN model

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In this paper, the macroscopic visualization experiments of HFC-134a refrigerant gas hydrate formation are investigated. According to the macroscopic photos and Mori's microscopic photos of HFC-134a hydrate formation process, the mechanism of gas hydrate formation is analyzed.A random inducement nucleation model is presented to describe the hydrate formation process. The factors affecting the fractal growth dimension in the model, such as step,branch increment and angle, are discussed.``

  3. PART II. HYDRATED CEMENTS

    Directory of Open Access Journals (Sweden)

    Milan Drabik

    2014-09-01

    Full Text Available Essential focus of the study has been to acquire thermoanalytical events, incl. enthalpies of decompositions - ΔH, of technological materials based on two types of Portland cements. The values of thermoanalytical events and also ΔH of probes of technological compositions, if related with the data of a choice of minerals of calcium-silicate-sulfate-aluminate hydrates, served as a valued input for the assessment of phases present and phase changes due to the topical hydraulic processes. The results indicate mainly the effects of "standard humidity" or "wet storage" of the entire hydration/hydraulic treatment, but also the presence of cement residues alongside calcium-silicate-sulfate-aluminate hydrates (during the tested period of treatment. "A diluting" effect of unhydrated cement residues upon the values of decomposition enthalpies in the studied multiphase system is postulated and discussed

  4. Dissociative disorders in medical settings.

    Science.gov (United States)

    MacPhee, Edward

    2013-10-01

    Despite the challenges of conducting research on dissociation and the dissociative disorders, our understanding has grown greatly over the past three decades, including our knowledge of the often overlooked sensorimotor manifestations of dissociation, more commonly referred to as somatoform dissociation. This article will first review the definitions and presentations of dissociation in general along with recent research on the concept of somatoform dissociation. Then, each of the dissociative disorders and conversion disorder will be discussed in further detail as well as how they might present in a medical setting. Current recommendations for diagnosis and treatment will also be provided.

  5. GLASS TRANSITION OF HYDRATED WHEAT GLIADIN POWDERS

    Institute of Scientific and Technical Information of China (English)

    Shao-min Sun; Li Zhao; Yi-hu Song; Qiang Zheng

    2011-01-01

    Modulated-temperature differential scanning calorimetric and dynamic mechanical analyses and dielectric spectroscopy were used to investigate the glass transition of hydrated wheat gliadin powders with moisture absorption ranged from 2.30 db% to 18.21 db%. Glass transition temperature (Tg) of dry wheat gliadin was estimated according to the GordonTaylor equation. Structural heterogeneity at high degrees of hydration was revealed in dielectric temperature and frequency spectra. The activation energies (Ea) of the two relaxations were calculated from Arrhenius equation.

  6. Quarkonium suppression: Gluonic dissociation vs. colour screening

    Indian Academy of Sciences (India)

    Binoy Krishna Patra; Dinesh Kumar Srivastava

    2003-05-01

    We evaluate the suppression of / production in an equilibrating quark gluon plasma for two competing mechanisms: Debye screening of colour interaction and dissociation due to energetic gluons. Results are obtained for S + S and Au + Au collisions at RHIC and LHC energies. At RHIC energies the gluonic dissociation of the charmonium is found to be equally important for both the systems while the screening of the interaction plays a significant role only for the larger systems. At LHC energies the Debye mechanism is found to dominate both the systems. While considering the suppression of directly produced $\\Upsilon$ at LHC energies, we find that only the gluonic dissociation mechanism comes into play for the initial conditions taken from the self screened parton cascade model in these studies.

  7. In-situ study of the thermal properties of hydrate slurry by high pressure DSC

    Energy Technology Data Exchange (ETDEWEB)

    Sari, O.; Hu, J.; Brun, F.; Erbeau, N. [Institute of Thermal Engineering, University of Applied Sciences of Western Switzerland, Yverdon-les-Bains (Switzerland); Homsy, P. [Nestec, Vevey (Switzerland); Logel, J.-C. [Axima Refrigeration, Bischheim (France)

    2008-07-01

    Knowing the enthalpy of hydrate slurry is very essential for energy balance and industrial applications. No direct measurement processes had been developed in this field in the past time. A new experimental method with special device has been developed to carry out on-line measurement of the thermal properties for hydrate slurry under dynamic conditions. With this special device, it is possible to deliver the hydrate slurry to the high pressure DSC (Differential Scanning Calorimetry) directly from the production tank or pipes. Thermal data acquisition will be performed afterwards by DSC. The investigated conditions were at pressure of 30 bar and temperature of {approx}+7 {sup o}C. The dissociation enthalpy of CO{sub 2} hydrate slurry was about 54 kJ/kg, corresponding 10.8% of solid fraction. The on-line measurement results for CO{sub 2} hydrate slurry give a good tendency to apply this phase change slurry to the industrial refrigeration process. (author)

  8. Modern faces of hysteria, or some of the dissociative disorders

    Directory of Open Access Journals (Sweden)

    Stefańska Alena

    2016-09-01

    Full Text Available The concept of “hysteria” comes from the Greek word “hystera” (uterus and dates back to the time of Hippocrates, at least. Modern classifications differ regarding the area encompassed by the concepts of dissociation and conversion differ. Mental health professionals in the United States (DSM-5 use a standard classification of mental disorders codifying dissociative disorders as a distinct class of disorders, but subsumes conversion disorders under “somatoform disorders”. The history of hysteria is as long as the history of mankind. Apparently, both the essence and mechanisms of dissociative disorders remain unchanged despite the fact that many years have passed. According to Owczarek et al., dissociative symptoms are caused by the malfunctioning of defence mechanisms and anxiety. This article provides an overview of the available literature on the etiology and pathogenesis of dissociative disorders as well as disorders such as amnesia, dissociative fugue, trance and possession.

  9. Implementation of subsea system to monitor in-situ temperature and formation pressure in methane hydrates sediments for the production test in 2017, offshore Japan

    Science.gov (United States)

    Nishimoto, K.

    2016-12-01

    The methane hydrates phase changes, from solid to fluid, is governed by pressure drop and heat transportation through a geological formation. For the world's first offshore production test of methane hydrates conducted in 2013, the MH21 research team installed distributed temperature sensing (DTS) cables and array type resistance temperature devices (RTD) behind the casings of the monitoring wells. The temperature monitoring was continued over the period of 18 months. As a result, the thermal response of the methane hydrate-bearing sediment during depressurization was observed, and the obtained data was used to evaluate the methane dissociation behavior and to estimate the dissociation front radius from a producer well. The second offshore production test is planned in the same area in 2017 with the extended period up to one month. Two sets of a pair of monitoring and producer well were drilled in 2016. A pair of monitoring and producer wells is only 20m apart. An improved monitoring system is prepared for the second test with additional pressure measurement capability with new features of subsea system. The planed formation pressure measurement is expected to contribute not only for the evaluation of methane hydrate phase changes and estimation of its areal distribution but also the analyzing the interference in the vicinity of the producer wells from the geo-mechanical point of view. The DTS resolution was improved with longer averaging time than the previously utilized system. To accomplish the continuous acquisition up running over longer than 18 months to cover pre-flow and post-flow periods, the subsea acquisition system was equipped with an exchangeable subsea batteries by ROV. As for the surface communication method, the acoustic transponder was added in the subsea system. In this technical presentation, the improvements on the monitoring system are discussed and the scientific objectives for new measurements such as formation pressure are presented.

  10. Interfacial phenomena in gas hydrate systems.

    Science.gov (United States)

    Aman, Zachary M; Koh, Carolyn A

    2016-03-21

    Gas hydrates are crystalline inclusion compounds, where molecular cages of water trap lighter species under specific thermodynamic conditions. Hydrates play an essential role in global energy systems, as both a hinderance when formed in traditional fuel production and a substantial resource when formed by nature. In both traditional and unconventional fuel production, hydrates share interfaces with a tremendous diversity of materials, including hydrocarbons, aqueous solutions, and inorganic solids. This article presents a state-of-the-art understanding of hydrate interfacial thermodynamics and growth kinetics, and the physiochemical controls that may be exerted on both. Specific attention is paid to the molecular structure and interactions of water, guest molecules, and hetero-molecules (e.g., surfactants) near the interface. Gas hydrate nucleation and growth mechanics are also presented, based on studies using a combination of molecular modeling, vibrational spectroscopy, and X-ray and neutron diffraction. The fundamental physical and chemical knowledge and methods presented in this review may be of value in probing parallel systems of crystal growth in solid inclusion compounds, crystal growth modifiers, emulsion stabilization, and reactive particle flow in solid slurries.

  11. Deep-ocean field test of methane hydrate formation from a remotely operated vehicle

    Science.gov (United States)

    Brewer, Peter G.; Orr, Franklin M., Jr.; Friederich, Gernot; Kvenvolden, Keith A.; Orange, Daniel L.; McFarlane, James; Kirkwood, William

    1997-05-01

    We have observed the process of formation of clathrate hydrates of methane in experiments conducted on the remotely operated vehicle (ROV) Ventana in the deep waters of Monterey Bay. A tank of methane gas, acrylic tubes containing seawater, and seawater plus various types of sediment were carried down on Ventana to a depth of 910 m where methane gas was injected at the base of the acrylic tubes by bubble stream. Prior calculations had shown that the local hydrographic conditions gave an upper limit of 525 m for the P-T boundary defining methane hydrate formation or dissociation at this site, and thus our experiment took place well within the stability range for this reaction to occur. Hydrate formation in free seawater occurred within minutes as a buoyant mass of translucent hydrate formed at the gas-water interface. In a coarse sand matrix the filling of the pore spaces with hydrate turned the sand column into a solidified block, which gas pressure soon lifted and ruptured. In a fine-grained black mud the gas flow carved out flow channels, the walls of which became coated and then filled with hydrate in larger discrete masses. Our experiment shows that hydrate formation is rapid in natural seawater, that sediment type strongly influences the patterns of hydrate formation, and that the use of ROV technologies permits the synthesis of large amounts of hydrate material in natural systems under a variety of conditions so that fundamental research on the stability and growth of these substances is possible.

  12. Formation process of structure 1 and 2 gas hydrates discovered in Kukuy, Lake Baikal

    Energy Technology Data Exchange (ETDEWEB)

    Hachikubo, A.; Sakagami, H.; Minami, H.; Nunokawa, Y.; Yamashita, S.; Takahashi, N.; Shoji, H. [Kitami Inst. of Technology, Kitami (Japan); Kida, M. [Advanced Industrial Science and Technology, Toyohira-ku, Sapporo, Hokkaido (Japan); Krylov, A. [All-Russia Research Inst. for Geology and Mineral Resources of the Ocean, St. Petersburg (Russian Federation); Khlystov, O.; Zemskaya, T. [Limnological Inst., Irkutsk (Russian Federation); Manakov, A. [Nikolaev Inst. of Inorganic Chemistry, Novosibirsk (Russian Federation); Kalmychkov, G. [Vinogradov Inst. of Geochemistry, Irkutsk (Russian Federation); Poort, J. [Ghent Univ., Krijgslaan (Belgium). Renard Centre of Marine Geology

    2008-07-01

    This study investigated the formation process of different crystal structures of gas hydrates found in Kukuy K-2, Lake Baikal, Russia. Gas compositions and isotopic ratios were taken from hydrate-bound gas and from dissolved gas in sediments by a headspace gas method. Structure 1 and 2 gas hydrates were observed in the same sediment cores of a mud volcano in the Kukuy Canyon, Lake Baikal. This paper discussed the results of the observations. The structure 2 gas hydrate contained about 13-15 per cent ethane, whereas the structure 1 gas hydrate contained about 1-5 per cent ethane and was placed beneath the structure 2 gas hydrate. The paper discussed the measurement of isotopic composition of dissociation gas from both type gas hydrates and dissolved gas in pore water. The paper also reported on these results. It was concluded that the current gas dissolved in pore water was not the source of these gas hydrates of both crystal structures in Kukuy K-2 mud volcano in Lake Baikal. In addition, isotopic data also provided useful information on how the double structure gas hydrates formed. 18 refs., 4 figs.

  13. Sponge Effect on Coal Mine Methane Separation Based on Clathrate Hydrate Method

    Institute of Scientific and Technical Information of China (English)

    ZHANG Baoyong; CHENG Yuanping; WU Qiang

    2011-01-01

    The findings were presented from laboratory investigations on the hydrate formation and dissociation processes employed to recover methane from coal mine gas.The separation process of coal mine methane(CMM) was carried out at 273.15K under 4.00 MPa.The key process variables of gas formation rate,gas volume stored in hydrate and separation concentration were closely investigated in twelve THF-SDS-sponge-gas systems to verify the sponge effect in these hydrate-based separation processes.The gas volume stored in hydrate is calculated based on the measured gas pressure.The CH4 mole fraction in hydrate phase is measured by gas chromatography to confirm the separation efficiency.Through close examination of the overall results,it was clearly verified that sponges with volumes of 40,60 and 80 cm 3 significantly increase gas hydrate formation rate and the gas volume stored in hydrate,and have little effect on the CH4 mole fraction in hydrate phase.The present study provides references for the application of the kinetic effect of porous sponge media in hydrate-based technology.This will contribute to CMM utilization and to benefit for local and global environment.

  14. Gas hydrates and magnetism : comparative geological settings for diagenetic analysis

    Energy Technology Data Exchange (ETDEWEB)

    Esteban, L.; Enkin, R.J. [Natural Resources Canada, Sidney, BC (Canada). Geological Survey of Canada; Hamilton, T. [Camosun College, Victoria, BC (Canada)

    2008-07-01

    Geophysical and geochemical methods assist in locating and quantifying natural gas hydrate deposits. They are also useful in understanding these resources, their climate impacts and their potential role in geohazards. In order to understand the mechanisms of gas hydrate formation and its natural distribution in sediments, magnetic studies were conducted on cores from three different geological settings. This paper presented the results of a detailed magnetic investigation, as well as petrological observations, that were conducted on cores from a permafrost setting in the Mackenzie Delta located in the Canadian Northwest Territories Mallik region, and two marine settings, from the Cascadia margin off Vancouver Island and the Indian National Gas Hydrate Program from the Bengal Fan. The paper provided background information on the permafrost setting in Mallik region of the Mackenzie Delta as well as the Cascadia margin. The magnetic properties of gas hydrate bearing sediments were found to be a combination of the original detrital content and the diagenetic transformations of iron minerals caused by the unique environment produced by gas hydrate formation. The availability of methane to provide food for bacteria coupled with the concentration of solutes outside gas hydrate accumulation zones led to the creation of iron sulphides. These new minerals were observable using magnetic techniques, which help in delineating the gas hydrate formation mechanism and may be developed into new geophysical methods of gas hydrate exploration. 7 refs., 7 figs.

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

    Science.gov (United States)

    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.

  16. Modeling DNA hydration: comparison of calculated and experimental hydration properties of nuclic acid bases.

    Science.gov (United States)

    Poltev, V I; Malenkov, G G; Gonzalez, E J; Teplukhin, A V; Rein, R; Shibata, M; Miller, J H

    1996-02-01

    Hydration properties of individual nucleic acid bases were calculated and compared with the available experimental data. Three sets of classical potential functions (PF) used in simulations of nucleic acid hydration were juxtaposed: (i) the PF developed by Poltev and Malenkov (PM), (ii) the PF of Weiner and Kollman (WK), which together with Jorgensen's TIP3P water model are widely used in the AMBER program, and (iii) OPLS (optimized potentials for liquid simulations) developed by Jorgensen (J). The global minima of interaction energy of single water molecules with all the natural nucleic acid bases correspond to the formation of two water-base hydrogen bonds (water bridging of two hydrophilic atoms of the base). The energy values of these minima calculated via PM potentials are in somewhat better conformity with mass-spectrometric data than the values calculated via WK PF. OPLS gave much weaker water-base interactions for all compounds considered, thus these PF were not used in further computations. Monte Carlo simulations of the hydration of 9-methyladenine, 1-methyluracil and 1-methylthymine were performed in systems with 400 water molecules and periodic boundary conditions. Results of simulations with PM potentials give better agreement with experimental data on hydration energies than WK PF. Computations with PM PF of the hydration energy of keto and enol tautomers of 9-methylguanine can account for the shift in the tautomeric equilibrium of guanine in aqueous media to a dominance of the keto form in spite of nearly equal intrinsic stability of keto and enol tautomers. The results of guanine hydration computations are discussed in relation to mechanisms of base mispairing errors in nucleic acid biosynthesis. The data presented in this paper along with previous results on simulation of hydration shell structures in DNA duplex grooves provide ample evidence for the advantages of PM PF in studies of nucleic-acid hydration.

  17. Development of a new type of high pressure calorimetric cell, mechanically agitated and equipped with a dynamic pressure control system: Application to the characterization of gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Plantier, F., E-mail: frederic.plantier@univ-pau.fr; Missima, D.; Torré, J.-P. [Univ Pau and Pays Adour, CNRS, TOTAL - UMR 5150 – LFC-R - Laboratoire des Fluides Complexes et leurs Réservoirs, BP 1155 – PAU, F-64013 (France); Marlin, L. [Univ Pau and Pays Adour, IPRA FR2952 - Fédération de Recherche- Atelier de Physique Générale, BP 1155 – PAU, F-64013 (France)

    2013-12-15

    A novel prototype of calorimetric cell has been developed allowing experiments under pressure with an in situ agitation system and a dynamic control of the pressure inside the cell. The use of such a system opens a wide range of potential practical applications for determining properties of complex fluids in both pressurized and agitated conditions. The technical details of this prototype and its calibration procedure are described, and an application devoted to the determination of phase equilibrium and phase change enthalpy of gas hydrates is presented. Our results, obtained with a good precision and reproducibility, were found in fairly good agreement with those found in literature, illustrate the various interests to use this novel apparatus.

  18. Study on gas hydrate as a new energy resource in the 21th century

    Energy Technology Data Exchange (ETDEWEB)

    Ryu, Byeong-Jae; Kwak Young-Hoon; Kim, Won-Sik [Korea Institute of Geology Mining and Materials, Taejon (KR)] (and others)

    1999-12-01

    Natural gas hydrate, a special type of clathrate hydrates, is a metastable solid compound which mainly consists of methane and water, and generally called as gas hydrate. It is stable in the specific low-temperature/high-pressure conditions. Gas hydrates play an important role as major reservoir of methane on the earth. On the other hand, the formation and dissociation of gas hydrates could cause the plugging in pipeline, gas kick during production, atmospheric pollution and geohazard. To understand the formation and dissociation of the gas hydrate, the experimental equilibrium conditions of methane hydrate were measured in pure water, 3 wt.% NaCl and MgCl{sub 2} solutions. The equilibrium conditions of propane hydrates were also measured in pure water. The relationship between methane hydrate formation time and overpressure was also analyzed through the laboratory work. The geophysical surveys using air-gun system and multibeam echo sounder were implemented to develop exploration techniques and to evaluate the gas hydrate potential in the East Sea, Korea. General indicators of submarine gas hydrates on seismic data is commonly inferred from the BSR developed parallel to the see floor, amplitude blanking at the upper part of the BSR, and phase reversal and decrease of the interval velocity at BSR. The field data were processed using Geobit 2.9.5 developed by KIGAM to detect the gas hydrate indicators. The accurate velocity analysis was performed by XVA (X-window based Velocity Analysis). Processing results show that the strong reflector occurred parallel to the sea floor were shown at about 1800 ms two way travel time. The interval velocity decrease at this strong reflector and at the reflection phase reversal corresponding to the reflection at the sea floor. Gas hydrate stability field in the study area was determined using the data of measured hydrate equilibrium condition, hydrothermal gradient and geothermal gradient. The depth of BSR detected in the seismic

  19. [Hydration in clinical practice].

    Science.gov (United States)

    Maristany, Cleofé Pérez-Portabella; Segurola Gurruchaga, Hegoi

    2011-01-01

    Water is an essential foundation for life, having both a regulatory and structural function. The former results from active and passive participation in all metabolic reactions, and its role in conserving and maintaining body temperature. Structurally speaking it is the major contributer to tissue mass, accounting for 60% of the basis of blood plasma, intracellular and intersticial fluid. Water is also part of the primary structures of life such as genetic material or proteins. Therefore, it is necessary that the nurse makes an early assessment of patients water needs to detect if there are signs of electrolyte imbalance. Dehydration can be a very serious problem, especially in children and the elderly. Dehydrations treatment with oral rehydration solution decreases the risk of developing hydration disorders, but even so, it is recommended to follow preventive measures to reduce the incidence and severity of dehydration. The key to having a proper hydration is prevention. Artificial nutrition encompasses the need for precise calculation of water needs in enteral nutrition as parenteral, so the nurse should be part of this process and use the tools for calculating the patient's requirements. All this helps to ensure an optimal nutritional status in patients at risk. Ethical dilemmas are becoming increasingly common in clinical practice. On the subject of artificial nutrition and hydration, there isn't yet any unanimous agreement regarding hydration as a basic care. It is necessary to take decisions in consensus with the health team, always thinking of the best interests of the patient.

  20. Controls on methane expulsion during melting of natural gas hydrate systems. Topic area 2

    Energy Technology Data Exchange (ETDEWEB)

    Flemings, Peter [Univ. of Texas, Austin, TX (United States)

    2016-01-14

    1.1. Project Goal The project goal is to predict, given characteristic climate-induced temperature change scenarios, the conditions under which gas will be expelled from existing accumulations of gas hydrate into the shallow ocean or directly to the atmosphere. When those conditions are met, the fraction of the gas accumulation that escapes and the rate of escape shall be quantified. The predictions shall be applicable in Arctic regions and in gas hydrate systems at the up dip limit of the stability zone on continental margins. The behavior shall be explored in response to two warming scenarios: longer term change due to sea level rise (e.g. 20 thousand years) and shorter term due to atmospheric warming by anthropogenic forcing (decadal time scale). 1.2. Project Objectives During the first budget period, the objectives are to review and categorize the stability state of existing well-studied hydrate reservoirs, develop conceptual and numerical models of the melting process, and to design and conduct laboratory experiments that dissociate methane hydrate in a model sediment column by systematically controlling the temperature profile along the column. The final objective of the first budget period shall be to validate the models against the experiments. In the second budget period, the objectives are to develop a model of gas flow into sediment in which hydrate is thermodynamically stable, and conduct laboratory experiments of this process to validate the model. The developed models shall be used to quantify the rate and volume of gas that escapes from dissociating hydrate accumulations. In addition, specific scaled simulations characteristic of Arctic regions and regions near the stability limit at continental margins shall be performed. 1.3. Project Background and Rationale The central hypothesis proposed is that hydrate melting (dissociation) due to climate change generates free gas that can, under certain conditions, propagate through the gas hydrate stability

  1. Non-equilibrium simulation of CH4 production through the depressurization method from gas hydrate reservoirs

    Science.gov (United States)

    Qorbani, Khadijeh; Kvamme, Bjørn

    2016-04-01

    Natural gas hydrates (NGHs) in nature are formed from various hydrate formers (i.e. aqueous, gas, and adsorbed phases). As a result, due to Gibbs phase rule and the combined first and second laws of thermodynamics CH4-hydrate cannot reach thermodynamic equilibrium in real reservoir conditions. CH4 is the dominant component in NGH reservoirs. It is formed as a result of biogenic degradation of biological material in the upper few hundred meters of subsurface. It has been estimated that the amount of fuel-gas reserve in NGHs exceed the total amount of fossil fuel explored until today. Thus, these reservoirs have the potential to satisfy the energy requirements of the future. However, released CH4 from dissociated NGHs could find its way to the atmosphere and it is a far more aggressive greenhouse gas than CO2, even though its life-time is shorter. Lack of reliable field data makes it difficult to predict the production potential, as well as safety of CH4 production from NGHs. Computer simulations can be used as a tool to investigate CH4 production through different scenarios. Most hydrate simulators within academia and industry treat hydrate phase transitions as an equilibrium process and those which employ the kinetic approach utilize simple laboratory data in their models. Furthermore, it is typical to utilize a limited thermodynamic description where only temperature and pressure projections are considered. Another widely used simplification is to assume only a single route for the hydrate phase transitions. The non-equilibrium nature of hydrate indicates a need for proper kinetic models to describe hydrate dissociation and reformation in the reservoir with respect to thermodynamics variables, CH4 mole-fraction, pressure and temperature. The RetrasoCodeBright (RCB) hydrate simulator has previously been extended to model CH4-hydrate dissociation towards CH4 gas and water. CH4-hydrate is added to the RCB data-base as a pseudo mineral. Phase transitions are treated

  2. RECENT ADVANCES IN HYDRATE-BASED TECHNOLOGIES FOR NATURAL GAS STORAGE--A REVIEW

    Institute of Scientific and Technical Information of China (English)

    Yasuhiko H. Mori

    2003-01-01

    Interest in the possibility of storing and transporting natural gas in the form of clathrate hydrates has been increasing in recent years, particularly in some gas-importing and exporting countries.The technologies necessary for realizing this possibility may be classified into those relevant to the four serial processes (a) the formation of a hydrate, (b) the processing (dewatering, pelletizing, etc. ) of the formed hydrate, (c) the storage and transportation of the processed hydrate, and (d) the regasification (dissociation) of the hydrate. The technological development of any of these processes is still at an early stage. For hydrate formation, for example, various rival operations have been proposed. However,many of them have never been subjected to actual tests for practical use. More efforts are required for examining the different hydrate-formation technologies and for rating them by comparison. The general design of the processing of the formed hydrate inevitably depends on both the hydrate-formation process and the storage/transportation process, hence it has a wide variability. The major uncertainty in the storage-process design lies in the as-yet unclarified utility of the "self-preservation" effect of the naturalgas hydrates. The process design as well as the relevant cost evaluation should strongly depend on whether the hydrates are well preserved at atmospheric pressure in large-scale storage facilities. The regasification process has been studied less extensively than the former processes. The state of the art of the technological development in each of the serial processes is reviewed, placing emphasis on the hydrate formation process.

  3. Well log characterization of natural gas-hydrates

    Science.gov (United States)

    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

  4. Investigating the Metastability of Clathrate Hydrates for Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    Koh, Carolyn Ann [Colorado School of Mines

    2014-11-18

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

  5. Phase equilibrium modeling of gas hydrate systems for CO2 capture

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen; Thomsen, Kaj; Abildskov, Jens

    2012-01-01

    Two thermodynamic models capable of describing dissociation pressures of mixed gas clathrate hydrates formed from ternary mixtures of CO2, N2 and liquid water, are presented. Both of the models utilize the Cubic-Plus-Association (CPA) equation of state (EOS) for the thermodynamic description of t...

  6. Hydrate phase equilibria of CO2+N2+aqueous solution of THF, TBAB or TBAF system

    DEFF Research Database (Denmark)

    Sfaxi, Imen Ben Attouche; Durand, Isabelle; Lugo, Rafael

    2014-01-01

    We report hydrate dissociation conditions of CO2 (15 and 30mol%)+N2 (85 and 70mol%) in the presence of aqueous solutions of THF, TBAB or TBAF. The concentrations of TBAB and TBAF in the aqueous solutions are 5wt% and 9wt% while THF concentration in aqueous solution is 3mol%. Two different experim...

  7. Characteristics of shallow gas hydrate in Okhotsk Sea

    Institute of Scientific and Technical Information of China (English)

    LUAN XiWu; JIN YoungKeun; Anatoly OBZHIROV; YUE BaoJing

    2008-01-01

    Multidisciplinary field investigations were carried out in Okhotsk Sea by R/V Akademik M.A. Lavrentyev (LV) of the Russian Academy of Sciences (RAS) in May 2006, supported by funding agencies from Korea, Russia, Japan and China. Geophysical data including echo-sounder, bottom profile, side-scansonar, and gravity core sample were obtained aimed to understand the characteristics and formation mechanism of shallow gas hydrates. Based on the geophysical data, we found that the methane flare detected by echo-sounder was the evidence of free gas in the sediment, while the dome structure detected by side-scan sonar and bottom profile was the root of gas venting. Gas hydrate retrieved from core on top of the dome structure which was interbedded as thin lamination or lenses with thickness varying from a few millimeters to 3 cm. Gas hydrate content in hydrate-bearing intervals visually amounted to 5%-30% of the sediment volume. This paper argued that gases in the sediment core were not all from gas hydrate decomposition during the gravity core lifting process, free gases must existed in the gas hydrate stability zone, and tectonic structure like dome structure in this paper was free gas central, gas hydrate formed only when gases over-saturated in this gas central, away from these struc tures, gas hydrate could not form due to low gas concentration.

  8. Characteristics of shallow gas hydrate in Okhotsk Sea

    Institute of Scientific and Technical Information of China (English)

    Anatoly; OBZHIROV

    2008-01-01

    Multidisciplinary field investigations were carried out in Okhotsk Sea by R/V Akademik M.A. Lavrentyev (LV) of the Russian Academy of Sciences (RAS) in May 2006, supported by funding agencies from Ko- rea, Russia, Japan and China. Geophysical data including echo-sounder, bottom profile, side-scan- sonar, and gravity core sample were obtained aimed to understand the characteristics and formation mechanism of shallow gas hydrates. Based on the geophysical data, we found that the methane flare detected by echo-sounder was the evidence of free gas in the sediment, while the dome structure de- tected by side-scan sonar and bottom profile was the root of gas venting. Gas hydrate retrieved from core on top of the dome structure which was interbedded as thin lamination or lenses with thickness varying from a few millimeters to 3 cm. Gas hydrate content in hydrate-bearing intervals visually amounted to 5%―30% of the sediment volume. This paper argued that gases in the sediment core were not all from gas hydrate decomposition during the gravity core lifting process, free gases must existed in the gas hydrate stability zone, and tectonic structure like dome structure in this paper was free gas central, gas hydrate formed only when gases over-saturated in this gas central, away from these struc- tures, gas hydrate could not form due to low gas concentration.

  9. On the dissociative electron attachment as a potential source of molecular hydrogen in irradiated liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Cobut, V.; Jay-Gerin, J.-P.; Frongillo, Y. [Sherbrooke Univ., PQ (Canada). Faculte de Medecine; Patau, J.P. [Toulouse-3 Univ., 31 (France)

    1996-02-01

    In the radiolysis of liquid water, different mechanisms for the formation of molecular hydrogen (H{sub 2}) are involved at different times after the initial energy disposition. It has been suggested that the contributions of the e{sub aq}{sup -} + e{sub aq}{sup -}, H + e{sub aq}{sup -} and H + H reactions between hydrated electrons (e{sub aq}{sup -}) and hydrogen atoms in the spurs are not sufficient to account for all of the observed H{sub 2} yield (0.45 molecules/100 eV) on the microsecond time scale. Addressing the question of the origin of an unscavengeable H{sub 2} yield of 0.15 molecules/100 eV produced before spur expansion, we suggest that the dissociative capture of the so-called vibrationally-relaxing electrons by H{sub 2}O molecules is a possible pathway for the formation of part of the initial H{sub 2} yield. Comparison of recent dissociative-electron-attachment H{sup -}-anion yield-distribution measurements from amorphous H{sub 2}O films with the energy spectrum of vibrationally-relaxing electrons in irradiated liquid water, calculated by Monte Carlo simulations, plays in favor of this hypothesis. (author).

  10. Water Retention Curve and Relative Permeability for Gas Production from Hydrate-Bearing Sediments

    Science.gov (United States)

    Mahabadi, N.; Dai, S.; Seol, Y.; Jang, J.

    2014-12-01

    Water retention curve (soil water characteristic curve SWCC) and relative permeability equations are important to determine gas and water production for gas hydrate development. However, experimental studies to determine fitting parameters of those equations are not available in the literature. The objective of this research is to obtain reliable parameters for capillary pressure functions and relative permeability equations applicable to hydrate dissociation and gas production. In order to achieve this goal, (1) micro X-ray Computer Tomography (CT) is used to scan the specimen under 10MPa effective stress, (2) a pore network model is extracted from the CT image, (3) hydrate dissociation and gas expansion are simulated in the pore network model, (4) the parameters for the van Genuchten-type soil water characteristic curve and relative permeability equation during gas expansion are suggested. The research outcome will enhance the ability of numerical simulators to predict gas and water production rate.

  11. Dissociative Identity Disorder

    Science.gov (United States)

    Schmidt, Tom

    2007-01-01

    Few psychological disorders in the Diagnostic Statistical Manual have generated as much controversy as Dissociative Identity Disorder (DID). For the past 35 years diagnoses of DID, previously referred to as Multiple Personality Disorder (MPD), have increased exponentially, causing various psychological researchers and clinicians to question the…

  12. Sexuality of dissocial persons

    Directory of Open Access Journals (Sweden)

    Marta Janus

    2016-02-01

    Full Text Available Introduction. The development of personality disorders as well as sexual disorders is defined by the common time spectrum as well as deficits and changes in such areas as biological, environmental and mental area. Dissocial (antisocial personality disorder is characterised by a pervasive pattern of disregard for, or violation of, the rights of others. The indices of the discussed disorder can be found in specific patterns of social inadequacy occurring during childhood and puberty. At the same time, characteristic indices of social functioning at a young age often indicate subsequent dysfunctions in the area of sexuality. Aim. The aim of this paper is to explain sexual functioning of persons with dissocial personality disorder (including the relation with sexual dysfunctions, and to ascertain issues that need further empirical studies. Method. As a result of analysis of available literature (matched with EBSCO database search fulfilling criteria of sample size, accuracy of examination procedure, conclusions and discussion 5 articles fulfilling criteria cited above has been found. Conclusions: Based on literature overview, it appeared to be impossible to determine one coherent way of sexual functioning of dissocial persons, and to establish causal relationship of sexual dysfunctions and dissocial personality disorder. However, it is possible to indicate group of most characteristic dysfunctional sexual behaviours. Noteworthy, available publication analyse only selected aspects of sexual behaviours in small, homogenous groups. There is a lack of review studies as well as multi-faceted studies.

  13. Pathological Dissociation as Measured by the Child Dissociative Checklist

    Science.gov (United States)

    Wherry, Jeffrey N.; Neil, Debra A.; Taylor, Tamara N.

    2009-01-01

    The component structure of the Child Dissociative Checklist was examined among abused children. A factor described as pathological dissociation emerged that was predicted by participants being male. There also were differences in pathological dissociation between groups of sexually abused and physically abused children. Replication of this factor…

  14. Linking basin-scale and pore-scale gas hydrate distribution patterns in diffusion-dominated marine hydrate systems

    Science.gov (United States)

    Nole, Michael; Daigle, Hugh; Cook, Ann E.; Hillman, Jess I. T.; Malinverno, Alberto

    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 (1-20 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-scale 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. Furthermore, we find that hydrate in fine-grained material can preserve high hydrate saturations in nearby thin sands with burial.Plain Language SummaryThis study combines one-, two-, and three-dimensional simulations to explore one potential process by which methane dissolved in water beneath the seafloor can be converted into solid methane hydrate. This work specifically examines one end-member methane transport

  15. Influence of Glass Powder on Hydration Kinetics of Composite Cementitious Materials

    Directory of Open Access Journals (Sweden)

    Xiaolin Chang

    2015-01-01

    Full Text Available The influence of glass powder (GP on hydration kinetics of composite cementitious materials has been investigated by isothermal calorimetry test and hydration kinetics methods in this paper. The hydration heat emission rate and hydration heat decrease gradually while the induction and acceleration period increase with the increase of GP content. According to Krstulovic-Dabic model, the hydration process of composite cementitious materials containing GP is controlled by a variety of complicated reaction mechanisms, which can be divided into three periods: nucleation and crystal growth (NG, phase boundary reaction (I, and diffusion (D. The NG and I process are shortened after incorporating GP.

  16. CO2 capture from simulated fuel gas mixtures using semiclathrate hydrates formed by quaternary ammonium salts.

    Science.gov (United States)

    Park, Sungwon; Lee, Seungmin; Lee, Youngjun; Seo, Yongwon

    2013-07-02

    In order to investigate the feasibility of semiclathrate hydrate-based precombustion CO2 capture, thermodynamic, kinetic, and spectroscopic studies were undertaken on the semiclathrate hydrates formed from a fuel gas mixture of H2 (60%) + CO2 (40%) in the presence of quaternary ammonium salts (QASs) such as tetra-n-butylammonium bromide (TBAB) and fluoride (TBAF). The inclusion of QASs demonstrated significantly stabilized hydrate dissociation conditions. This effect was greater for TBAF than TBAB. However, due to the presence of dodecahedral cages that are partially filled with water molecules, TBAF showed a relatively lower gas uptake than TBAB. From the stability condition measurements and compositional analyses, it was found that with only one step of semiclathrate hydrate formation with the fuel gas mixture from the IGCC plants, 95% CO2 can be enriched in the semiclathrate hydrate phase at room temperature. The enclathration of both CO2 and H2 in the cages of the QAS semiclathrate hydrates and the structural transition that results from the inclusion of QASs were confirmed through Raman and (1)H NMR measurements. The experimental results obtained in this study provide the physicochemical background required for understanding selective partitioning and distributions of guest gases in the QAS semiclathrate hydrates and for investigating the feasibility of a semiclathrate hydrate-based precombustion CO2 capture process.

  17. Modeling Hydrates and the Gas Hydrate Markup Language

    Directory of Open Access Journals (Sweden)

    Weihua Wang

    2007-06-01

    Full Text Available Natural gas hydrates, as an important potential fuels, flow assurance hazards, and possible factors initiating the submarine geo-hazard and global climate change, have attracted the interest of scientists all over the world. After two centuries of hydrate research, a great amount of scientific data on gas hydrates has been accumulated. Therefore the means to manage, share, and exchange these data have become an urgent task. At present, metadata (Markup Language is recognized as one of the most efficient ways to facilitate data management, storage, integration, exchange, discovery and retrieval. Therefore the CODATA Gas Hydrate Data Task Group proposed and specified Gas Hydrate Markup Language (GHML as an extensible conceptual metadata model to characterize the features of data on gas hydrate. This article introduces the details of modeling portion of GHML.

  18. Overview: Nucleation of clathrate hydrates

    Science.gov (United States)

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

    2016-12-01

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

  19. A study on gas hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Byoung Jae; Jung, Tae Jin; Sunwoo, Don [Korea Institute of Geology Mining and Materials, Taejon (Korea, Republic of)

    1996-12-01

    Sufficient documents were reviewed to understand solid components of water and gaseous hydrocarbon known as gas hydrates, which represent an important potential energy resource of the future. The review provides us with valuable information on crystal structures, kinetics, origin and distribution of gas hydrates. In addition, the review increased our knowledge of exploration and development methods of gas hydrates. Large amounts of methane, the principal component of natural gas, in the form of solid gas hydrate are found mainly offshore in outer continental margin sediment and, to a lesser extent, in polar regions commonly associated with permafrost. Natural gas hydrates are stable in some environments where the hydrostatic pressure exerted by overlying water column is sufficient for hydrate formation and stability. The required high pressures generally restrict gas hydrate to sediments beneath water of approximately 400 m. Higher sediment temperatures at greater subbottom depths destabilize gas hydrates. Based on the pressure- temperature condition, the outer continental margin of East Sea where water depth is deep enough to form gas hydrate is considered to have high potential of gas hydrate accumulations. (author). 56 refs., tabs., figs.

  20. Three dimensions of dissociative amnesia.

    Science.gov (United States)

    Dell, Paul F

    2013-01-01

    Principal axis factor analysis with promax rotation extracted 3 factors from the 42 memory and amnesia items of the Multidimensional Inventory of Dissociation (MID) database (N = 2,569): Discovering Dissociated Actions, Lapses of Recent Memory and Skills, and Gaps in Remote Memory. The 3 factors' shared variance ranged from 36% to 64%. Construed as scales, the 3 factor scales had Cronbach's alpha coefficients of .96, .94, and .93, respectively. The scales correlated strongly with mean Dissociative Experiences Scale scores, mean MID scores, and total scores on the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised (SCID-D-R). What is interesting is that the 3 amnesia factors exhibited a range of correlations with SCID-D-R Amnesia scores (.52, .63, and .70, respectively), suggesting that the SCID-D-R Amnesia score emphasizes gaps in remote memory over amnesias related to dissociative identity disorder. The 3 amnesia factor scales exhibited a clinically meaningful pattern of significant differences among dissociative identity disorder, dissociative disorder not otherwise specified-1, dissociative amnesia, depersonalization disorder, and nonclinical participants. The 3 amnesia factors may have greater clinical utility for frontline clinicians than (a) amnesia as discussed in the context of the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition, nosology of the dissociative disorders or (b) P. Janet's (1893/1977 ) 4-fold classification of dissociative amnesia. The author recommends systematic study of the phenomenological differences within specific dissociative symptoms and their differential relationship to specific dissociative disorders.

  1. Textural and mechanical characterization of C-S-H gels from hydration of synthetic T1-C{sub 3}S, {beta}-C{sub 2}S and their blends; Caracterizacion textural y mecanica de geles C-S-H formados en la hidratacion de muestras sinteticas T1-C{sub 3}S, {beta}-C{sub 2}S y sus mezclas

    Energy Technology Data Exchange (ETDEWEB)

    Goni, S.; Guerrero, A.; Puertas, F.; Hernandez, M. S.; Palacios, M.; Dolado, J. S.; Zhu, W.; Howind, T.

    2011-07-01

    The textural and mechanical characterization of C-S-H gels formed from the hydration of pure T1-C{sub 3}S, {beta}-C{sub 2}S and their blends are studied by Nitrogen sorption and nano indentation experiments. The surface area and nano porosity of C-S-H gels formed from the hydration of {beta}-C{sub 2}S and the 30-70 (T1-C{sub 3}S and {beta}-C{sub 2}S mixture) are higher than those from hydration of T1-C{sub 3}S, and 70-30, with the difference decreasing with hydration age. Such changes are well supported by findings of nano indentation study, which shows the greater relative volume of C-S-H phases with lower densities in the {beta}-C{sub 2}S and the 30-70 pastes. With the increase in hydration age, the relative volume of C-S-H phases with higher densities increased at the expenses of those with lower density. Important quantitative correlations were found among these textural characteristics and the mean chain length, determined from {sup 2}9Si magic-angle-spinning (MAS) NMR, of the C-S-H gels. (Author) 36 refs.

  2. Gas and Gas Hydrate Potential Offshore Amasra,Bartin and Zonguldak and Possible Agent for Multiple BSR Occurrence

    Science.gov (United States)

    Mert Küçük, Hilmi; Dondurur, Derman; Özel, Özkan; Sınayuç, Çağlar; Merey, Şükrü; Parlaktuna, Mahmut; Çifçi, Günay

    2015-04-01

    Gas hydrates, shallow gases and mud volcanoes have been studied intensively in the Black Sea in recent years. Researches have shown that the Black Sea region has an important potential about hydrocarbon. BSR reflections in the seismic sections and seabed sampling studies also have proven the formations of hydrates clearly. In this respect, total of 2400 km multichannel seismic reflection, chirp and multibeam bathymetry data were collected along shelf to abyssal plain in 2010 and 2012 offshore Amasra, Bartın, Zonguldak-Kozlu in the central Black Sea.. Collected data represent BSRs, bright spots and transparent zones. It has been clearly observed that possible gas chimneys cross the base of gas hydrate stability zones as a result of possible weak zones in the gas hydrate bearing sediments. Seabed samples were collected closely to possible gas chimneys due to shallow gas anomalies in the data. Head space gas cromatography was applied to seabed samples to observe gas composition and the gas cromatography results represented hydrocarbon gases such as Methane, Ethane, Propane, i-Butane, n-Butane, i-Pentane, n-Pentane and Hexane. Thermogenic gas production by Turkish Petroleum Corp. from Akçakoca-1 and Ayazlı-1 well is just located at the southwest of the study area and the observations of the study area point out there is also thermogenic gas potential at the eastern side of the Akçakoca. In addition, multiple-BSRs were observed in the study area and it is thought the key point of the multiple-BSRs are different gas compositions. This suggests that hydrate formations can be formed by gas mixtures. Changing of the thermobaric conditions can trigger dissociation of the gas hydrates in the marine sediments due to sedimentary load and changing of the water temperature around seabed. Our gas hydrate modelling study suggest that gas hydrates are behaving while their dissociation process if the gas hydrates are generated by gas mixture. Monitoring of our gas hydrate

  3. The effect of polymethylsiloxanes on hydration of clinker phases

    Science.gov (United States)

    Stoch, A.; Zdaniewicz, M.; Paluszkiewicz, Cz.

    1999-11-01

    The effect of the polydimethylsiloxane (PDMS) admixture on hydration of pure clinker phases: alite, belite or tricalcium aluminate was studied by means of FTIR spectroscopy. It was shown that PDMS, introduced to a clinker phase paste during the hydration process reduces the carbonation reaction, improves the crystallization of hydrates in tricalcium aluminate and considerably increases water resistance without significantly changing the mechanical parameters. Our FTIR results were also confirmed by XRD, DTA and SEM study of the morphology of the newly formed phases. Introduction of as much as 5 wt.% of the PDMS increases the wetting angle by up to 80-120°.

  4. Effect on Hydration and Hardening of Tricalcium Phosphate Bone Cement

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    The bioactive α-Ca3 (PO4)2 bone cement was studied by XRD , SEM and isothermal calorimetric measurements. The results showed that a mixed pattern of TCP and hydroxylapatite were obtained after hydration and hardening. The mechanism of hydration and hardening of the α-Ca3 ( PO4 )2 was dissolution-precipitation,(NH4) H2 PO4 was the best set accelerator to the α-Ca3 ( PO4 )2 cement, and the HAP powers and the(NH4) H2 PO4 concentration had a great effect on the hydration rate of α-Ca3 ( PO4 )2.

  5. Calorimetric Determination of Enthalpy of Formation of Natural Gas Hydrates%天然气水合物生成焓的实验研究

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    This paper reports the measurements of enthalpies of natural gas hydrates in typical natural gas mixturecontaining methane, ethane, propane and iso-butane at pressure in the vicinity of 2000 kPa (300 psi) and 6900 kPa(1000psi). The measurements were made in a multi-cell differential scanning calorimeter using modified highpressure cells. The enthalpy of water and the enthalpy of dissociation of the gas hydrate were determined fromthe calorimeter response during slow temperature scanning at constant pressure. The amount of gas released fromthe dissociation of hydrate was determined from the pumped volume of the high pressure pump. The occupationratio (mole ratio) of the water to gas and the enthalpy of hydrate formation are subject to uncertainty of 1.5%.The results show that the enthalpy of hydrate formation and the occupation ratio are essentially independent of pressure.

  6. Rapid gas hydrate formation process

    Science.gov (United States)

    Brown, Thomas D.; Taylor, Charles E.; Unione, Alfred J.

    2013-01-15

    The disclosure provides a method and apparatus for forming gas hydrates from a two-phase mixture of water and a hydrate forming gas. The two-phase mixture is created in a mixing zone which may be wholly included within the body of a spray nozzle. The two-phase mixture is subsequently sprayed into a reaction zone, where the reaction zone is under pressure and temperature conditions suitable for formation of the gas hydrate. The reaction zone pressure is less than the mixing zone pressure so that expansion of the hydrate-forming gas in the mixture provides a degree of cooling by the Joule-Thompson effect and provides more intimate mixing between the water and the hydrate-forming gas. The result of the process is the formation of gas hydrates continuously and with a greatly reduced induction time. An apparatus for conduct of the method is further provided.

  7. Childhood maltreatment and intimate partner violence in dissociative disorder patients

    Directory of Open Access Journals (Sweden)

    Aliya R. Webermann

    2014-09-01

    Full Text Available Background: Childhood maltreatment (CM is a risk factor for subsequent intimate partner violence (IPV in adulthood, with high rates of retrospectively reported CM among IPV victims and perpetrators. A theorized mechanism of the link between CM and IPV is dissociation. Dissociation may allow perpetrators of violence to remain emotionally distant from their behavior and minimize empathy toward those they victimize, enabling them to commit acts of violence similar to their own experiences. Indeed, elevated rates of dissociation and dissociative disorders (DD have been found among IPV survivors and perpetrators. In addition, in pilot studies, DD clinicians have reported high levels of violent behavior among DD patients. Objective: The present study investigates IPV among DD patients with Dissociative Identity Disorder and Dissociative Disorder Not Otherwise Specified, a group with CM rates of 80–95% and severe dissociative symptoms. Methods: DD clinicians reported on rates of CM and IPV among 275 DD patients in outpatient treatment. DD patients also completed a self-report measure of dissociation. Analyses assessed the associations between CM typologies and IPV, as well as trait dissociation and IPV. Results: Physical and emotional child abuse were associated with physical IPV, and childhood witnessing of domestic violence (DV and childhood neglect were associated with emotional IPV. Conclusions: The present study is the first to provide empirical support for a possible CM to adult IPV developmental trajectory among DD patients. Future research is needed to better understand the link between CM and IPV among those with trauma and DD.

  8. Evaluation of Gas Production Potential of Hydrate Deposits in Alaska North Slope using Reservoir Simulations

    Science.gov (United States)

    Nandanwar, M.; Anderson, B. J.

    2015-12-01

    Over the past few decades, the recognition of the importance of gas hydrates as a potential energy resource has led to more and more exploration of gas hydrate as unconventional source of energy. In 2002, U.S. Geological Survey (USGS) started an assessment to conduct a geology-based analysis of the occurrences of gas hydrates within northern Alaska. As a result of this assessment, many potential gas hydrate prospects were identified in the eastern National Petroleum Reserve Alaska (NPRA) region of Alaska North Slope (ANS) with total gas in-place of about 2 trillion cubic feet. In absence of any field test, reservoir simulation is a powerful tool to predict the behavior of the hydrate reservoir and the amount of gas that can be technically recovered using best suitable gas recovery technique. This work focuses on the advanced evaluation of the gas production potential of hydrate accumulation in Sunlight Peak - one of the promising hydrate fields in eastern NPRA region using reservoir simulations approach, as a part of the USGS gas hydrate development Life Cycle Assessment program. The main objective of this work is to develop a field scale reservoir model that fully describes the production design and the response of hydrate field. Due to the insufficient data available for this field, the distribution of the reservoir properties (such as porosity, permeability and hydrate saturation) are approximated by correlating the data from Mount Elbert hydrate field to obtain a fully heterogeneous 3D reservoir model. CMG STARS is used as a simulation tool to model multiphase, multicomponent fluid flow and heat transfer in which an equilibrium model of hydrate dissociation was used. Production of the gas from the reservoir is carried out for a period of 30 years using depressurization gas recovery technique. The results in terms of gas and water rate profiles are obtained and the response of the reservoir to pressure and temperature changes due to depressurization and hydrate

  9. The strength and rheology of methane clathrate hydrate

    Science.gov (United States)

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

    2003-01-01

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

  10. Simulating the gas hydrate production test at Mallik using the pilot scale pressure reservoir LARS

    Science.gov (United States)

    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

  11. Computer simulation of alkali metal cation-montmorillonite hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Fang-Ru Chou [Columbia Univ., Palisades, NY (United States); Skipper, N.T. [Univ. College, London (United Kingdom); Sposito, G. [Lawrence Berkeley National Lab., CA (United States)

    1997-12-31

    Molecular structure in the interlayers of Li-, Na-, or K-Wyoming montmorillonite with one, two, or three adsorbed water layers was investigated for the first time by concurrent Monte Carlo and molecular dynamics (MD) simulation, based on the Matsouka-Clementi-Yoshimine, (MCY) model of water-water interactions. Calculated layer spacings, as well as interlayer-species self-diffusion coefficients, were in good agreement with available experimental data. Inner-sphere surface complexes of the cations with tetrahedral charge sites were observed for all hydrates, whereas outer-sphere surface complexes of the cations with octahedral charge sites, found also in the one-layer hydrate, tended to dissociate from the clay mineral basal planes into a diffuse layer in the two- and three-layer hydrates. Differences in the interlayer water structure among the hydrates mainly reflected cation solvation, although some water molecules were entrapped within cavities in the montmorillonite surface. All of the interlayer cation and water species exchanged on the time scale (0.2 ns) of the MD simulations. Comparisons with results obtained using, instead of the MCY model, the TIP4P model for water-water, cation-water, and cation-clay interactions indicated that layer spacings and interlayer species mobilities tend to be under-predicted by the TIP4P model.

  12. A computational study of ultrafast acid dissociation and acid-base neutralization reactions. I. The model.

    Science.gov (United States)

    Maurer, Patrick; Thomas, Vibin; Rivard, Ugo; Iftimie, Radu

    2010-07-28

    Ultrafast, time-resolved investigations of acid-base neutralization reactions have recently been performed using systems containing the photoacid 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) and various Bronsted bases. Two conflicting neutralization mechanisms have been formulated by Mohammed et al. [Science 310, 83 (2005)] and Siwick et al. [J. Am. Chem. Soc. 129, 13412 (2007)] for the same acid-base system. Herein an ab initio molecular dynamics based computational model is formulated, which is able to investigate the validity of the proposed mechanisms in the general context of ground-state acid-base neutralization reactions. Our approach consists of using 2,4,6-tricyanophenol (exp. pKa congruent with 1) as a model for excited-state HPTS( *) (pKa congruent with 1.4) and carboxylate ions for the accepting base. We employ our recently proposed dipole-field/quantum mechanics (QM) treatment [P. Maurer and R. Iftimie, J. Chem. Phys. 132, 074112 (2010)] of the proton donor and acceptor molecules. This approach allows one to tune the free energy of neutralization to any desired value as well as model initial nonequilibrium hydration effects caused by a sudden increase in acidity, making it possible to achieve a more realistic comparison with experimental data than could be obtained via a full-QM treatment of the entire system. It is demonstrated that the dipole-field/QM model reproduces correctly key properties of the 2,4,6-tricyanophenol acid molecule including gas-phase proton dissociation energies and dipole moments, and condensed-phase hydration structure and pKa values.

  13. Dynamics of Hydration Water in Sugars and Peptides Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Perticaroli, Stefania [ORNL; Nakanishi, Masahiro [ORNL; Pashkovski, Eugene [Unilever R& D Trumbull, Trumbull CT; Sokolov, Alexei P [ORNL

    2013-01-01

    We analyzed solute and solvent dynamics of sugars and peptides aqueous solutions using extended epolarized light scattering (EDLS) and broadband dielectric spectroscopies (BDS). Spectra measured with both techniques reveal the same mechanism of rotational diffusion of peptides molecules. In the case of sugars, this solute reorientational relaxation can be isolated by EDLS measurements, whereas its ontribution to the dielectric spectra is almost negligible. In the presented analysis, we characterize the hydration water in terms of hydration number and retardation ratio between relaxation times of hydration and bulk water. Both techniques provide similar estimates of . The retardation imposed on the hydration water by sugars is 3.3 1.3 and involves only water molecules hydrogen-bonded (HB) to solutes ( 3 water molecules per sugar OH-group). In contrast, polar peptides cause longer range erturbations beyond the first hydration shell, and between 2.8 and 8, increasing with the number of chemical groups engaged in HB formation. We demonstrate that chemical heterogeneity and specific HB interactions play a crucial role in hydration dynamics around polar solutes. The obtained results help to disentangle the role of excluded volume and enthalpic contributions in dynamics of hydration water at the interface with biological molecules.

  14. Theory of dissociative tunneling ionization

    CERN Document Server

    Svensmark, Jens; Madsen, Lars Bojer

    2016-01-01

    We present a theoretical study of the dissociative tunneling ionization process. Analytic expressions for the nuclear kinetic energy distribution of the ionization rates are derived. A particularly simple expression for the spectrum is found by using the Born-Oppenheimer (BO) approximation in conjunction with the reflection principle. These spectra are compared to exact non-BO ab initio spectra obtained through model calculations with a quantum mechanical treatment of both the electronic and nuclear degrees freedom. In the regime where the BO approximation is applicable imaging of the BO nuclear wave function is demonstrated to be possible through reverse use of the reflection principle, when accounting appropriately for the electronic ionization rate. A qualitative difference between the exact and BO wave functions in the asymptotic region of large electronic distances is shown. Additionally the behavior of the wave function across the turning line is seen to be reminiscent of light refraction. For weak fiel...

  15. Hydrate-based heavy metal separation from aqueous solution

    Science.gov (United States)

    Song, Yongchen; Dong, Hongsheng; Yang, Lei; Yang, Mingjun; Li, Yanghui; Ling, Zheng; Zhao, Jiafei

    2016-02-01

    A novel hydrate-based method is proposed for separating heavy metal ions from aqueous solution. We report the first batch of experiments and removal characteristics in this paper, the effectiveness and feasibility of which are verified by Raman spectroscopy analysis and cross-experiment. 88.01-90.82% of removal efficiencies for Cr3+, Cu2+, Ni2+, and Zn2+ were obtained. Further study showed that higher R141b-effluent volume ratio contributed to higher enrichment factor and yield of dissociated water, while lower R141b-effluent volume ratio resulted in higher removal efficiency. This study provides insights into low-energy, intensive treatment of wastewater.

  16. Hydration and physical performance.

    Science.gov (United States)

    Murray, Bob

    2007-10-01

    There is a rich scientific literature regarding hydration status and physical function that began in the late 1800s, although the relationship was likely apparent centuries before that. A decrease in body water from normal levels (often referred to as dehydration or hypohydration) provokes changes in cardiovascular, thermoregulatory, metabolic, and central nervous function that become increasingly greater as dehydration worsens. Similarly, performance impairment often reported with modest dehydration (e.g., -2% body mass) is also exacerbated by greater fluid loss. Dehydration during physical activity in the heat provokes greater performance decrements than similar activity in cooler conditions, a difference thought to be due, at least in part, to greater cardiovascular and thermoregulatory strain associated with heat exposure. There is little doubt that performance during prolonged, continuous exercise in the heat is impaired by levels of dehydration >or= -2% body mass, and there is some evidence that lower levels of dehydration can also impair performance even during relatively short-duration, intermittent exercise. Although additional research is needed to more fully understand low-level dehydration's effects on physical performance, one can generalize that when performance is at stake, it is better to be well-hydrated than dehydrated. This generalization holds true in the occupational, military, and sports settings.

  17. Comparison of hydration reactions for "piano-stool" RAPTA-B and [Ru(η6- arene)(en)Cl]+ complexes: Density functional theory computational study

    Science.gov (United States)

    Chval, Zdeněk; Futera, Zdeněk; Burda, Jaroslav V.

    2011-01-01

    The hydration process for two Ru(II) representative half-sandwich complexes: Ru(arene)(pta)Cl2 (from the RAPTA family) and [Ru(arene)(en)Cl]+ (further labeled as Ru_en) were compared with analogous reaction of cisplatin. In the study, quantum chemical methods were employed. All the complexes were optimized at the B3LYP/6-31G(d) level using Conductor Polarizable Continuum Model (CPCM) solvent continuum model and single-point (SP) energy calculations and determination of electronic properties were performed at the B3LYP/6-311++G(2df,2pd)/CPCM level. It was found that the hydration model works fairly well for the replacement of the first chloride by water where an acceptable agreement for both Gibbs free energies and rate constants was obtained. However, in the second hydration step worse agreement of the experimental and calculated values was achieved. In agreement with experimental values, the rate constants for the first step can be ordered as RAPTA-B > Ru_en > cisplatin. The rate constants correlate well with binding energies (BEs) of the Pt/Ru-Cl bond in the reactant complexes. Substitution reactions on Ru_en and cisplatin complexes proceed only via pseudoassociative (associative interchange) mechanism. On the other hand in the case of RAPTA there is also possible a competitive dissociation mechanism with metastable pentacoordinated intermediate. The first hydration step is slightly endothermic for all three complexes by 3-5 kcal/mol. Estimated BEs confirm that the benzene ligand is relatively weakly bonded assuming the fact that it occupies three coordination positions of the Ru(II) cation.

  18. Charge-transport-induced dissociation in donor-bridge-acceptor complexes.

    Science.gov (United States)

    Brisker, Daria; Peskin, Uri

    2008-12-28

    Possible mechanisms for charge-transport-induced dissociation in donor-bridge-acceptor complexes are studied. Two mechanisms for dissociation at the molecular bridge are captured within a simple model of an anharmonic bridge vibration coupled nonlinearly to an electronic degree of freedom. A direct mechanism is associated with vibronic excitations to the nuclear continuum and an alternative dissociation mechanism involves intermediate quasibound vibrational states (Feshbach resonances). The two different mechanisms of charge-transport-induced dissociation are analyzed and their interplay as a function of the system parameters is examined. A parameter regime is suggested where the phenomenon should be experimentally accessible.

  19. Some thermodynamical aspects of protein hydration water

    Energy Technology Data Exchange (ETDEWEB)

    Mallamace, Francesco, E-mail: francesco.mallamace@unime.it [Dipartimento di Fisica e Scienze della Terra, Università di Messina and CNISM, I-98168 Messina (Italy); Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Center for Polymer Studies and Department of Physics, Boston University, Boston, Massachusetts 02215 (United States); Corsaro, Carmelo [Dipartimento di Fisica e Scienze della Terra, Università di Messina and CNISM, I-98168 Messina (Italy); CNR-IPCF, Viale F. Stagno D’Alcontres 37, I-98158 Messina (Italy); Mallamace, Domenico [Dipartimento SASTAS, Università di Messina, I-98166 Messina (Italy); Vasi, Sebastiano [Dipartimento di Fisica e Scienze della Terra, Università di Messina and CNISM, I-98168 Messina (Italy); Vasi, Cirino [CNR-IPCF, Viale F. Stagno D’Alcontres 37, I-98158 Messina (Italy); Stanley, H. Eugene [Center for Polymer Studies and Department of Physics, Boston University, Boston, Massachusetts 02215 (United States); Chen, Sow-Hsin [Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

    2015-06-07

    We study by means of nuclear magnetic resonance the self-diffusion of protein hydration water at different hydration levels across a large temperature range that includes the deeply supercooled regime. Starting with a single hydration shell (h = 0.3), we consider different hydrations up to h = 0.65. Our experimental evidence indicates that two phenomena play a significant role in the dynamics of protein hydration water: (i) the measured fragile-to-strong dynamic crossover temperature is unaffected by the hydration level and (ii) the first hydration shell remains liquid at all hydrations, even at the lowest temperature.

  20. Study on the recovery of hydrogen from refinery (hydrogen+methane) gas mixtures using hydrate technology

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A novel technique for separating hydrogen from (H2 + CH4) gas mixtures through hydrate formation/dissociation was proposed. In this work, a systematic experimental study was performed on the separation of hydrogen from (H2 + CH4) feed mixtures with various hydrogen contents (mole fraction x = 40%-90%). The experimental results showed that the hydrogen content could be enriched to as high as ~94% for various feed mixtures using the proposed hydrate technology under a temperature slightly above 0℃ and a pressure below 5.0 MPa. With the addition of a small amount of suitable additives, the rate of hydrate formation could be increased significantly. Anti-agglomeration was used to disperse hydrate particles into the condensate phase. Instead of preventing hydrate growth (as in the kinetic inhibitor tests), hydrates were allowed to form, but only as small dispersed particles. Anti-agglomeration could keep hydrate particles suspended in a range of condensate types at 1℃ and 5 MPa in the water-in-oil emulsion.

  1. Study on the recovery of hydrogen from refinery (hydrogen + methane) gas mixtures using hydrate technology

    Institute of Scientific and Technical Information of China (English)

    WANG XiuLin; CHEN GuangJin; YANG LanYing; ZHANG LinWei

    2008-01-01

    A novel technique for separating hydrogen from (H2 + CH4) gas mixtures through hydrate forma-tion/dissociation was proposed.In this work, a systematic experimental study was performed on the separation of hydrogen from (H2+CH4) feed mixtures with various hydrogen contents (mole fraction x =40%-90%).The experimental results showed that the hydrogen content could be enriched to as high as~94% for various feed mixtures using the proposed hydrate technology under a temperature slightly above 0℃ and a pressure below 5.0 MPa.With the addition of a small amount of suitable additives, the rate of hydrate formation could be increased significantly.Anti-agglomeration was used to disperse hydrate particles into the condensate phase.Instead of preventing hydrate growth (as in the kinetic inhibitor tests), hydrates were allowed to form, but only as small dispersed particles.Anti-agglomera-tion could keep hydrate particles suspended in a range of condensate types at 1℃ and 5 MPa in the water-in-oil emulsion.

  2. Low temperature X-ray diffraction studies of natural gas hydrate samples from the Gulf of Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Rawn, C.J. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Materials Science and Technology Div.; Sassen, R. [Texas A and M Univ., College Station, TX (United States). Geochemical and Environmental Research Group; Ulrich, S.M.; Phelps, T.J. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Biosciences Div.; Chakoumakos, B.C. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Neutron Scattering Science Div.; Payzant, E.A. [Oak Ridge National Laboratory, Oak Ridge, TN (United States). Center for Nanophase Materials Science

    2008-07-01

    Quantitative studies of natural clathrate hydrates are hampered by the difficulties associated with obtaining pristine samples for the sea floor without comprising their integrity. This paper discussed X-ray power diffraction studies conducted to measure natural gas hydrate samples obtained from the Green Canyon in the Gulf of Mexico. Data on the hydrate deposits were initially collected in 2002. The X-ray diffraction data were collected in order to examine the structure 2 (s2) gas hydrates as functions of temperature and time. A diffractometer with a theta-theta goniometer modified with a helium closed cycle refrigerator and temperature controller was used. Aragonite, quartz and halite phases were determined in the decomposed sample. Refined phase fractions for both the ice and the s2 hydrate were obtained as a function of temperature. Results of the study demonstrated that the amount of hydrates decreased with increasing temperatures and amounts of time. Large pieces of the hydrate showed heterogenous ice content. Dissociation rates were higher at lower temperatures. It was concluded that unusual trends observed for the smaller lattice parameter of the hydrates resulted from the formation of ice layers that acted as barriers to the released gases and caused increased isostatic pressures around the hydrate core. 9 refs., 6 figs.

  3. Recurrent dissociative fugue

    Directory of Open Access Journals (Sweden)

    Abhishek Mamarde

    2013-01-01

    Full Text Available Dissociative fugue is a rarely reported diagnostic entity. It is one of the least understood and yet clinically one of the most fascinating disorders in mental health. Here, we describe a case of fugue in a 32-year-old man who was brought to mental hospital with complete loss of memory for events pertaining to identity of self. This case illustrates the nature of presentation in hospital setting like mental hospital and effort taken to reintegrate his identity and reunite with his family.

  4. The hydration/dehydration behavior of aspartame revisited.

    Science.gov (United States)

    Guguta, C; Meekes, H; de Gelder, R

    2008-03-13

    Aspartame, l-aspartyl-l-phenylalanine methyl ester, has two hydrates (IA and IB), a hemi-hydrate (IIA) and an anhydrate (IIB). The hydration/dehydration behavior of aspartame was investigated using hot-humidity stage X-ray powder diffraction (XRPD) and molecular mechanics modeling in combination with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results of this study are compared to earlier studies on aspartame as described in literature. It is shown that earlier transition studies were hampered by incomplete conversions and wrong assignment of the forms. The combination of the techniques applied in this study now shows consistent results for aspartame and yields a clear conversion scheme for the hydration/dehydration behavior of the four forms.

  5. Perspective: Structure and ultrafast dynamics of biomolecular hydration shells

    Directory of Open Access Journals (Sweden)

    Damien Laage

    2017-07-01

    Full Text Available The structure and function of biomolecules can be strongly influenced by their hydration shells. A key challenge is thus to determine the extent to which these shells differ from bulk water, since the structural fluctuations and molecular excitations of hydrating water molecules within these shells can cover a broad range in both space and time. Recent progress in theory, molecular dynamics simulations, and ultrafast vibrational spectroscopy has led to new and detailed insight into the fluctuations of water structure, elementary water motions, and electric fields at hydrated biointerfaces. Here, we discuss some central aspects of these advances, focusing on elementary molecular mechanisms and processes of hydration on a femto- to picosecond time scale, with some special attention given to several issues subject to debate.

  6. The Hydrated Electron -- Jekyll And Hyde In A Test Tube

    Science.gov (United States)

    Robinson, G. W.; Hameka, H. F.

    1987-01-01

    Experimental evidence pertaining to the structure of the hydrated electron is reviewed. In agreement with recent picosecond optoelectronic data, it is concluded that at low or moderate temperatures the hydrated electron is not an electron at all! Rather, it is very likely a hydrated semi-ionic pair (OH...H30)(aq), having the chemical properties of either OH-(aq) or H(aq). However, under certain conditions, where the hydrogen-bond structure of the solvent is weak, the hydrated electron may delocalize somewhat into the surrounding water medium.to become "its old self", behaving more like an electron in a cavity. This fragmented personality of one of chemistry's most celebrated fundamental particles is further substantiated by ab initio quantum mechanical calculations.

  7. Dissociative Experiences in Psychiatric Inpatients

    OpenAIRE

    Ali Firoozabadi; Nooshin Reza Alizadeh

    2016-01-01

    Dissociative disorders are conditions that involve disruptions of memory, awareness, identity, or perception. Data collected in diverse geographic locations underline the consistency in clinical symptoms of dissociative disorders. In this cross-sectional descriptive study, prevalence of dissociative experiences has been screened in hospitalized patients in psychiatric wards of Shiraz University of Medical Sciences in Iran. One hundred and sixty patients in two hospitals entered the study. Our...

  8. Investigation on Gas Storage in Methane Hydrate

    Institute of Scientific and Technical Information of China (English)

    Zhigao Sun; Rongsheng Ma; Shuanshi Fan; Kaihua Guo; Ruzhu Wang

    2004-01-01

    The effect of additives (anionic surfactant sodium dodecyl sulfate (SDS), nonionic surfactant alkyl polysaccharide glycoside (APG), and liquid hydrocarbon cyclopentane (CP)) on hydrate induction time and formation rate, and storage capacity was studied in this work. Micelle surfactant solutions were found to reduce hydrate induction time, increase methane hydrate formation rate and improve methane storage capacity in hydrates. In the presence of surfactant, hydrate could form quickly in a quiescent system and the energy costs of hydrate formation were reduced. The critical micelle concentrations of SDS and APG water solutions were found to be 300× 10-6 and 500× 10-6 for methane hydrate formation system respectively. The effect of anionic surfactant (SDS) on methane storage in hydrates is more pronounced compared to a nonionic surfactant (APG). CP also reduced hydrate induction time and improved hydrate formation rate, but could not improve methane storage in hydrates.

  9. Dissociative Experiences in Psychiatric Inpatients

    Directory of Open Access Journals (Sweden)

    Ali Firoozabadi

    2016-11-01

    Full Text Available Dissociative disorders are conditions that involve disruptions of memory, awareness, identity, or perception. Data collected in diverse geographic locations underline the consistency in clinical symptoms of dissociative disorders. In this cross-sectional descriptive study, prevalence of dissociative experiences has been screened in hospitalized patients in psychiatric wards of Shiraz University of Medical Sciences in Iran. One hundred and sixty patients in two hospitals entered the study. Our tool to screen the prevalence of dissociative experiences was Dissociative Experience Scale (DES. Linear regression analysis shows that gender and age are predictors of high DES scores to some extent while psychiatric disorders are not good predictors. Age, gender and psychiatric disorders are poor predictors (almost 7% of high DES scores in this study (R square=0.69. In this study, patients with Borderline Personality Disorder had higher dissociative experiences based on DES score (Mean: 56.44, followed by Schizophrenic patients (Mean: 28.22 and patients with Bipolar Personality Disorder (Mean: 25.18. This study showed that we might be able to create a new category in psychological disorders based on dissociative experiences. As age, gender and psychological disorders were poor predictors of dissociative experiences, stronger predictors such as positive childhood psychological traumas could be responsible for dissociative disorders.

  10. [Dissociative disorders and affective disorders].

    Science.gov (United States)

    Montant, J; Adida, M; Belzeaux, R; Cermolacce, M; Pringuey, D; Da Fonseca, D; Azorin, J-M

    2014-12-01

    The phenomenology of dissociative disorders may be complex and sometimes confusing. We describe here two cases who were initially misdiagnosed. The first case concerned a 61 year-old woman, who was initially diagnosed as an isolated dissociative fugue and was actually suffering from severe major depressive episode. The second case concerned a 55 year-old man, who was suffering from type I bipolar disorder and polyvascular disease, and was initially diagnosed as dissociative fugue in a mooddestabilization context, while it was finally a stroke. Yet dissociative disorders as affective disorder comorbidity are relatively unknown. We made a review on this topic. Dissociative disorders are often studied through psycho-trauma issues. Litterature is rare on affective illness comorbid with dissociative disorders, but highlight the link between bipolar and dissociative disorders. The later comorbidity often refers to an early onset subtype with also comorbid panic and depersonalization-derealization disorder. Besides, unipolar patients suffering from dissociative symptoms have more often cyclothymic affective temperament. Despite the limits of such studies dissociative symptoms-BD association seems to correspond to a clinical reality and further works on this topic may be warranted. Copyright © 2014 L’Encéphale. Published by Elsevier Masson SAS.. All rights reserved.

  11. Dissociation Energies of Diatomic Molecules

    Institute of Scientific and Technical Information of China (English)

    FAN Qun-Chao; SUN Wei-Guo

    2008-01-01

    Molecular dissociation energies of 10 electronic states of alkali molecules of KH, 7LID, 7LiH, 6LiH, NaK, NaLi and NaRb are studied using the highest three accurate vibrational energies of each electronic state, and an improved parameter-free analytical formula which is obtained starting from the LeRoy-Bernstein vibrational energy expression near the dissociation limit. The results show that as long as the highest three vibrational energies are accurate, the current analytical formula will give accurate theoretical dissociation energies Detheory, which are in excellent agreement with the experimental dissociation energies Dexpte.

  12. Determination of pKa and Hydration Constants for a Series of α-Keto-Carboxylic Acids Using Nuclear Magnetic Resonance Spectrometry.

    Science.gov (United States)

    Lopalco, Antonio; Douglas, Justin; Denora, Nunzio; Stella, Valentino J

    2016-02-01

    The determination of the acid-base dissociation constants, and thus the pKa values, of α-keto acids such as pyruvic acid is complex because of the existence of these acids in their hydrated and nonhydrated or oxo state. Equilibria involved in the hydration and dehydration of the α-keto group of pyruvic acid and three other α-keto acids, 3-methyl-2-oxobutanoic acid, 4-methyl-2-oxopentanoic acid, and 2-oxo-2-phenylacetic acid, were investigated by proton and carbon nuclear magnetic resonance spectrometry, at constant ionic strength, 0.15, and 25 °C. Dissociation constants for the oxo (pKa(oxo)) and hydrated (pKa(hyd)) acids of each compound were estimated from the change in the degree of hydration with changes in pH and directly from the changes in chemical shifts of various hydrogen and carbons nuclei with pH. α-Keto acids showed greater hydration in their acidic forms than their carboxylate forms. The degree of hydration was sensitive to steric and electronic/resonance factors. As expected, the oxo forms of the acids were stronger acids compared with their hydrated analogs, and their dissociation constants were also sensitive to steric and electronic factors.

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

    Science.gov (United States)

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

    2015-08-03

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

  14. Dissociative State and Competence

    Directory of Open Access Journals (Sweden)

    Yu-Ju Lin

    2007-10-01

    Full Text Available This report presents the results of forensic evaluation of the civil competence of a case of alleged dissociative identity disorder (DID and discusses whether such dissociative states substantially jeopardize civil competence. A 40-year-old woman claimed that she had had many personalities since her college days. From the age of 37 to 40, she shopped excessively, which left her with millions of dollars of debt. She ascribed her shopping to a certain identity state, over which she had no control. (In this article, we use the term identity state to replace personality as an objective description of a mental state. She thus raised the petition of civil incompetence. During the forensic evaluation, it was found that the identity states were relatively stable and mutually aware of each other. The switch into another identity state was sometimes under voluntary control. The subject showed consistency and continuity in behavioral patterns across the different identity states, and no matter which identity state she was in, there was no evidence of impairment in her factual knowledge of social situations and her capacity for managing personal affairs. We hence concluded that she was civilly competent despite the claimed DID. Considering that the existence and diagnosis of DID are still under dispute and a diagnosis of DID alone is not sufficient to interdict a person's civil right, important clinical and forensic issues remain to be answered.

  15. Dissociative Electron Attachment

    Science.gov (United States)

    Arreola, Esmeralda; Esmeralda Arreola Collaboration; Leigh Hargreaves Collaboration

    Since the pioneering work of Boudiaffa et al., it has been understood that electrons, even with energies near or below the ionization threshold, are capable of initiating strand-breaks in human DNA. This discovery raised important questions for cancer treatments, since sub-ionizing electrons are known to be the most copiously produced secondary product of radiation therapy. But even to date these factors are largely excluded from dosimetry calculations. This lack of inclusion is, at least in part, certainly due to the dearth of fundamental data describing low-energy electron interactions with nucleotide molecules that form the basis of DNA. Understanding of how such slow electrons are able to damage DNA remains incomplete, but the strongly peaked nature of Boudiaffa et al.'s data gives strong hints at resonantly driven collision processes. DNA damage is therefore most likely driven by ``dissociative electron attachment'' (DEA). DEA is a rather complicated process to model due to the coupling of electronic and nuclear degrees of freedom in the molecule. At the California State University Fullerton, we are currently commissioning a new spectrometer to study dissociation channels, reaction rates and orientation effects in DEA collisions between slow electrons and nucleotide molecules. At the meeting we will present design parameters and commissioning data for this new apparatus.

  16. The impact of increased sedimentation rates associated with the decay of the Fennoscandian ice-sheet on gas hydrate stability and focused fluid flow at the Nyegga pockmark field, offshore mid-Norway

    Science.gov (United States)

    Karstens, Jens; Haflidason, Haflidi; Becker, Lukas; Petter Sejrup, Hans; Berndt, Christian; Planke, Sverre; Dahlgreen, Torbjørn

    2016-04-01

    Climatic changes since the Last Glacial Maximum (LGM) have affected the stability of gas hydrate systems on glaciated margins by sea-level changes, bottom water temperature changes, isostatic uplift or subsidence and variability in sedimentation rates. While subsidence and sea-level rise stabilize gas hydrate deposits, bottom water temperature warming, uplift and enhanced sedimentation have the opposite effect. The response of gas hydrate systems to post-glaciation warming is therefore a complex phenomenon and highly depends on the timing and magnitude of each of these processes. While the impact of bottom water warming on the dissociation of gas hydrates have been addressed in numerous studies, the potential of methane release due to basal gas hydrate dissociation during periods of warming has received less attention. Here, we present results from numerical simulations which show that rapid sedimentation associated with the decay of the Fennoscandian ice-sheet was capable of causing significant basal gas hydrate dissociation. The modeling is constrained by a high-resolution three-dimensional sedimentation rate reconstruction of the Nyegga pockmark field, offshore mid-Norway, obtained by integrating chrono-stratigraphic information derived from sediments cores and a seismo-stratigraphic framework. The model run covers the period between 28,000 and 15,000 calendar years before present and predict that the maximum sedimentation rate-related gas hydrate dissociation coincides temporally and spatially with enhanced focused fluid flow activity in the study area. Basal gas hydrate dissociation due to rapid sedimentation may have occurred as well in other glaciated continental margins after the LGM and may have caused the release of significant amounts of methane to the hydrosphere and atmosphere. The major post glaciation deposition centers are the location of some of the largest known submarine slide complexes. The release of free gas due to basal gas hydrate

  17. Kinetics and mechanism of the barotropic lamellar gel/lamellar liquid crystal phase transition in fully hydrated dihexadecylphosphatidylethanolamine: a time-resolved x-ray diffraction study using pressure jump.

    Science.gov (United States)

    Cheng, A; Hummel, B; Mencke, A; Caffrey, M

    1994-07-01

    The kinetics and mechanism of the barotropic lamellar gel (L beta')/lamellar liquid crystal (L alpha) phase transition in fully hydrated 1,2-dihexadecyl-sn-glycero-3-phosphoethanolamine (DHPE) has been studied using time-resolved x-ray diffraction (TRXRD). The phase transition was induced by pressure jumps of varying amplitudes in both the pressurization and depressurization directions at controlled temperature (78 degrees C). Both low- and wide-angle diffracted x rays were recorded simultaneously in live time using an x-ray-sensitive image intensifier coupled to a CCD camera and Super-VHS videotape recorder. Such an arrangement allowed for the direct and quantitative characterization of the long- (lamellar repeat spacing) and short-range order (chain packing) during a kinetic experiment. The image-processed live-time x-ray diffraction data were fitted using a nonlinear least-squares model, and the parameters of the fits were monitored continuously throughout the transition. The pressure-induced transitions from the L alpha to the L beta' phase and from the L beta' to the L alpha phase was two-state (no formation of intermediates apparent during the transition) to within the sensitivity limits of the method. The corresponding transit time (the time during which both phases coexist) associated with the long- and short-range order of the pressurization-induced L alpha-to-L beta' phase transition decreased to a limiting value of approximately 50 ms with increasing pressure jump amplitude. This limiting value was close to the response time of the detector/recording system. Thus, the intrinsic transit time of this transition in fully hydrated DHPE at 78 degrees C was less than or equal to 50 ms. In contrast, the depressurization-induced L beta'-to-L alpha phase transition was slower, taking approximately 1 s to complete, and occurred with no obvious dependence of the transit time on pressure jump amplitude. In the depressurization jump experiment, the lipid responded

  18. Study on molecular controlled mining system of methane hydrate; Methane hydrate no bunshi seigyo mining ni kansuru kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    Kuriyagawa, M.; Saito, T.; Kobayashi, H.; Karasawa, H.; Kiyono , F.; Nagaoki, R.; Yamamoto, Y.; Komai, T.; Haneda, H.; Takahashi, Y. [National Institute for Resources and Environment, Tsukuba (Japan); Nada, H. [Science and Technology Agency, Tokyo (Japan)

    1997-02-01

    Basic studies are conducted for the collection of methane from the methane hydrate that exists at levels deeper than 500m in the sea. The relationship between the hydrate generation mechanism and water cluster structure is examined by use of mass spectronomy. It is found that, among the stable liquid phase clusters, the (H2O)21H{sup +} cluster is the most stable. Stable hydrate clusters are in presence in quantities, and participate in the formation of hydrate crystal nuclei. For the elucidation of the nucleus formation mechanism, a kinetic simulation is conducted of molecules in the cohesion system consisting of water and methane molecules. Water molecules that array near methane molecules at the normal pressure is disarrayed under a higher pressure for rearray into a hydrate structure. Hydrate formation and breakdown in the three-phase equilibrium state of H2O, CH4, and CO2 at a low temperature and high pressure are tested, which discloses that supercooling is required for formation, that it is possible to extract CH4 first for replacement by guest molecule CO2 since CO2 is stabler than CH4 at a lower pressure or higher temperature, and that formation is easier to take place when the grain diameter is larger at the formation point since larger grain diameters result in a higher formation temperature. 3 figs.

  19. Growth mechanism of a gas clathrate hydrate from a dilute aqueous gas solution: a molecular dynamics simulation of a three-phase system.

    Science.gov (United States)

    Nada, Hiroki

    2006-08-24

    A molecular dynamics simulation of a three-phase system including a gas clathrate, liquid water, and a gas was carried out at 298 K and high pressure in order to investigate the growth mechanism of the clathrate from a dilute aqueous gas solution. The simulation indicated that the clathrate grew on interfaces between the clathrate and the liquid water, after transfer of the gas molecules from the gas phase to the interfaces. The results suggest a two-step process for growth: first, gas molecules are arranged at cage sites, and second, H(2)O molecules are ordered near the gas molecules. The results also suggest that only the H(2)O molecules, which are surrounded or sandwiched by the gas molecules, form the stable polygons that constitute the cages of the clathrate. In addition, the growth of the clathrate from a concentrated aqueous gas solution was also simulated, and the results suggested a growth mechanism in which many H(2)O and gas molecules correctively form the structure of the clathrate. The clathrate grown from the concentrated solution contained some empty cages, whereas the formation of empty cages was not observed during the growth from the dilute solution. The results obtained by both simulations are compared with the results of an experimental study, and the growth mechanism of the clathrate in a real system is discussed.

  20. Theoretical study on mechanisms of structural rearrangement and ionic dissociation in the HCl(H 2O) 4 cluster with path-integral molecular dynamics simulations

    Science.gov (United States)

    Sugawara, Shuichi; Yoshikawa, Takehiro; Takayanagi, Toshiyuki; Tachikawa, Masanori

    2011-01-01

    The structural rearrangement process for the HCl(H2O)4 cluster has been studied by path-integral molecular dynamics simulations, where 'on-the-fly' calculation of the potential energy surface is done with the PM3-MAIS semiempirical level. The mechanisms of the rearrangement were analyzed using appropriate collective coordinates as well as detailed potential energy diagrams derived from low-lying stationary points. It was found that the vibrational entropy mainly determines the stability of the cluster structure especially at high temperatures. We have also found that the acidity of HCl in the cluster correlates with the coordination number of chlorine with respect water molecules.

  1. Electron Capture Dissociation of Weakly Bound Polypeptide Polycationic Complexes

    DEFF Research Database (Denmark)

    Haselmann, Kim F; Jørgensen, Thomas J D; Budnik, Bogdan A;

    2002-01-01

    We have previously reported that, in electron capture dissociation (ECD), rupture of strong intramolecular bonds in weakly bound supramolecular aggregates can proceed without dissociation of weak intermolecular bonds. This is now illustrated on a series of non-specific peptide-peptide dimers...... as well as specific complexes of modified glycopeptide antibiotics with their target peptide. The weak nature of bonding is substantiated by blackbody infrared dissociation, low-energy collisional excitation and force-field simulations. The results are consistent with a non-ergodic ECD cleavage mechanism....

  2. Scapulothoracic Dissociation: A Rare Variant: A Case Report

    Directory of Open Access Journals (Sweden)

    Rajat Jangir

    2014-07-01

    Full Text Available Scapulothoracic dissociation is a rare injury involving separation of scapula from the thorax along with the upper extremity. Majority of the patients have concomitant neurovascular injury and the prognosis is uniformly poor in such cases. We present a case of scapulothoracic dissociation with comminuted fracture of scapula and acromioclavicular joint disruption without neurovascular deficit. There were associated avulsion fractures of the spinous processes of vertebrae (T3-T5. Such presentation is rare in an already rare scapulothoracic dissociation injury. A discussion regarding the probable mechanism of injury, management and prognosis is presented.

  3. Hydrates fighting tools; Des outils de lutte contre les hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    2003-04-01

    Shell Exploration and Production company (SEPCo) is the operator of the 'Popeye' deep offshore field in the Gulf of Mexico. Thanks to the introduction of a low dosing hydrates inhibitor (LDHI) elaborated by Shell Global Solutions, the company has added a 7.5 Gpc extra volume of gas to its recoverable reserves. This new technology avoids the plugging of pipes by hydrates formation. (J.S.)

  4. Deep-ocean field test of methane hydrate formation from a remotely operated vehicle

    Science.gov (United States)

    Brewer, P.G.; Orr, F.M.; Friederich, G.; Kvenvolden, K.A.; Orange, D.L.; McFarlane, J.; Kirkwood, W.

    1997-01-01

    We have observed the process of formation of clathrate hydrates of methane in experiments conducted on the remotely operated vehicle (ROY) Ventana in the deep waters of Monterey Bay. A tank of methane gas, acrylic tubes containing seawater, and seawater plus various types of sediment were carried down on Ventana to a depth of 910 m where methane gas was injected at the base of the acrylic tubes by bubble stream. Prior calculations had shown that the local hydrographic conditions gave an upper limit of 525 m for the P-T boundary defining methane hydrate formation or dissociation at this site, and thus our experiment took place well within the stability range for this reaction to occur. Hydrate formation in free sea-water occurred within minutes as a buoyant mass of translucent hydrate formed at the gas-water interface. In a coarse sand matrix the Filling of the pore spaces with hydrate turned the sand column into a solidified block, which gas pressure soon lifted and ruptured. In a fine-grained black mud the gas flow carved out flow channels, the walls of which became coated and then filled with hydrate in larger discrete masses. Our experiment shows that hydrate formation is rapid in natural seawater, that sediment type strongly influences the patterns of hydrate formation, and that the use of ROV technologies permits the synthesis of large amounts of hydrate material in natural systems under a variety of conditions so that fundamental research on the stability and growth of these substances is possible.

  5. Influence of ultra-fine fly ash on hydration shrinkage of cement paste

    Institute of Scientific and Technical Information of China (English)

    GAO Ying-li; ZHOU Shi-qiong

    2005-01-01

    Hydration shrinkage generated by cement hydration is the cause of autogenous shrinkage of high strength concrete. It may result in the volume change and even cracking of mortar and concrete. According to the data analysis in a series of experimental studies, the influence of ultra-fine fly ash on the hydration shrinkage of composite cementitious materials was investigated. It i