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Sample records for hydrated fluid phase

  1. Coupled mass transfer through a fluid phase and volume preservation during the hydration of granulite: An example from the Bergen Arcs, Norway

    NASA Astrophysics Data System (ADS)

    Centrella, Stephen; Austrheim, Håkon; Putnis, Andrew

    2015-11-01

    The Precambrian granulite facies rocks of Lindås Nappe, Bergen Arcs, Caledonides of W. Norway are partially hydrated at amphibolite and eclogite facies conditions. The Lindås Nappe outcrops over an area of ca. 1000 km2 where relict granulite facies lenses make up only ca. 10%. At Hillandsvatnet, garnetite displays sharp hydration fronts across which the granulite facies assemblage composed of garnet (55%) and clinopyroxene (45%) is replaced by an amphibolite facies mineralogy defined by chlorite, epidote and amphibole. The major element bulk composition does not change significantly across the hydration front, apart from the volatile components (loss on ignition, LOI) that increases from 0.17 wt.% in the granulite to 2.43 wt.% in the amphibolite. However the replacements of garnet and of clinopyroxene are pseudomorphic so that the grain shapes of the garnet and clinopyroxene are preserved even when they are completely replaced. The textural evolution during the replacement of garnet by pargasite, epidote and chlorite and of pyroxene by hornblende and quartz in our rock sample conforms to that expected by a coupled dissolution-precipitation mechanism. SEM and electron microprobe analysis coupled with the software XMapTools V 1.06.1 were used to quantify the local mass transfer required during the replacement processes. The element losses and gains in replacing the garnet are approximately balanced by the opposite gains and losses associated with the replacement of clinopyroxene. The coupling between dissolution and precipitation on both the grain and whole rock spatial scale preserves the volume of the rock throughout the hydration process. However, the hydration involves reduction of rock density and mass balance calculations, together with volume preservation (isovolumetric reaction) require a significant loss of the mass of the rock to the fluid phase. This suggests a mechanism for coupling between the local stress generated by hydration reactions and mass

  2. Hydration forces at solid and fluid biointerfaces.

    PubMed

    Shrestha, Buddha Ratna; Banquy, Xavier

    2016-03-01

    The authors review the different molecular mechanisms giving rise to the repulsive hydration force between biologically relevant surfaces such as lipid bilayers and bioceramics. As the authors will show, the hydration force manifests itself in very different and subtle ways depending on the substrates. Soft, mobile surfaces such as lipid bilayers tend to exhibit monotonic, decaying hydration force, originated from the entropic constriction of the lipid head groups. Solid surfaces, on the other hand, tend to exhibit a periodic oscillatory hydration force, originated from the surface induced polarization of water molecules. In this review, the authors will describe both subtle faces of this important interaction by first describing the early experiments performed on solid surfaces and their interpretation by recent simulation studies. Then, the authors will describe the hydration force between fluid interfaces such as bilayers and explain how experimentally researchers have unraveled the dominant role of the lipid head groups' conformation. PMID:26795057

  3. Fuel cell membrane hydration and fluid metering

    DOEpatents

    Jones, Daniel O.; Walsh, Michael M.

    1999-01-01

    A hydration system includes fuel cell fluid flow plate(s) and injection port(s). Each plate has flow channel(s) with respective inlet(s) for receiving respective portion(s) of a given stream of reactant fluid for a fuel cell. Each injection port injects a portion of liquid water directly into its respective flow channel in order to mix its respective portion of liquid water with the corresponding portion of the stream. This serves to hydrate at least corresponding part(s) of a given membrane of the corresponding fuel cell(s). The hydration system may be augmented by a metering system including flow regulator(s). Each flow regulator meters an injecting at inlet(s) of each plate of respective portions of liquid into respective portion(s) of a given stream of fluid by corresponding injection port(s).

  4. Fuel cell membrane hydration and fluid metering

    DOEpatents

    Jones, Daniel O.; Walsh, Michael M.

    2003-01-01

    A hydration system includes fuel cell fluid flow plate(s) and injection port(s). Each plate has flow channel(s) with respective inlet(s) for receiving respective portion(s) of a given stream of reactant fluid for a fuel cell. Each injection port injects a portion of liquid water directly into its respective flow channel. This serves to hydrate at least corresponding part(s) of a given membrane of the corresponding fuel cell(s). The hydration system may be augmented by a metering system including flow regulator(s). Each flow regulator meters an injecting at inlet(s) of each plate of respective portions of liquid into respective portion(s) of a given stream of fluid by corresponding injection port(s).

  5. Phase Transition of Methane Gas Hydrate and Response of Marine Gas Hydrate Systems to Environmental Changes

    NASA Astrophysics Data System (ADS)

    Xu, W.

    2003-12-01

    Gas hydrates, which contain mostly methane as the gas component in marine sediment, are stable under relatively high pressure and low temperature conditions such as those found along continental margins and permafrost regions. Its stability is mostly controlled by in-situ pressure, temperature and salinity of pore fluid. Environmentally introduced changes in pressure and temperature can affect the stability of gas hydrate in marine sediment. While certain changes may enhance the process of gas hydrate formation, we are much more interested in the resultant dissociation processes, which may contribute to sub-marine slope instability, seafloor sediment failure, formation of mud volcanoes and pock marks, potential vulnerability of engineering structures, and the risk to drilling and production. We have been developing models to quantify phase transition processes of marine gas hydrates and to investigate the response of marine gas hydrate systems to environmental changes. Methane gas hydrate system is considered as a three-component (water, methane, salt) four-phase (liquid, gas, hydrate, halite) system. Pressure, temperature and salinity of pore fluid constrain the stability of gas hydrate and affect phase transition processes via their effects on methane solubility and fluid density and enthalpy. Compared to the great quantity of studies on its stability in the literature, in-depth research on phase transition of gas hydrate is surprisingly much less. A method, which employs pressure, enthalpy, salinity and methane content as independent variables, is developed to calculate phase transition processes of the three-component four-phase system. Temperature, an intensive thermodynamic parameter, is found not sufficient in describing phase transition of gas hydrate. The extensive thermodynamic parameter enthalpy, on the other hand, is found to be sufficient both in calculation of the phase transition processes and in modeling marine gas hydrate systems. Processes

  6. Impact of Compound Hydrate Dynamics on Phase Boundary Changes

    NASA Astrophysics Data System (ADS)

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

    2006-12-01

    Compound hydrate reactions are affected by the local concentration of hydrate forming materials (HFM). The relationship between HFM composition and the phase boundary is as significant as temperature and pressure. Selective uptake and sequestration of preferred hydrate formers (PF) has wide ranging implications for the state and potential use of natural hydrate formation, including impact on climate. Rising mineralizing fluids of hydrate formers (such as those that occur on Earth and are postulated to exist elsewhere in the solar system) will sequester PF before methane, resulting in a positive relationship between depth and BTU content as ethane and propane are removed before methane. In industrial settings the role of preferred formers can separate gases. When depressurizing gas hydrate to release the stored gas, the hydrate initial composition will set the decomposition phase boundary because the supporting solution takes on the composition of the hydrate phase. In other settings where hydrate is formed, transported, and then dissociated, similar effects can control the process. The behavior of compound hydrate systems can primarily fit into three categories: 1) In classically closed systems, all the material that can form hydrate is isolated, such as in a sealed laboratory vessel. In such systems, formation and decomposition are reversible processes with observed hysteresis related to mass or heat transfer limitations, or the order and magnitude in which individual hydrate forming gases are taken up from the mixture and subsequently released. 2) Kinetically closed systems are exposed to a solution mass flow across a hydrate mass. These systems can have multiple P-T phase boundaries based on the local conditions at each face of the hydrate mass. A portion of hydrate that is exposed to fresh mineralizing solution will contain more preferred hydrate formers than another portion that is exposed to a partially depleted solution. Examples of kinetically closed

  7. Indications of shallow fluid recirculation on Hydrate Ridge

    NASA Astrophysics Data System (ADS)

    Gubsch, S.; Gust, G.; Linke, P.; Sommer, S.; Viergutz, T.; Wallmann, K.

    2003-04-01

    Hydrate Ridge is a region of near-surface gas hydrates with considerable methane-rich fluid release. The release rate of methane is estimated up to 10 mmol/m^2/d. Tidal flows and topography strongly mix the water column, yet depending on the inhomogeneous distribution of gas hydrates located below the surface a distinct horizontal zonation of biological activity exists. Bacterial mats of Beggiatoa sp and clam fields of the genus Calyptogena sp are biomarkers for near surface gas hydrates. These regions are assumed to provide an intense fluid-porewater exchange. Guided by the discharge data from Linke and Tryon from this site, a newly developed FLUFO chamber was used on cruise Sonne 165-1 to quantify 2-phase fluid exchange across the sea floor and to determine both driving force and the high-frequency end of its temporal and spatial pattern. Monitoring of bottom current and hydrostatic pressure provided the environmental conditions during deployments, revealing strong tidal flows up to 50 cm/s. The device performed well, and at 5 locations on Hydrate Ridge inflow and outflow events were recorded during deployments lasting up to 72 hours. Of these locations, three were grouped very close on the Southern Summit with an average distance of 50 m amongst each other. The fourth location (control) had a distance of 500 m to this group. The remaining deployment site was selected in the Eastern Basin at a distance of 67 km. The unexpected result was a fluid exchange across the sea floor which involved per tidal phase a water layer of < 28mm height. We observed mostly inflow at 2.5 and 5 ml/min at two sites, mostly outflow at 2 ml/min at one site and nearly-balanced inflow and outflow at one site per tidal cycle. Combining the venting/inflow directions and speeds with the tide signal confirms the relation between fluid flux and tide reported by Linke. Upon closer examination, tidal flow rather than tidal phase controlled the fluid exchange, which is very low and very shallow

  8. Method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, Jr., Earle D.

    1995-01-01

    Discussed is a process for preventing clathrate hydrate masses from impeding the flow of fluid in a fluid system. An additive is contacted with clathrate hydrate masses in the system to prevent those clathrate hydrate masses from impeding fluid flow. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member and/or six member cyclic chemical groupings. Additives include poly(N-vinyl-2-pyrrolidone) and hydroxyethylcellulose, either in combination or alone.

  9. Hydration biomarkers and dietary fluid consumption of women.

    PubMed

    Armstrong, Lawrence E; Johnson, Evan C; Munoz, Colleen X; Swokla, Brittany; Le Bellego, Laurent; Jimenez, Liliana; Casa, Douglas J; Maresh, Carl M

    2012-07-01

    Normative values and confidence intervals for the hydration indices of women do not exist. Also, few publications have precisely described the fluid types and volumes that women consume. This investigation computed seven numerical reference categories for widely used hydration biomarkers (eg, serum and urine osmolality) and the dietary fluid preferences of self-reported healthy, active women. Participants (n=32; age 20±1 years; body mass 59.6±8.5 kg; body mass index [calculated as kg/m(2)] 21.1±2.4) were counseled in the methods to record daily food and fluid intake on 2 consecutive days. To reduce day-to-day body water fluctuations, participants were tested only during the placebo phase of the oral contraceptive pill pack. Euhydration was represented by the following ranges: serum osmolality=293 to 294 mOsm/kg; mean 24-hour total fluid intake=2,109 to 2,506 mL/24 hours; mean 24-hour total beverage intake=1,300 to 1,831 mL/24 hours; urine volume=951 to 1,239 mL/24 hours; urine specific gravity=1.016 to 1.020; urine osmolality=549 to 705 mOsm/kg; and urine color=5. However, only 3% of women experienced a urine specific gravity <1.005, and only 6% exhibited a urine color of 1 or 2. Water (representing 45.3% and 47.9% of 24-hour total fluid intake), tea, milk, coffee, and fruit juice were consumed in largest volumes. In conclusion, these data provide objective normative values for hyperhydration, euhydration, and dehydration that can be used by registered dietitians and clinicians to counsel women about their hydration status. PMID:22889635

  10. Hydration states of AFm cement phases

    SciTech Connect

    Baquerizo, Luis G.; Matschei, Thomas; Scrivener, Karen L.; Saeidpour, Mahsa; Wadsö, Lars

    2015-07-15

    The AFm phase, one of the main products formed during the hydration of Portland and calcium aluminate cement based systems, belongs to the layered double hydrate (LDH) family having positively charged layers and water plus charge-balancing anions in the interlayer. It is known that these phases present different hydration states (i.e. varying water content) depending on the relative humidity (RH), temperature and anion type, which might be linked to volume changes (swelling and shrinkage). Unfortunately the stability conditions of these phases are insufficiently reported. This paper presents novel experimental results on the different hydration states of the most important AFm phases: monocarboaluminate, hemicarboaluminate, strätlingite, hydroxy-AFm and monosulfoaluminate, and the thermodynamic properties associated with changes in their water content during absorption/desorption. This data opens the possibility to model the response of cementitious systems during drying and wetting and to engineer systems more resistant to harsh external conditions.

  11. Fe-containing phases in hydrated cements

    SciTech Connect

    Dilnesa, B.Z.; Wieland, E.; Lothenbach, B.; Dähn, R.; Scrivener, K.L.

    2014-04-01

    In this study synchrotron X-ray absorption spectroscopy (XAS) has been applied, an element specific technique which allows Fe-containing phases to be identified in the complex mineral mixture of hydrated cements. Several Fe species contributed to the overall Fe K-edge spectra recorded on the cement samples. In the early stage of cement hydration ferrite was the dominant Fe-containing mineral. Ferrihydrite was detected during the first hours of the hydration process. After 1 day the formation of Al- and Fe-siliceous hydrogarnet was observed, while the amount of ferrihydrite decreased. The latter finding agrees with thermodynamic modeling, which predicts the formation of Fe-siliceous hydrogarnet in Portland cement systems. The presence of Al- and Fe-containing siliceous hydrogarnet was further substantiated in the residue of hydrated cement by performing a selective dissolution procedure. - Highlights: • Fe bound to ferrihydrite at early age hydration • Fe found to be stable in siliceous hydrogarnet at longer term age hydration • Fe-containing AFt and AFm phases are less stable than siliceous hydrogarnet. • The study demonstrates EXAFS used to identify amorphous or poorly crystalline phases.

  12. Salinity of multivolatile fluid inclusions determined from clathrate hydrate stability

    NASA Astrophysics Data System (ADS)

    Diamond, Larryn W.

    1994-01-01

    Measurements of the final dissociation temperature of gas-clathrate hydrates ( TmCLA) are routinely used to determine the salinity of fluid inclusions which contain a volatile component in addition to water. Traditionally, experimental data are used to quantitatively relate TmCLA to the inclusion electrolyte concentration. Because of limitations in the experimental database, however, this method has hitherto not been applicable to the multivolatile fluid inclusions that are common in crustal rocks. A general solution to this problem is provided by statistical thermodynamics predictions of multivolatile clathrate stability. Published theoretical models explicitly account for the effect of aqueous NaCl in depressing the stability of clathrates composed of any mixture of CO 2, N 2, H 2S, CH 4 and higher-order hydrocarbons. Analysis of phase relations in complex clathrate systems shows that such theoretical predictions yield model salinities if the following fluid inclusion data are available: (1) the identity of the phase assemblage at TmCLA, (2) the relative concentrations of the volatile species, and (3) either the homogenization temperature of the volatile fluid fraction (bubble point or dew point, either stable or metastable), or an independent estimate of internal pressure at TmCLA. Additional data on fluid inclusion cation ratios can be incorporated in the calculations to recast equivalent weight percent aqueous NaCl in terms of effective electrolyte concentrations. New experimental data on mixed N 2-CO 2 clathrates, obtained from synthetic fluid inclusions, provide a test of both the model predictions and of the analytical procedure proposed for natural fluid inclusions. While the accuracy of the predictions varies between volatile compositions, the uncertainties in the salinities derived from the statistical thermodynamics method are generally of the order acceptable for geochemical applications. Applications to multivolatile, multi-electrolyte fluid

  13. Analysis of the theoretical model of drilling fluid invading into oceanic gas hydrates-bearing sediment

    NASA Astrophysics Data System (ADS)

    Zhang, L.; Ning, F.; Jiang, G.; Wu, N.; Wu, D.

    2009-12-01

    Oceanic gas hydrate-bearing sediment is usually porous media, with the temperature and pressure closer to the curve of hydrate phase equilibrium than those in the permafrost region. In the case of near-balanced or over-balanced drilling through this sediment, the water-based drilling fluid used invades into this sediment, and hydrates decompose with heat transfer between drilling fluid and this sediment. During these processes, there are inevitably energy and mass exchanges between drilling fluid and the sediment, which will affect the logging response, borehole stability and reservoir evaluation. When drilling fluid invades into this sediment, solid and liquid phases of drilling fluid permeate into the wellbore and displace original fluids and solids, and water content of formation increases. With the temperature and pressure changing, gas hydrates in the sediment decompose into gas and water, and water content of formation further changes. When the filter cakes form, the invasion of drilling fluid is weakened. This process is accompanied by the heat and mass transfer within the range from wellbore to undisturbed area, including heat conduction of rock matrix, the convective heat transfer of fluids invaded, the heat absorbing of hydrate decomposition and the mass exchange between fluids invaded and the gas and water generated by hydrate decomposition. As a result, dynamic balance is built up and there are generally four different regions from wellbore to undisturbed area, i.e. filter cakes region, filter liquor region, water/free gas region, and water/free gas/hydrate region. According to the analysis on the invasion of drilling fuild into sediment, the whole invasion process can be described as an anisothermal and unstable displacement and diffusion process coupled with phase change. Refering to models of drilling fuilds invasion into normal oil and gas formation and natrual gas production from hydrate deposit by heating, the model of the invasion of drilling

  14. Method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, Jr., Earle D.

    1995-01-01

    Discussed is a process for preventing clathrate hydrate masses from impeding the flow of fluid in a fluid system. An additive is contacted with clathrate hydrate masses in the system to prevent those clathrate hydrate masses from impeding fluid flow. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include poly(N-vinyl-2-pyrrolidone) and hydroxyethylcellulose, either in combination or alone. Additives can also contain multiple cyclic chemical groupings having different size rings. One such additive is sold under the name Gaffix VC-713.

  15. Method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, E.D. Jr.

    1995-07-11

    Discussed is a process for preventing clathrate hydrate masses from impeding the flow of fluid in a fluid system. An additive is contacted with clathrate hydrate masses in the system to prevent those clathrate hydrate masses from impeding fluid flow. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include poly(N-vinyl-2-pyrrolidone) and hydroxyethylcellulose, either in combination or alone. Additives can also contain multiple cyclic chemical groupings having different size rings. One such additive is sold under the name Gaffix VC-713.

  16. The phase behavior of hydrated cholesterol.

    PubMed

    Loomis, C R; Shipley, G G; Small, D M

    1979-05-01

    The thermotropic phase behavior of cholesterol monohydrate in water was investigated by differential scanning calorimetry, polarizing light microscopy, and x-ray diffraction. In contrast to anhydrous cholesterol which undergoes a polymorphic crystalline transition at 39 degrees C and a crystalline to liquid transition at 151 degrees C, the closed system of cholesterol monohydrate and water exhibited three reversible endothermic transitions at 86, 123, and 157 degrees C. At 86 degrees C, cholesterol monohydrate loses its water of hydration, forming the high temperature polymorph of anhydrous cholesterol. At least 24 hours were required for re-hydration of cholesterol and the rate of hydration was dependent on the polymorphic crystalline form of anhydrous cholesterol. At 123 degrees C, anhydrous crystalline cholesterol in the presence of excess water undergoes a sharp transition to a birefringent liquid crystalline phase of smectic texture. The x-ray diffraction pattern obtained from this phase contained two sharp low-angle reflections at 37.4 and 18.7 A and a diffuse wide-angle reflection centered at 5.7 A, indicating a layered smectic type of liquid crystalline structure with each layer being two cholesterol molecules thick. The liquid crystalline phase is stable over the temperature range of 123 to 157 degrees C before melting to a liquid dispersed in water. The observation of a smectic liquid crystalline phase for hydrated cholesterol correlates with its high surface activity and helps to explain its ability to exist in high concentrations in biological membranes. PMID:458269

  17. Hydration and vascular fluid shifts during exercise in the heat

    SciTech Connect

    Sawka, M.N.; Francesconi, R.P.; Pimental, N.A.; Pandolf, K.B.

    1984-01-01

    The present study has the primary objective to determine the effects of hydration level on vascular fluid shifts during exercise in the heat. The effect of gender on these fluid shifts was also investigated. The subjects employed in the tests included six male and six female volunteers. It was found that hemoconcentration occurs when subjects are hypohydrated and are performing light intensity exercise in the heat. A decrease in total plasma protein was observed under these test conditions. Gender does not alter vascular fluid shifts during exercise in the heat when subjects are matched with respect to fitness level. It is concluded that hydration level alters vascular fluid shifts during exercise in a hot environment.

  18. Soft hydrated sliding interfaces as complex fluids.

    PubMed

    Kim, Jiho; Dunn, Alison C

    2016-08-21

    Hydrogel surfaces are biomimics for sensing and mobility systems in the body such as the eyes and large joints due to their important characteristics of flexibility, permeability, and integrated aqueous component. Recent studies have shown polymer concentration gradients resulting in a less dense region in the top micrometers of the surface. Under shear, this gradient is hypothesized to drive lubrication behavior due to its rheological similarity to a semi-dilute polymer solution. In this work we map 3 distinct lubricating regimes between a polyacrylamide surface and an aluminum annulus using stepped-velocity tribo-rheometry over 5 decades of sliding speed in increasing and decreasing steps. These regimes, characterized by weakly or strongly time-dependent response and thixotropy-like hysteresis, provide the skeleton of a lubrication curve for hydrogel-against-hard material interfaces and support hypotheses of polymer mechanics-driven lubrication. Tribo-rheometry is particularly suited to uncover the lubrication mechanisms of complex interfaces such as are formed with hydrated hydrogel surfaces and biological surfaces. PMID:27425448

  19. Hydration and endocrine responses to intravenous fluid and oral glycerol.

    PubMed

    van Rosendal, S P; Strobel, N A; Osborne, M A; Fassett, R G; Coombes, J S

    2015-06-01

    Athletes use intravenous (IV) saline in an attempt to maximize rehydration. The diuresis from IV rehydration may be circumvented through the concomitant use of oral glycerol. We examined the effects of rehydrating with differing regimes of oral and IV fluid, with or without oral glycerol, on hydration, urine, and endocrine indices. Nine endurance-trained men were dehydrated by 4% bodyweight, then rehydrated with 150% of the fluid lost via four protocols: (a) oral = oral fluid only; (b) oral glycerol = oral fluid with added glycerol (1.5 g/kg); (c) IV = 50% IV fluid, 50% oral fluid; and (d) IV with oral glycerol = 50% IV fluid, 50% oral fluid with added glycerol (1.5 g/kg), using a randomized, crossover design. They then completed a cycling performance test. Plasma volume restoration was highest in IV with oral glycerol > IV > oral glycerol  > oral. Urine volume was reduced in both IV trials compared with oral. IV and IV with oral glycerol resulted in lower aldosterone levels during rehydration and performance, and lower cortisol levels during rehydration. IV with oral glycerol resulted in the greatest fluid retention. In summary, the IV conditions resulted in greater fluid retention compared with oral and lower levels of fluid regulatory and stress hormones compared with both oral conditions. PMID:25943662

  20. Subcutaneous fluid administration and the hydration of older people.

    PubMed

    Gabriel, Janice

    Hypodermoclysis, or the subcutaneous administration of fluids, is a method of rehydration that is not routinely used in the UK. Yet it is a simple and effective method of fluid administration for individuals with mild-to-moderate dehydration, especially for the frail and elderly (Sasson and Shvartzman, 2001). Subcutaneous infusion is an alternative route of parenteral administration. It provides a number of advantages over the intravenous route for those individuals unable to tolerate enteral fluids, as it is associated with fewer complications, as well as a wider range of infusion sites. This makes it particularly advantageous for frail and/or older patients requiring low-volume hydration in the community setting. This article discusses indications and contraindications for subcutaneous infusions, as well as patient assessment, placement, securement and potential complications. PMID:25158361

  1. Subcutaneous fluid administration and the hydration of older people.

    PubMed

    Gabriel, Janice

    2014-07-01

    Hypodermoclysis, or the subcutaneous administration of fluids, is a method of rehydration that is not routinely used in the UK. Yet it is a simple and effective method of fluid administration for individuals with mild-to-moderate dehydration, especially for the frail and elderly ( Sasson and Shvartzman, 2001 ). Subcutaneous infusion is an alternative route of parenteral administration. It provides a number of advantages over the intravenous route for those individuals unable to tolerate enteral fluids, as it is associated with fewer complications, as well as a wider range of infusion sites. This makes it particularly advantageous for frail and/or older patients requiring low-volume hydration in the community setting. This article discusses indications and contraindications for subcutaneous infusions, as well as patient assessment, placement, securement and potential complications. PMID:25062366

  2. Additives and method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, E.D. Jr.; Christiansen, R.L.; Lederhos, J.P.; Long, J.P.; Panchalingam, V.; Du, Y.; Sum, A.K.W.

    1997-06-17

    Discussed is a process for preventing clathrate hydrate masses from detrimentally impeding the possible flow of a fluid susceptible to clathrate hydrate formation. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include polymers having lactam rings. Additives can also contain polyelectrolytes that are believed to improve conformance of polymer additives through steric hindrance and/or charge repulsion. Also, polymers having an amide on which a C{sub 1}-C{sub 4} group is attached to the nitrogen and/or the carbonyl carbon of the amide may be used alone, or in combination with ring-containing polymers for enhanced effectiveness. Polymers having at least some repeating units representative of polymerizing at least one of an oxazoline, an N-substituted acrylamide and an N-vinyl alkyl amide are preferred.

  3. Additives and method for controlling clathrate hydrates in fluid systems

    DOEpatents

    Sloan, Jr., Earle Dendy; Christiansen, Richard Lee; Lederhos, Joseph P.; Long, Jin Ping; Panchalingam, Vaithilingam; Du, Yahe; Sum, Amadeu Kun Wan

    1997-01-01

    Discussed is a process for preventing clathrate hydrate masses from detrimentally impeding the possible flow of a fluid susceptible to clathrate hydrate formation. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include polymers having lactam rings. Additives can also contain polyelectrolytes that are believed to improve conformance of polymer additives through steric hinderance and/or charge repulsion. Also, polymers having an amide on which a C.sub.1 -C.sub.4 group is attached to the nitrogen and/or the carbonyl carbon of the amide may be used alone, or in combination with ring-containing polymers for enhanced effectiveness. Polymers having at least some repeating units representative of polymerizing at least one of an oxazoline, an N-substituted acrylamide and an N-vinyl alkyl amide are preferred.

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

    PubMed

    Rayne, Sierra; Forest, Kaya

    2016-01-01

    The SPARC software program and comparative density functional theory (DFT) calculations were used to investigate the aqueous phase hydration equilibrium constants (Khyd) of perfluoroalkyl aldehydes (PFAlds) and n:2 fluorotelomer aldehydes (FTAlds). Both classes are degradation products of known industrial compounds and environmental contaminants such as fluorotelomer alcohols, iodides, acrylates, phosphate esters, and other derivatives, as well as hydrofluorocarbons and hydrochlorofluorocarbons. Prior studies have generally failed to consider the hydration, and subsequent potential hydrate acidity, of these compounds, resulting in incomplete and erroneous predictions as to their environmental behavior. In the current work, DFT calculations suggest that all PFAlds will be dominantly present as the hydrated form in aqueous solution. Both SPARC and DFT calculations suggest that FTAlds will not likely be substantially hydrated in aquatic systems or in vivo. PFAld hydrates are expected to have pKa values in the range of phenols (ca. 9 to 10), whereas n:2 FTAld hydrates are expected to have pKa values ca. 2 to 3 units higher (ca. 12 to 13). In order to avoid spurious modeling predictions and a fundamental misunderstanding of their fate, the molecular and/or dissociated hydrate forms of PFAlds and FTAlds need to be explicitly considered in environmental, toxicological, and waste treatment investigations. The results of the current study will facilitate a more complete examination of the environmental fate of PFAlds and FTAlds. PMID:26980678

  5. Gas hydrate formation rates from dissolved-phase methane in porous laboratory specimens

    USGS Publications Warehouse

    Waite, William F.; Spangenberg, E.K.

    2013-01-01

    Marine sands highly saturated with gas hydrates are potential energy resources, likely forming from methane dissolved in pore water. Laboratory fabrication of gas hydrate-bearing sands formed from dissolved-phase methane usually requires 1–2 months to attain the high hydrate saturations characteristic of naturally occurring energy resource targets. A series of gas hydrate formation tests, in which methane-supersaturated water circulates through 100, 240, and 200,000 cm3 vessels containing glass beads or unconsolidated sand, show that the rate-limiting step is dissolving gaseous-phase methane into the circulating water to form methane-supersaturated fluid. This implies that laboratory and natural hydrate formation rates are primarily limited by methane availability. Developing effective techniques for dissolving gaseous methane into water will increase formation rates above our observed (1 ± 0.5) × 10−7 mol of methane consumed for hydrate formation per minute per cubic centimeter of pore space, which corresponds to a hydrate saturation increase of 2 ± 1% per day, regardless of specimen size.

  6. Anomalous and anisotropic nanoscale diffusion of hydration water molecules in fluid lipid membranes.

    PubMed

    Toppozini, Laura; Roosen-Runge, Felix; Bewley, Robert I; Dalgliesh, Robert M; Perring, Toby; Seydel, Tilo; Glyde, Henry R; García Sakai, Victoria; Rheinstädter, Maikel C

    2015-11-14

    We have studied nanoscale diffusion of membrane hydration water in fluid-phase lipid bilayers made of 1,2-dimyristoyl-3-phosphocholine (DMPC) using incoherent quasi-elastic neutron scattering. Dynamics were fit directly in the energy domain using the Fourier transform of a stretched exponential. By using large, 2-dimensional detectors, lateral motions of water molecules and motions perpendicular to the membranes could be studied simultaneously, resulting in 2-dimensional maps of relaxation time, τ, and stretching exponent, β. We present experimental evidence for anomalous (sub-diffusive) and anisotropic diffusion of membrane hydration water molecules over nanometer distances. By combining molecular dynamics and Brownian dynamics simulations, the potential microscopic origins for the anomaly and anisotropy of hydration water were investigated. Bulk water was found to show intrinsic sub-diffusive motion at time scales of several picoseconds, likely related to caging effects. In membrane hydration water, however, the anisotropy of confinement and local dynamical environments leads to an anisotropy of relaxation times and stretched exponents, indicative of anomalous dynamics. PMID:26338138

  7. Calculation of liquid water-hydrate-methane vapor phase equilibria from molecular simulations.

    PubMed

    Jensen, Lars; Thomsen, Kaj; von Solms, Nicolas; Wierzchowski, Scott; Walsh, Matthew R; Koh, Carolyn A; Sloan, E Dendy; Wu, David T; Sum, Amadeu K

    2010-05-01

    Monte Carlo simulation methods for determining fluid- and crystal-phase chemical potentials are used for the first time to calculate liquid water-methane hydrate-methane vapor phase equilibria from knowledge of atomistic interaction potentials alone. The water and methane molecules are modeled using the TIP4P/ice potential and a united-atom Lennard-Jones potential, respectively. The equilibrium calculation method for this system has three components, (i) thermodynamic integration from a supercritical ideal gas to obtain the fluid-phase chemical potentials, (ii) calculation of the chemical potential of the zero-occupancy hydrate system using thermodynamic integration from an Einstein crystal reference state, and (iii) thermodynamic integration to obtain the water and guest molecules' chemical potentials as a function of the hydrate occupancy. The three-phase equilibrium curve is calculated for pressures ranging from 20 to 500 bar and is shown to follow the Clapeyron behavior, in agreement with experiment; coexistence temperatures differ from the latter by 4-16 K in the pressure range studied. The enthalpy of dissociation extracted from the calculated P-T curve is within 2% of the experimental value at corresponding conditions. While computationally intensive, simulations such as these are essential to map the thermodynamically stable conditions for hydrate systems. PMID:20392117

  8. Numerical investigations of the fluid flows at deep oceanic and arctic permafrost-associated gas hydrate deposits

    NASA Astrophysics Data System (ADS)

    Frederick, Jennifer Mary

    , allows us a unique opportunity to study the response of methane hydrate deposits to warming. Gas hydrate stability in the Arctic and the permeability of the shelf sediments to gas migration is thought to be closely linked with relict submarine permafrost. Submarine permafrost extent depends on several environmental factors, such as the shelf lithology, sea level variations, mean annual air temperature, ocean bottom water temperature, geothermal heat flux, groundwater hydrology, and the salinity of the pore water. Effects of submarine groundwater discharge, which introduces fresh terrestrial groundwater off-shore, can freshen deep marine sediments and is an important control on the freezing point depression of ice and methane hydrate. While several thermal modeling studies suggest the permafrost layer should still be largely intact near-shore, many recent field studies have reported elevated methane levels in Arctic coastal waters. The permafrost layer is thought to create an impermeable barrier to fluid and gas flow, however, talik formation (unfrozen regions within otherwise continuous permafrost) below paleo-river channels can create permeable pathways for gas migration from depth. This is the first study of its kind to make predictions of the methane gas flux to the water column from the Arctic shelf sediments using a 2D multi-phase fluid flow model. Model results show that the dissociation of methane hydrate deposits through taliks can supersaturate the overlying water column at present-day relative to equilibrium with the atmosphere when taliks are large (> 1 km width) or hydrate saturation is high within hydrate layers (> 50% pore volume). Supersaturated waters likely drive a net flux of methane into the atmosphere, a potent greenhouse gas. Effects of anthropogenic global warming will certainly increase gas venting rates if ocean bottom water temperatures increase, but likely won't have immediately observable impacts due to the long response times.

  9. Venting of carbon dioxide-rich fluid and hydrate formation in mid-okinawa trough backarc basin.

    PubMed

    Sakai, H; Gamo, T; Kim, E S; Tsutsumi, M; Tanaka, T; Ishibashi, J; Wakita, H; Yamano, M; Oomori, T

    1990-06-01

    Carbon dioxide-rich fluid bubbles, containing approximately 86 percent CO(2), 3 percent H(2)S, and 11 percent residual gas (CH(4) + H(2)), were observed to emerge from the sea floor at 1335- to 1550-m depth in the JADE hydrothermal field, mid-Okinawa Trough. Upon contact with seawater at 3.8 degrees C, gas hydrate immediately formed on the surface of the bubbles and these hydrates coalesced to form pipes standing on the sediments. Chemical composition and carbon, sulfur, and helium isotopic ratios indicate that the CO(2)-rich fluid was derived from the same magmatic source as dissolved gases in 320 degrees C hydrothermal solution emitted from a nearby black smoker chimney. The CO(2)-rich fluid phase may be separated by subsurface boiling of hydrothermal solutions or by leaching of CO(2)-rich fluid inclusion during posteruption interaction between pore water and volcanogenic sediments. PMID:17733370

  10. Hydration-Induced Phase Transitions in Surfactant and Lipid Films.

    PubMed

    Björklund, Sebastian; Kocherbitov, Vitaly

    2016-05-31

    For several surfactant and lipid systems, it is crucial to understand how hydration influences the physical and chemical properties. When humidity changes, it affects the degree of hydration by adding or removing water molecules. In many cases, this process induces transitions between liquid crystalline phases. This phenomenon is of general interest for numerous applications simply because of the fact that humidity variations are ubiquitous. Of particular interest are hydration-induced phase transitions in amphiphilic films, which in many cases appear as the frontier toward a vapor phase with changing humidity. Considering this, it is important to characterize the film thickness needed for the formation of 3D liquid crystalline phases and the lyotropic phase behavior of this kind of film. In this work, we study this issue by employing a recently developed method based on the humidity scanning quartz crystal microbalance with dissipation monitoring (HS QCM-D), which enables continuous scanning of the film hydration. We investigate five surfactants films (DDAO, DTAC, CTAC, SDS, and n-octylβ-d-glucoside) and one lipid film (monoolein) and show that HS QCM-D enables the fast characterization of hydration-induced phase transitions with small samples. Film thicknesses range from tens to hundreds of nanometers, and clear phase transitions are observed in all cases. It is shown that phase transitions in films occur at the same water activities as for corresponding bulk samples. This allows us to conclude that surfactant and lipid films, with a thickness of as low as 50 nm, are in fact assembled as 3D-structured liquid crystalline phases. Furthermore, liquid crystalline phases of surfactant films show liquidlike behavior, which decreases the accuracy of the absorbed water mass measurement. On the other hand, the monoolein lipid forms more rigid liquid crystalline films, allowing for an accurate determination of the water sorption isotherm, which is also true for the

  11. Artificial Nutrition (Food) and Hydration (Fluids) at the End of Life

    MedlinePlus

    Artificial Nutrition (Food) and Hydration (Fluids) at the End of Life It is very common for doctors to provide fluids and food to people who are very sick ... to understand how the body processes food and fluids. The information below explains the medical facts about ...

  12. Phase field modeling of CH4 hydrate conversion into CO2 hydrate in the presence of liquid CO2.

    PubMed

    Tegze, G; Gránásy, L; Kvamme, B

    2007-06-28

    We present phase field simulations to estimate the conversion rate of CH(4) hydrate to CO(2) hydrate in the presence of liquid CO(2) under conditions typical for underwater gas hydrate reservoirs. In the computations, all model parameters are evaluated from physical properties taken from experiment or molecular dynamics simulations. It has been found that hydrate conversion is a diffusion controlled process, as after a short transient, the displacement of the conversion front scales with t(1/2). Assuming a diffusion coefficient of D(s) = 1.1 x 10(-11) m(2) s(-1) in the hydrate phase, the predicted time dependent conversion rate is in reasonable agreement with results from magnetic resonance imaging experiments. This value of the diffusion coefficient is higher than expected for the bulk hydrate phase, probably due to liquid inclusions remaining in the porous sample used in the experiment. PMID:17612734

  13. X-ray computed tomography observations of phase distribution during methane hydrate formation and dissociation process in a sediment sample

    NASA Astrophysics Data System (ADS)

    Ahn, Taewoong; Lee, Jaehyoung; Lee, Joo Yong; Kim, Se-Joon; Seo, Young-ju

    2016-04-01

    The recovery schemes for natural gas caged in the solid state have not been commercialized. Depressurization has been known as a promising method due to its economic feasibility according to previous lab-scale experiments and simulation studies. However, the results of few field tests showed that the production characteristics of real field differed from that of predicted results. To reliably predict the production performance of real fields, it is necessary to understand quantitative changes of phase distribution and fluid flow in sediments in response to hydrate dissociation by depressurization. In this study, we observed and analyzed the phase distribution and flow behavior during methane hydrate formation and dissociation using X-ray computed tomography which provides high-resolution density distribution. Artificial particles having similar grain size distribution of sandy layers found in real hydrate field were packed into X-ray transparent aluminum vessel. Information on pore distribution within a sediment sample was achieved by comparing CT images between dry condition and fully water-saturated condition. Dynamic changes of phase saturation were observed during gas flooding, through which potential flow pathway was estimated. Hydrate formation and dissociation significantly affected phase distribution and flow pathway. Hydrate distribution was extremely heterogeneous in every tests of hydrate formation repeated with same amount of water. It was inferred that water saturation prior to hydrate formation was not directly correlated to the hydrate distribution. There were definite differences of hydrate dissociation behavior between gas-saturated and water-saturated hydrate-bearing sample. The production of gas and water lasted quite a while even after the production pressure reached the target level of depressurization.

  14. 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

    NASA Astrophysics Data System (ADS)

    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

  15. Computational phase diagrams of noble gas hydrates under pressure

    SciTech Connect

    Teeratchanan, Pattanasak Hermann, Andreas

    2015-10-21

    We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-I{sub h}, ice-I{sub c}, ice-II, and C{sub 0} interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C{sub 0} water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C{sub 0} hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.

  16. Computational phase diagrams of noble gas hydrates under pressure.

    PubMed

    Teeratchanan, Pattanasak; Hermann, Andreas

    2015-10-21

    We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-Ih, ice-Ic, ice-II, and C0 interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C0 water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C0 hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems. PMID:26493915

  17. Computational phase diagrams of noble gas hydrates under pressure

    NASA Astrophysics Data System (ADS)

    Teeratchanan, Pattanasak; Hermann, Andreas

    2015-10-01

    We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-Ih, ice-Ic, ice-II, and C0 interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C0 water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C0 hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.

  18. Comparing the mechanical properties of the porcine knee meniscus when hydrated in saline versus synovial fluid.

    PubMed

    Lakes, Emily H; Kline, Courtney L; McFetridge, Peter S; Allen, Kyle D

    2015-12-16

    As research progresses to find a suitable knee meniscus replacement, accurate in vitro testing becomes critical for feasibility and comparison studies of mechanical integrity. Within the knee, the meniscus is bathed in synovial fluid, yet the most common hydration fluid in laboratory testing is phosphate buffered saline (PBS). PBS is a relatively simple salt solution, while synovial fluid is a complex non-Newtonian fluid with multiple lubricating factors. As such, PBS may interact with meniscal tissue differently than synovial fluid, and thus, the hydration fluid may be an important factor in obtaining accurate results during in vitro testing. To evaluate these effects, medial porcine menisci were used to evaluate tissue mechanics in tension (n=11) and compression (n=15). In all tests, two samples from the same meniscus were taken, where one sample was hydrated in PBS and the other was hydrated in synovial fluid. Statistical analysis revealed no significant differences between the mean mechanical properties of samples tested in PBS compared to synovial fluid; however, compressive testing revealed the variability between samples was significantly reduced if samples were tested in synovial fluid. For example, the compressive Young׳s Modulus was 12.69±7.49MPa in PBS versus 12.34±4.27MPa in synovial fluid. These results indicate testing meniscal tissue in PBS will largely not affect the mean value of the mechanical properties, but performing compression testing in synovial fluid may provide more consistent results between samples and assist in reducing sample numbers in some experiments. PMID:26592438

  19. Study of Mix CO2/CH4 Hydrate Phase Transitions vs the Thickness of Surrounding Water Film

    NASA Astrophysics Data System (ADS)

    Kvamme, B.; Baig, K.; Kuznetsova, T.

    2014-12-01

    Conversion of reservoir CH4 hydrate into CO2 hydrate is an interesting option offering a win-win combination of energy production with safe long-term storage of CO2 to minimize the CO2 footprint. As described theoretically and verified experimentally, CO2 is capable of inducing and maintaining a solid state exchange process of conversion. This mechanism will be slow since it is kinetically controlled by solid state mass transport through the hydrate. In parallel to this, the injected CO2 will form new hydrate from free water trapped in pores. Heat released by this process will contribute to dissociation of in situ CH4 hydrate and thus provide a second conversion mechanism with its rate controlled by liquid state transport processes. Understanding the kinetics of gas hydrate formation and dissociation is crucial for the development of theoretical models describing gas exchange processes and providing a basis for efficient design of production schemes. In this work, we combine a non-equilibrium description of hydrate and fluid thermodynamics with the phase field theory (PFT) for simulation of phase transition kinetics. The phase field theory approach allows one to minimize the free energy while taking into account the implicit couplings to mass and heat transport as well as hydrodynamics. The hydrodynamic treatment is important to distinguish between situations when gas released in the course of dissociation will dissolve into surrounding water (slow dissociation), and more rapid dissociation creating dispersed gas bubbles that will affect the available dissociation interface and influence heat transport. We studied the conversion of CH4 hydrate into either CO2 hydrate or mixed CO2-CH4 hydrate to investigate the relative impact of the two mechanisms. The efficiency of mechanism based on formation of new CO2 hydrate will depend on the contact area between injected CO2 and liquid water. We have therefore investigated three CH4 hydrate systems surrounded by varying

  20. Mapping the Fluid Pathways and Permeability Barriers of a Large Gas Hydrate Reservoir

    NASA Astrophysics Data System (ADS)

    Campbell, A.; Zhang, Y. L.; Sun, L. F.; Saleh, R.; Pun, W.; Bellefleur, G.; Milkereit, B.

    2012-12-01

    An understanding of the relationship between the physical properties of gas hydrate saturated sedimentary basins aids in the detection, exploration and monitoring one of the world's upcoming energy resources. A large gas hydrate reservoir is located in the MacKenzie Delta of the Canadian Arctic and geophysical logs from the Mallik test site are available for the gas hydrate stability zone (GHSZ) between depths of approximately 850 m to 1100 m. The geophysical data sets from two neighboring boreholes at the Mallik test site are analyzed. Commonly used porosity logs, as well as nuclear magnetic resonance, compressional and Stoneley wave velocity dispersion logs are used to map zones of elevated and severely reduced porosity and permeability respectively. The lateral continuity of horizontal permeability barriers can be further understood with the aid of surface seismic modeling studies. In this integrated study, the behavior of compressional and Stoneley wave velocity dispersion and surface seismic modeling studies are used to identify the fluid pathways and permeability barriers of the gas hydrate reservoir. The results are compared with known nuclear magnetic resonance-derived permeability values. The aim of investigating this heterogeneous medium is to map the fluid pathways and the associated permeability barriers throughout the gas hydrate stability zone. This provides a framework for an understanding of the long-term dissociation of gas hydrates along vertical and horizontal pathways, and will improve the knowledge pertaining to the production of such a promising energy source.

  1. Direct Visualization of the Hydration Layer on Alumina Nanoparticles with the Fluid Cell STEM in situ

    PubMed Central

    Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya

    2015-01-01

    Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions. We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. Our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles. PMID:25996055

  2. Phase equilibria of carbon dioxide and methane gas-hydrates predicted with the modified analytical S-L-V equation of state

    NASA Astrophysics Data System (ADS)

    Vinš, Václav; Jäger, Andreas; Hrubý, Jan; Span, Roland

    2012-04-01

    Gas-hydrates (clathrates) are non-stoichiometric crystallized solutions of gas molecules in the metastable water lattice. Two or more components are associated without ordinary chemical union but through complete enclosure of gas molecules in a framework of water molecules linked together by hydrogen bonds. The clathrates are important in the following applications: the pipeline blockage in natural gas industry, potential energy source in the form of natural hydrates present in ocean bottom, and the CO2 separation and storage. In this study, we have modified an analytical solid-liquid-vapor equation of state (EoS) [A. Yokozeki, Fluid Phase Equil. 222-223 (2004)] to improve its ability for modeling the phase equilibria of clathrates. The EoS can predict the formation conditions for CO2- and CH4-hydrates. It will be used as an initial estimate for a more complicated hydrate model based on the fundamental EoSs for fluid phases.

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

    SciTech Connect

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin

    2014-05-01

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

  4. Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates.

    PubMed

    Miskowiec, Andrew; Kirkegaard, Marie C; Huq, Ashfia; Mamontov, Eugene; Herwig, Kenneth W; Trowbridge, Lee; Rondinone, Adam; Anderson, Brian

    2015-12-10

    We report a novel production method for uranium oxyfluoride [(UO2)7F14(H2O)7]·4H2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl fluoride, UO2F2, through the gas phase at ambient temperatures followed by desiccation by equilibration with a dry environment. We follow the structure of [(UO2)7F14(H2O)7]·4H2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous structure), and a water molecule binds as an equatorial ligand to the uranyl ion. Quasielastic neutron scattering results compare well with previous measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform restricted motion on a length scale commensurate with the O-H bond (r = 0.92 Å). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps(-1)) than their hydrogen-bonded partners (Dr = 28.7 ps(-1)). PMID:26575434

  5. Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates

    SciTech Connect

    Miskowiec, Andrew J.; Kirkegaard, Marie C.; Huq, Ashfia; Mamontov, Eugene; Herwig, Kenneth W.; Trowbridge, Lee D.; Rondinone, Adam Justin; Anderson, Brian B.

    2015-11-17

    We report a novel production method for uranium oxy uoride [(UO2)7F14(H2O)7] 4H2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl uoride, UO2F2, through the gas phase at ambient temperatures fol- lowed by desiccation by equilibration with a dry environment. We follow the structure of [(UO2)7F14(H2O)7] 4H2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous struc- ture), and a water molecule binds as an equatorial ligand to the uranyl ion. Quasielas- tic neutron scattering results compare well with previous measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform re- stricted motion on a length scale commensurate with the O{H bond (r = 0.92 A). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps-1) than their hydrogen-bonded partners (Dr = 28.7 ps-1).

  6. Structural Phase Transitions and Water Dynamics in Uranyl Fluoride Hydrates

    DOE PAGESBeta

    Miskowiec, Andrew J.; Kirkegaard, Marie C.; Huq, Ashfia; Mamontov, Eugene; Herwig, Kenneth W.; Trowbridge, Lee D.; Rondinone, Adam Justin; Anderson, Brian B.

    2015-11-17

    We report a novel production method for uranium oxy uoride [(UO2)7F14(H2O)7] 4H2O, referred to as structure D. Structure D is produced as a product of hydrating anhydrous uranyl uoride, UO2F2, through the gas phase at ambient temperatures fol- lowed by desiccation by equilibration with a dry environment. We follow the structure of [(UO2)7F14(H2O)7] 4H2O through an intermediate, liquid-like phase, wherein the coordination number of the uranyl ion is reduced to 5 (from 6 in the anhydrous struc- ture), and a water molecule binds as an equatorial ligand to the uranyl ion. Quasielas- tic neutron scattering results compare well with previousmore » measurements of mineral hydrates. The two groups of structurally distinct water molecules in D perform re- stricted motion on a length scale commensurate with the O{H bond (r = 0.92 A). The more tightly bound equatorial ligand waters rotate slower (Dr = 2.2 ps-1) than their hydrogen-bonded partners (Dr = 28.7 ps-1).« less

  7. Fluid and chemical cycling at Bush Hill: Implications for gas- and hydrate-rich environments

    NASA Astrophysics Data System (ADS)

    Tryon, Michael D.; Brown, Kevin M.

    2004-12-01

    The results of a deployment of aqueous flux meters at the Bush Hill hydrate mound show that persistent hydrologic instability is a primary feature of the globally abundant gas- and hydrate-rich cold seep environment. Seven flux meters were deployed for 14 weeks in the area of the Bush Hill hydrate mound. Instruments were deployed on microbial mats, bivalves, adjacent to the surface hydrate mound, and a site without visible fauna. Flow rates were observed to range from downflow of 0.01 mm/day to upflow of >15 mm/day. Temporal variability and a major hydrological event were observed to occur on all instruments. There is evidence that this event was related to a gas expulsion episode. The two instruments which exhibited downflow during the event were near surface hydrates and bubbling vents. Nearby instruments recorded a rapid increase in flow rates at the time of the event with a subsequent decrease in rates to the previous background values. Two instruments showed significant output of seawater-like fluids, while the others output typical methane seep-type pore fluids. These results at a passive margin site, along with our previously published convergent margin results at gas-rich northeast Pacific cold seeps (Hydrate Ridge, Eel River margin), illustrate the hydrologic complexity of these environments. We now propose that these and our earlier results are characteristic of seafloor environments which have abundant free gas and hydrates. These mechanisms have major consequences for the near-surface geochemical and microbial environment and for the way we interpret measurements made in these areas.

  8. The impact of fluid advection on gas hydrate stability: Investigations at sites of methane seepage offshore Costa Rica

    NASA Astrophysics Data System (ADS)

    Crutchley, G. J.; Klaeschen, D.; Planert, L.; Bialas, J.; Berndt, C.; Papenberg, C.; Hensen, C.; Hornbach, M. J.; Krastel, S.; Brueckmann, W.

    2014-09-01

    Fluid flow through marine sediments drives a wide range of processes, from gas hydrate formation and dissociation, to seafloor methane seepage including the development of chemosynthetic ecosystems, and ocean acidification. Here, we present new seismic data that reveal the 3D nature of focused fluid flow beneath two mound structures on the seafloor offshore Costa Rica. These mounds have formed as a result of ongoing seepage of methane-rich fluids. We show the spatial impact of advective heat flow on gas hydrate stability due to the channelled ascent of warm fluids towards the seafloor. The base of gas hydrate stability (BGHS) imaged in the seismic data constrains peak heat flow values to ∼60 mW m and ∼70 mW m beneath two separate seep sites known as Mound 11 and Mound 12, respectively. The initiation of pronounced fluid flow towards these structures was likely controlled by fault networks that acted as efficient pathways for warm fluids ascending from depth. Through the gas hydrate stability zone, fluid flow has been focused through vertical conduits that we suggest developed as migrating fluids generated their own secondary permeability by fracturing strata as they forced their way upwards towards the seafloor. We show that Mound 11 and Mound 12 (about 1 km apart on the seafloor) are sustained by independent fluid flow systems through the hydrate system, and that fluid flow rates across the BGHS are probably similar beneath both mounds. 2D seismic data suggest that these two flow systems might merge at approximately 1 km depth, i.e. much deeper than the BGHS. This study provides a new level of detail and understanding of how channelled, anomalously-high fluid flow towards the seafloor influences gas hydrate stability. Thus, gas hydrate systems have good potential for quantifying the upward flow of subduction system fluids to seafloor seep sites, since the fluids have to interact with and leave their mark on the hydrate system before reaching the seafloor.

  9. Stratigraphic mapping of hydrated phases in Western Ius Chasma, Mars

    NASA Astrophysics Data System (ADS)

    Cull, S.; McGuire, P. C.; Gross, C.; Dumke, A.

    2013-12-01

    Recent mapping with the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) and Observatoire pour la Minéralogie, l'Eau, les Glaces et l'Activité (OMEGA) has revealed a wide range of hydrated minerals throughout Valles Marineris. Noctis Labyrinthus has interbedded polyhydrated and monohydrated sulfates, with occasional beds of nontronite (Weitz et al. 2010, Thollot et al. 2012). Tithonium Chasma has interbedded poly- and monohydrated sulfates (Murchie et al. 2012); Juventae has poly- and monohydrated sulfates and an anhydrous ferric hydroxysulfate-bearing material (Bishop et al. 2009); and Melas and Eastern Candor contain layers of poly- and monohydrated sulfates (e.g., Roach et al. 2009). Though each chasm displays its own mineralogy, in general, the eastern valles tend to be dominated by layered sequences with sulfates; whereas, the far western valles (Noctis Labyrinthus) has far more mineral phases, possibly due to a wider variety of past environments or processes affecting the area. Ius Chasma, which is situated between Noctis Labyrinthus and the eastern valles and chasmata, also displays a complex mineralogy, with polyhydrated sulfates, Fe/Mg smectites, hydrated silica, and kieserite (e.g. Roach et al. 2010). Here, we present mapping of recently acquired CRISM observations over Ius Chasma, combining the recent CRISM cubes with topographic terrains produced using High Resolution Stereo Camera (HRSC) data from the Mars Express spacecraft. Stratigraphic columns are produced along the length of Ius Chasma, and compared to stratigraphic columns produced throughout the Valles Marineris

  10. North Cascadia heat flux and fluid flow from gas hydrates: Modeling 3-D topographic effects

    NASA Astrophysics Data System (ADS)

    Li, Hong-lin; He, Tao; Spence, George D.

    2014-01-01

    The bottom-simulating reflector (BSR) of gas hydrate is well imaged from two perpendicular seismic grids in the region of a large carbonate mound, informally called Cucumber Ridge off Vancouver Island. We use a new method to calculate 3-D heat flow map from the BSR depths, in which we incorporate 3-D topographic corrections after calibrated by the drilling results from nearby (Integrated) Ocean Drilling Program Site 889 and Site U1327. We then estimate the associated fluid flow by relating it to the topographically corrected heat flux anomalies. In the midslope region, a heat flux anomaly of 1 mW/m2 can be associated with an approximate focused fluid flow rate of 0.09 mm/yr. Around Cucumber Ridge, high rates of focused fluid flow were observed at steep slopes with values more than double the average regional diffusive fluid discharge rate of 0.56 mm/yr. As well, in some areas of relatively flat seafloor, the focused fluid flow rates still exceeded 0.5 mm/yr. On the seismic lines the regions of focused fluid flow were commonly associated with seismic blanking zones above the BSR and sometimes with strong reflectors below the BSR, indicating that the faults/fractures provide high-permeability pathways for fluids to carry methane from BSR depths to the seafloor. These high fluid flow regions cover mostly the western portion of our area with gas hydrate concentration estimations of ~6% based on empirical correlations from Hydrate Ridge in south off Oregon, significantly higher than previously recognized values of ~2.5% in the eastern portion determined from Site U1327.

  11. Elasticity of methane hydrate phases at high pressure

    NASA Astrophysics Data System (ADS)

    Beam, Jennifer; Yang, Jing; Liu, Jin; Liu, Chujie; Lin, Jung-Fu

    2016-04-01

    Determination of the full elastic constants (cij) of methane hydrates (MHs) at extreme pressure-temperature environments is essential to our understanding of the elastic, thermodynamic, and mechanical properties of methane in MH reservoirs on Earth and icy satellites in the solar system. Here, we have investigated the elastic properties of singe-crystal cubic MH-sI, hexagonal MH-II, and orthorhombic MH-III phases at high pressures in a diamond anvil cell. Brillouin light scattering measurements, together with complimentary equation of state (pressure-density) results from X-ray diffraction and methane site occupancies in MH from Raman spectroscopy, were used to derive elastic constants of MH-sI, MH-II, and MH-III phases at high pressures. Analysis of the elastic constants for MH-sI and MH-II showed intriguing similarities and differences between the phases' compressional wave velocity anisotropy and shear wave velocity anisotropy. Our results show that these high-pressure MH phases can exhibit distinct elastic, thermodynamic, and mechanical properties at relevant environments of their respective natural reservoirs. These results provide new insight into the determination of how much methane exists in MH reservoirs on Earth and on icy satellites elsewhere in the solar system and put constraints on the pressure and temperature conditions of their environment.

  12. Pressure induced reactions amongst calcium aluminate hydrate phases

    SciTech Connect

    Moon, Ju-hyuk; Oh, Jae Eun; Balonis, Magdalena; Glasser, Fredrik P.; Clark, Simon M.; Monteiro, Paulo J.M.

    2011-06-15

    The compressibilities of two AFm phases (straetlingite and calcium hemicarboaluminate hydrate) and hydrogarnet were obtained up to 5 GPa by using synchrotron high-pressure X-ray powder diffraction with a diamond anvil cell. The AFm phases show abrupt volume contraction regardless of the molecular size of the pressure-transmitting media. This volume discontinuity could be associated to a structural transition or to the movement of the weakly bound interlayer water molecules in the AFm structure. The experimental results seem to indicate that the pressure-induced dehydration is the dominant mechanism especially with hygroscopic pressure medium. The Birch-Murnaghan equation of state was used to compute the bulk modulus of the minerals. Due to the discontinuity in the pressure-volume diagram, a two stage bulk modulus of each AFm phase was calculated. The abnormal volume compressibility for the AFm phases caused a significant change to their bulk modulus. The reliability of this experiment is verified by comparing the bulk modulus of hydrogarnet with previous studies.

  13. Elasticity of methane hydrate phases at high pressure.

    PubMed

    Beam, Jennifer; Yang, Jing; Liu, Jin; Liu, Chujie; Lin, Jung-Fu

    2016-04-21

    Determination of the full elastic constants (cij) of methane hydrates (MHs) at extreme pressure-temperature environments is essential to our understanding of the elastic, thermodynamic, and mechanical properties of methane in MH reservoirs on Earth and icy satellites in the solar system. Here, we have investigated the elastic properties of singe-crystal cubic MH-sI, hexagonal MH-II, and orthorhombic MH-III phases at high pressures in a diamond anvil cell. Brillouin light scattering measurements, together with complimentary equation of state (pressure-density) results from X-ray diffraction and methane site occupancies in MH from Raman spectroscopy, were used to derive elastic constants of MH-sI, MH-II, and MH-III phases at high pressures. Analysis of the elastic constants for MH-sI and MH-II showed intriguing similarities and differences between the phases' compressional wave velocity anisotropy and shear wave velocity anisotropy. Our results show that these high-pressure MH phases can exhibit distinct elastic, thermodynamic, and mechanical properties at relevant environments of their respective natural reservoirs. These results provide new insight into the determination of how much methane exists in MH reservoirs on Earth and on icy satellites elsewhere in the solar system and put constraints on the pressure and temperature conditions of their environment. PMID:27389226

  14. Fluid and salt supplementation effect on body hydration and electrolyte homeostasis during bed rest and ambulation

    NASA Astrophysics Data System (ADS)

    Zorbas, Yan G.; Kakurin, Vassily J.; Kuznetsov, Nikolai A.; Yarullin, Vladimir L.

    2002-06-01

    Bed rest (BR) induces significant urinary and blood electrolyte changes, but little is known about the effect of fluid and salt supplements (FSS) on catabolism, hydration and electrolytes. The aim was to measure the effect of FSS on catabolism, body hydration and electrolytes during BR. Studies were done during 7 days of a pre-bed rest period and during 30 days of a rigorous bed rest period. Thirty male athletes aged, 24.6±7.6 years were chosen as subjects. They were divided into three groups: unsupplemented ambulatory control subjects (UACS), unsupplemented bed rested subjects (UBRS) and supplemented bed rested subjects (SBRS). The UBRS and SBRS groups were kept under a rigorous bed rest regime for 30 days. The SBRS daily took 30 ml water per kg body weight and 0.1 sodium chloride per kg body weight. Plasma sodium (Na), potassium (K), calcium (Ca) and magnesium (Mg) levels, urinary Na, K, Ca and Mg excretion, plasma osmolality, plasma protein level, whole blood hemoglobin (Hb) and hematocrit (Hct) level increased significantly ( p≤0.05), while plasma volume (PV), body weight, body fat, peak oxygen uptake, food and fluid intake decreased significantly ( p≤0.05) in the UBRS group when compared with the SBRS and UACS groups. In contrast, plasma and urinary electrolytes, osmolality, protein level, whole blood Hct and Hb level decreased significantly ( p≤0.05), while PV, fluid intake, body weight and peak oxygen uptake increased significantly ( p≤0.05) in the SBRS group when compared with the UBRS group. The measured parameters did not change significantly in the UACS group when compared with their baseline control values. The data indicate that FSS stabilizes electrolytes and body hydration during BR, while BR alone induces significant changes in electrolytes and body hydration. We conclude that FSS may be used to prevent catabolism and normalize body hydration status and electrolyte values during BR.

  15. Phase I (CATTS Theory), Phase II (Milne Point), Phase III (Hydrate Ridge)

    SciTech Connect

    None, None

    2009-10-31

    This study introduces a new type of cumulative seismic attribute (CATT) which quantifies gas hydrates resources in Hydrate Ridge offshore Oregon. CATT is base on case-specific transforms that portray hydrated reservoir properties. In this study we used a theoretical rock physics model to correct measured velocity log data.

  16. Hydration Status and Fluid Balance of Elite European Youth Soccer Players during Consecutive Training Sessions

    PubMed Central

    Phillips, Saun M.; Sykes, Dave; Gibson, Neil

    2014-01-01

    The objective of the study was to investigate the hydration status and fluid balance of elite European youth soccer players during three consecutive training sessions. Fourteen males (age 16.9 ± 0.8 years, height 1.79 ± 0.06 m, body mass (BM) 70.6 ± 5.0 kg) had their hydration status assessed from first morning urine samples (baseline) and pre- and post-training using urine specific gravity (USG) measures, and their fluid balance calculated from pre- to post-training BM change, corrected for fluid intake and urine output. Most participants were hypohydrated upon waking (USG >1.020; 77% on days 1 and 3, and 62% on day 2). There was no significant difference between first morning and pre-training USG (p = 0.11) and no influence of training session (p = 0.34) or time (pre- vs. post-training; p = 0.16) on USG. Significant BM loss occurred in sessions 1-3 (0.69 ± 0.22, 0.42 ± 0.25, and 0.38 ± 0.30 kg respectively, p < 0.05). Mean fluid intake in sessions 1-3 was 425 ± 185, 355 ± 161, and 247 ± 157 ml, respectively (p < 0.05). Participants replaced on average 71.3 ± 64.1% (range 0-363.6%) of fluid losses across the three sessions. Body mass loss, fluid intake, and USG measures showed large inter-individual variation. Elite young European soccer players likely wake and present for training hypohydrated, when a USG threshold of 1.020 is applied. When training in a cool environment with ad libitum access to fluid, replacing ~71% of sweat losses results in minimal hypohydration (<1% BM). Consumption of fluid ad libitum throughout training appears to prevent excessive (≥2% BM) dehydration, as advised by current fluid intake guidelines. Current fluid intake guidelines appear applicable for elite European youth soccer players training in a cool environment. Key Points The paper demonstrates a notable inter-participant variation in first morning, pre- and post-training hydration status and fluid balance of elite young European soccer players. On average, elite young

  17. Association of gas hydrate formation in fluid discharges with anomalous hydrochemical profiles

    NASA Astrophysics Data System (ADS)

    Matveeva, T.

    2009-04-01

    Numerous investigations worldwide have shown that active underwater fluid discharge produces specific structures on the seafloor such as submarine seepages, vents, pockmarks, and collapse depressions. Intensive fluxes of fluids, especially of those containing hydrocarbon gases, result in specific geochemical and physical conditions favorable for gas hydrate (GH) formation. GH accumulations associated with fluid discharge are usually controlled by fluid conduits such as mud volcanoes, diapirs or faults. During last decade, subaqueous GHs become the subject of the fuel in the nearest future. However, the expediency of their commercial development can be proved solely by revealing conditions and mechanisms of GH formation. Kinetic of GH growth (although it is incompletely understood) is one of the important parameters controlling their formation among with gas solubility, pressure, temperature, gas quantity and others. Original large dataset on hydrate-related interstitial fluids obtained from different fluid discharge areas at the Sea of Okhotsk, Black Sea, Gulf of Cadiz, Lake Baikal (Eastern Siberia) allow to suggest close relation of the subaqueous GH formation process to anomalous hydrochemical profiles. We have studied the chemical and isotopic composition of interstitial fluids from GH-bearing and GH-free sediments obtained at different GH accumulations. Most attention was paid to possible influence of the interstitial fluid chemistry on the kinetic of GH formation in a porous media. The influence of salts on methane solubility within hydrate stability zones was considered by Handa (1990), Zatsepina & Buffet (1998), and later by Davie et al. (2004) from a theoretical point of view. Our idea is based on the experimentally proved fact that fugacity coefficient of methane dissolved in saline gas-saturated water which is in equilibrium with hydrates, is higher than that in more fresh water though the solubility is lower. Therefore, if a gradient of water salinity

  18. Hydration of gas-phase ytterbium ion complexes studied by experiment and theory

    SciTech Connect

    Rutkowski, Philip X; Michelini, Maria C.; Bray, Travis H.; Russo, Nino; Marcalo, Joaquim; Gibson, John K.

    2011-02-11

    Hydration of ytterbium (III) halide/hydroxide ions produced by electrospray ionization was studied in a quadrupole ion trap mass spectrometer and by density functional theory (DFT). Gas-phase YbX{sub 2}{sup +} and YbX(OH){sup +} (X = OH, Cl, Br, or I) were found to coordinate from one to four water molecules, depending on the ion residence time in the trap. From the time dependence of the hydration steps, relative reaction rates were obtained. It was determined that the second hydration was faster than both the first and third hydrations, and the fourth hydration was the slowest; this ordering reflects a combination of insufficient degrees of freedom for cooling the hot monohydrate ion and decreasing binding energies with increasing hydration number. Hydration energetics and hydrate structures were computed using two approaches of DFT. The relativistic scalar ZORA approach was used with the PBE functional and all-electron TZ2P basis sets; the B3LYP functional was used with the Stuttgart relativistic small-core ANO/ECP basis sets. The parallel experimental and computational results illuminate fundamental aspects of hydration of f-element ion complexes. The experimental observations - kinetics and extent of hydration - are discussed in relationship to the computed structures and energetics of the hydrates. The absence of pentahydrates is in accord with the DFT results, which indicate that the lowest energy structures have the fifth water molecule in the second shell.

  19. Phase Transition of a Structure II Cubic Clathrate Hydrate to a Tetragonal Form.

    PubMed

    Takeya, Satoshi; Fujihisa, Hiroshi; Yamawaki, Hiroshi; Gotoh, Yoshito; Ohmura, Ryo; Alavi, Saman; Ripmeester, John A

    2016-08-01

    The crystal structure and phase transition of cubic structure II (sII) binary clathrate hydrates of methane (CH4 ) and propanol are reported from powder X-ray diffraction measurements. The deformation of host water cages at the cubic-tetragonal phase transition of 2-propanol+CH4 hydrate, but not 1-propanol+CH4 hydrate, was observed below about 110 K. It is shown that the deformation of the host water cages of 2-propanol+CH4 hydrate can be explained by the restriction of the motion of 2-propanol within the 5(12) 6(4) host water cages. This result provides a low-temperature structure due to a temperature-induced symmetry-lowering transition of clathrate hydrate. This is the first example of a cubic structure of the common clathrate hydrate families at a fixed composition. PMID:27346760

  20. Hydrogen sulfide hydrates and saline fluids in the continental margin of South Australia

    NASA Astrophysics Data System (ADS)

    Swart, P. K.; Wortmann, U. G.; Mitterer, R. M.; Malone, M. J.; Smart, P. L.; Feary, D. A.; Hine, A. C.

    2000-11-01

    During the drilling of the southern Australian continental margin (Leg 182 of the Ocean Drilling Program), fluids with unusually high salinities (to 106‰) were encountered in Miocene to Pleistocene sediments. At three sites (1127, 1129, and 1131), high contents of H2S (to 15%), CH4 (50%), and CO2 (70%) were also encountered. These levels of H2S are the highest yet reported during the history of either the Deep Sea Drilling Project or the Ocean Drilling Program. The high concentrations of H2S and CH4 are associated with anomalous Na+/Cl- ratios in the pore waters. Although hydrates were not recovered, and despite the shallow water depth of these sites (200 400 m) and relative warm bottom water temperatures (11 14 °C), we believe that these sites possess disseminated H2S-dominated hydrates. This contention is supported by calculations using the measured gas concentrations and temperatures of the cores, and depths of recovery. High concentrations of H2S necessary for the formation of hydrates under these conditions were provided by the abundant SO42- caused by the high salinities of the pore fluids, and the high concentrations of organic material. One hypothesis for the origin of these fluids is that they were formed on the adjacent continental shelf during previous lowstands of sea level and were forced into the sediments under the influence of hydrostatic head.

  1. TOUGH-Fx/Hydrate

    Energy Science and Technology Software Center (ESTSC)

    2005-02-01

    TOUGH-Fx/HYORATL can model the non-isothermal gas release. phase behavior and flow of fluids and heat in complex geologic media. The code can simulate production from natural gas hydrate deposits in the subsurtace (i.e., in the permafrost and in deep ocean sediments), as well as laboratory experiments of hydrate dissociation/formation in porous/fractured media. T006H-Fx/HYDRATE vi .0 includes both an equilibrium and a kinetic model of hydrate Ibmiation and dissociation. The model accounts for heat and upmore » 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.« less

  2. Impacts of Hydrate Pore Habit on Physical Properties of Hydrate Bearing Sediments

    NASA Astrophysics Data System (ADS)

    Seol, Y.; Dai, S.; Choi, J. H.

    2014-12-01

    The physical properties of gas hydrate bearing sediments, to a large extent, are governed by the volume fraction and spatial distribution of the hydrate phase. For sediments containing the same amount of hydrates, their overall physical properties may vary several orders of magnitude depending on hydrate pore habit. We investigate the interplay among hydrate formation methods, hydrate pore habits, and fundamental physical properties of hydrate bearing sediments. We have developed a new method to synthesize noncementing hydrate in sands, a multi-properties characterization chamber to test the hydrate bearing sediments, and pore network models to simulate fluid flow processes in hydrate bearing sediments. We have found that (1) the growth pattern of hydrate crystal in the pore spaces of water saturated sediments is dominated by the relative magnitude of the capillary force (between hydrate crystal and pore fluid) and the skeleton force, which will result in pore-filling or grain-displacing type of hydrate pore character; (2) the existing capillary tube models of water permeability in hydrate bearing sediments are sensitive to pore geometry and hydrate pore habit; and (3) preliminary CT results suggest that hydrate nucleation in partially water saturated sands tends to agglomerate in patches, rather than in an uniformly-distributed contact-cementing morphology. Additional CT results with a small amount of fines (5wt%) and visualization via micro-CT of hydrate pore habits in sediments using different hydrate formation methods will be discussed.

  3. Decreased stability of methane hydrates in marine sediments owing to phase-boundary roughness.

    PubMed

    Wood, W T; Gettrust, J F; Chapman, N R; Spence, G D; Hyndman, R D

    2002-12-12

    Below water depths of about 300 metres, pressure and temperature conditions cause methane to form ice-like crystals of methane hydrate. Marine deposits of methane hydrate are estimated to be large, amassing about 10,000 gigatonnes of carbon, and are thought to be important to global change and seafloor stability, as well as representing a potentially exploitable energy resource. The extent of these deposits can usually be inferred from seismic imaging, in which the base of the methane hydrate stability zone is frequently identifiable as a smooth reflector that runs parallel to the sea floor. Here, using high-resolution seismic sections of seafloor sediments in the Cascadia margin off the coast of Vancouver Island, Canada, we observe lateral variations in the base of the hydrate stability zone, including gas-rich vertical intrusions into the hydrate stability zone. We suggest that these vertical intrusions are associated with upward flow of warmer fluids. Therefore, where seafloor fluid expulsion and methane hydrate deposits coincide, the base of the hydrate stability zone might exhibit significant roughness and increased surface area. Increased area implies that significantly more methane hydrate lies close to being unstable and hence closer to dissociation in the event of a lowering of pressure due to sea-level fall. PMID:12478290

  4. Fluid Migration Patterns in Gas Hydrate System of Four-Way-Closure Ridge Offshore Southwestern Taiwan

    NASA Astrophysics Data System (ADS)

    Chen, Liwen; Chi, Wu-Cheng; Lin, Yu-Hsieh; Berndt, Christian; Lin, Saulwood

    2016-04-01

    Four-Way-Closure (4WC) Ridge shows great potential as a hydrate prospect from collected multitude of marine geophysical datasets offshore southwestern Taiwan. The aim of my study is to better understand the fluid migration patterns and the possible source locations of the methane at this site. It is a cold seep site with an elongated NW-SE trending anticlinal ridge, which is formed by fault-related folds in the frontal segment of the lower slope domain of the Taiwan accretionary prism along its convergent boundary. So I detail recognized the regional feature structures of the 4WC Ridge, including the thrust faulting and a seismic chimney beneath the seepage sites. I plan to study the temperature perturbation at the 4WC Ridge to better understand gas hydrate system there. To quantify the amount of temperature perturbation near the fault zone, we need to correct the temperature field data for other geological processes. One important correction we want to make concerns the topographic effects on the shallow crust temperature field. So we used 3D finite element method to quantify how much temperature perturbation can be attributed to the local bathymetry at the 4WC Ridge. This model will give us a temperature field based on pure thermal conduction. Then, we can compare the model temperature field with the temperature field derived from thousands of BSRs from the seismic cube, and interpret any resulting temperature discrepancy. As our previous study, we known several geological processes can cause such a discrepancy, including advective fluid migration. If the fault zone fluid migration hypothesis is correct and gas hydrate system reacts to the deep warm fluids from below it, we expect that the BSR will become shallower near the fluid pathways, and the BSR-based temperature field might be a few degrees Celsius higher than in the 3D thermal conductive temperature field. Otherwise, the two temperature fields should be similar. This study is important for hydrate

  5. Capillary effects on gas hydrate three-phase stability in marine sediments

    NASA Astrophysics Data System (ADS)

    Liu, X.; Flemings, P. B.

    2013-12-01

    We study the three-phase (Liquid + Gas + Hydrate) stability of the methane hydrate system in marine sediments by considering the capillary effects on both hydrate and free gas phases. The aqueous CH4 solubilities required for forming hydrate (L+H) and free gas (L+G) in different pore sizes can be met in a three-phase zone. The top of the three-phase zone shifts upward in sediments as the water depth increases and the mean pore size decreases. The thickness of the three-phase zone increases as the pore size distribution widens. The top of the three-phase zone can either overlie the three-phase stability depth at deepwater Blake Ridge or underlie the three-phase stability depth at Hydrate Ridge in shallow water. Our model prediction is compatible with worldwide observations that the bottom-simulating reflector is systematically shifted upward relative to the bulk equilibrium depth as water depth (pressure) is increased. The gas hydrate and free gas saturations of the three-phase zone at Blake Ridge Comparison of the globally compiled BSR temperatures with the three-phase equilibrium curves for the systems of pure CH4 + 3.5 wt.% seawater (solid line) and pure CH4 + 2.0 wt.% seawater (dotted line). The discrepancies between the observed BSR temperature and the calculated three-phase temperature are systematically larger in deep water than in shallow water.

  6. Effect of organic matters on CO2 hydrate phase equilibrium conditions in Na-montmorillonite clay

    NASA Astrophysics Data System (ADS)

    Park, T.; Kyung, D.; Lee, W.

    2013-12-01

    Formation of gas hydrates provides an attractive idea for storing greenhouse gases in a long-term stable geological formation. Since the phase equilibrium conditions of gas hydrates indicate the stability of hydrates, estimation of the phase equilibrium conditions of gas hydrates in marine geological conditions is necessary. In this study, we have identified the effects of organic matters (glycine, glucose, and urea) and solid surface (montmorillonite (MMT)) on the three-phase (liquid-hydrate-vapor) equilibrium conditions of CO2 hydrate. CO2 phase equilibrium experiments were conducted using 0.5mol% organic matter solutions with and without 10g soil mineral were experimentally conducted. Addition of organic matters shifted the phase equilibrium conditions of CO2 hydrate to the higher pressure or lower pressure region because of higher competition of water molecules due to the dissolved organic matters. Presence of MMT also leaded to the higher equilibrium pressure due to the interaction of cations with water molecules. By addition of organic matters to the clay suspension, the hydrate phase equilibrium conditions were less inhibited compared to those of MMT and organic matters independently. The diminished magnitudes by addition of organic matters to the clay suspension (MMT > MMT+urea > MMT+glycine > MMT+glucose > DIW) were different to the order of inhibition degree without MMT (Glucose > glycine > urea > DIW). X-ray diffraction (XRD), scanning electron microscope (SEM), and ion chromatography (IC) analysis were conducted to support the hypothesis that the organic matters interact with cations in MMT interlayer space, and leads to the less inhibition of phase equilibrium conditions. The present study provides basic information for the formation and dissociation of CO2 hydrates in the geological formation when sequestering CO2 as a form of CO2 hydrate.

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

    NASA Astrophysics Data System (ADS)

    Tang, Xiaojia; Guo, Lin; Chen, Chen; Liu, Quan; Li, Tie; Zhu, Yimin

    2014-05-01

    In order to investigate the magnesium oxide hydration process in gas-liquid-solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid-solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phase system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH)2 precipitation, Mg(OH)2 peeling off from MgO particle and leaving behind fresh MgO surface.

  8. Direct visualization of the hydration layer on alumina nanoparticles with the fluid cell STEM in situ

    DOE PAGESBeta

    Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya

    2015-05-21

    Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions.more » We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. As a result, our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles.« less

  9. Effect of organic matter on CO(2) hydrate phase equilibrium in phyllosilicate suspensions.

    PubMed

    Park, Taehyung; Kyung, Daeseung; Lee, Woojin

    2014-06-17

    In this study, we examined various CO2 hydrate phase equilibria under diverse, heterogeneous conditions, to provide basic knowledge for successful ocean CO2 sequestration in offshore marine sediments. We investigated the effect of geochemical factors on CO2 hydrate phase equilibrium. The three-phase (liquid-hydrate-vapor) equilibrium of CO2 hydrate in the presence of (i) organic matter (glycine, glucose, and urea), (ii) phyllosilicates [illite, kaolinite, and Na-montmorillonite (Na-MMT)], and (iii) mixtures of them was measured in the ranges of 274.5-277.0 K and 14-22 bar. Organic matter inhibited the phase equilibrium of CO2 hydrate by association with water molecules. The inhibition effect decreased in the order: urea < glycine < glucose. Illite and kaolinite (unexpandable clays) barely affected the CO2 hydrate phase equilibrium, while Na-MMT (expandable clay) affected the phase equilibrium because of its interlayer cations. The CO2 hydrate equilibrium conditions, in the illite and kaolinite suspensions with organic matter, were very similar to those in the aqueous organic matter solutions. However, the equilibrium condition in the Na-MMT suspension with organic matter changed because of reduction of its inhibition effect by intercalated organic matter associated with cations in the Na-MMT interlayer. PMID:24844562

  10. Molecular dynamics simulations of a fully hydrated dimyristoylphosphatidylcholine membrane in liquid-crystalline phase

    NASA Astrophysics Data System (ADS)

    Zubrzycki, Igor Z.; Xu, Yan; Madrid, Marcela; Tang, Pei

    2000-02-01

    Molecular dynamics (MD) simulations were performed to investigate the structure of a fully hydrated 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) bilayer in liquid-crystalline (fluid) phase at 30 °C. The bilayer consists of 200 DMPC lipid molecules with nw=27.4 water molecules per lipid. The membrane was built with reference to the coordinates of a previously published 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) membrane patch. A four-step dynamic procedure (110 ps) with Berendsen pressure rescaling (P=0 and 1 bar), applied in all three directions, was used to rapidly prepare the bilayer. This system was then subjected to two separate constant pressure and temperature simulations at 1 bar and 30 °C for ˜380 ps, using the Nosé-Hoover NPT method with periodical boundaries and Berendsen temperature and pressure rescaling method, respectively. The resultant bilayer has an area per lipid of 59.2 Å2 and a head-to-head thickness (DHH) of 36.3 Å. These values are in good agreement with the x-ray diffraction data of 59.7 Å2 and 34.4 Å, respectively, for DMPC at 30 °C with nw of 25.7 [H. I. Petrache, S. Tristram-Nagle, and J. F. Nagle, Chem. Phys. Lipids 95, 83 (1998)]. The fractions of trans and gauche bonds in the hydrocarbon chains, averaged for the last 94 ps of simulation, are 81.7% and 18.3%, respectively, suggesting a fluid phase of the membrane. The electron density profile resembles closely that measured by x-ray diffraction. Water density profile suggests a significant penetration of water molecules into the bilayer head region to as deep as the carbonyl groups, with phosphate groups being strongly hydrated.

  11. Hydration of potassiated amino acids in the gas phase.

    PubMed

    Wincel, Henryk

    2007-12-01

    The thermochemistry of stepwise hydration of several potassiated amino acids was studied by measuring the gas-phase equilibria, AAK(+)(H(2)O)(n-1) + H(2)O = AAK(+)(H(2)O)(n) (AA = Gly, AL, Val, Met, Pro, and Phe), using a high-pressure mass spectrometer. The AAK(+) ions were obtained by electrospray and the equilibrium constants K(n-1,n) were measured in a pulsed reaction chamber at 10 mbar bath gas, N(2), containing a known partial pressure of water vapor. Determination of the equilibrium constants at different temperatures was used to obtain the DeltaH(n)(o), DeltaS(n)(o), and DeltaG(n)(o) values. The results indicate that the water binding energy in AAK(+)(H(2)O) decreases as the K(+) affinity to AA increases. This trend in binding energies is explained in terms of changes in the side-chain substituent, which delocalize the positive charge from K(+) to AA in AAK(+) complexes, varying the AAK(+)-H(2)O electrostatic interaction. PMID:17928233

  12. Controlled-source electromagnetic and seismic delineation of subseafloor fluid flow structures in a gas hydrate province, offshore Norway

    NASA Astrophysics Data System (ADS)

    Attias, Eric; Weitemeyer, Karen; Minshull, Tim A.; Best, Angus I.; Sinha, Martin; Jegen-Kulcsar, Marion; Hölz, Sebastian; Berndt, Christian

    2016-08-01

    Deep sea pockmarks underlain by chimney-like or pipe structures that contain methane hydrate are abundant along the Norwegian continental margin. In such hydrate provinces the interaction between hydrate formation and fluid flow has significance for benthic ecosystems and possibly climate change. The Nyegga region, situated on the western Norwegian continental slope, is characterized by an extensive pockmark field known to accommodate substantial methane gas hydrate deposits. The aim of this study is to detect and delineate both the gas hydrate and free gas reservoirs at one of Nyegga's pockmarks. In 2012, a marine controlled-source electromagnetic (CSEM) survey was performed at a pockmark in this region, where high-resolution 3-D seismic data were previously collected in 2006. 2-D CSEM inversions were computed using the data acquired by ocean bottom electrical field receivers. Our results, derived from unconstrained and seismically constrained CSEM inversions, suggest the presence of two distinctive resistivity anomalies beneath the pockmark: a shallow vertical anomaly at the underlying pipe structure, likely due to gas hydrate accumulation, and a laterally extensive anomaly attributed to a free gas zone below the base of the gas hydrate stability zone. This work contributes to a robust characterization of gas hydrate deposits within subseafloor fluid flow pipe structures.

  13. Effect of fluid and salt supplementation on body hydration of athletes during prolonged hypokinesia

    NASA Astrophysics Data System (ADS)

    Zorbas, Yan G.; Petrov, Kirill L.; Yarullin, Vladimir L.; Kakurin, Vassily J.; Popov, Vladimir K.; Deogeneov, Viktor A.

    Body hydration decreases significantly during hypokinesia (HK) (diminished movement), but little is known about the effect of fluid and salt supplements (FSS) on body hydration during HK. The aim of this study was to measure the effect of FSS on body hydration during HK. Studies were done during 30 days pre HK period and 364 days HK period. Thirty male athletes aged 24.5±6.6 yr were chosen as subjects. They were equally divided into three groups: unsupplemented ambulatory control subjects (UACS), unsupplemented hypokinetic subjects (UHKS) and supplemented hypokinetic subjects (SHKS). Hypokinetic subjects were limited to an average walking distance of 0.7 km day -1. The SHKS group took daily 30 ml of water/kg body weight and 0.1 g of sodium chloride (NaCl)/kg body weight. Control subjects experienced no changes in their professional training and routine daily activities. Plasma volume (PV), urinary and plasma sodium (Na) and potassium (K), plasma osmolality, plasma protein, whole blood hemoglobin (Hb) and hematocrit (Hct), plasma renin activity (PRA) plasma aldosterone (PA) levels, physical characteristics, food and fluid intakes were measured. Plasma osmolality, plasma protein, urinary and plasma Na and K, whole blood Hct and Hb, PRA and PA levels decreased significantly ( p⩽0.01), while PV and body weight increased significantly ( p⩽0.01) in the SHKS group when compared with the UHKS group and did not change when compared with the UACS group. Plasma osmolality, plasma protein, urinary and plasma Na and K, PRA and PA, whole blood Hb and Hct levels increased significantly ( p⩽0.01), while PV body weight, food and fluid intakes decreased significantly ( p⩽0.01) in UHKS group when compared with the SHKS and UACS groups. The measured parameters did not change in the UACS group when compared with their baseline control values. It was shown that during HK body hydration decreased significantly, while during HK and FSS body hydration increased significantly. It

  14. A composite phase diagram of structure H hydrates using Schreinemakers' geometric approach

    USGS Publications Warehouse

    Mehta, A.P.; Makogon, T.Y.; Burruss, R.C.; Wendlandt, R.F.; Sloan, E.D.

    1996-01-01

    A composite phase diagram is presented for Structure H (sH) clathrate hydrates. In this work, we derived the reactions occurring among the various phases along each four-phase (Ice/Liquid water, liquid hydrocarbon, vapor, and hydrate) equilibrium line. A powerful method (though seldom used in chemical engineering) for multicomponent equilibria developed by Schreinemakers is applied to determine the relative location of all quadruple (four-phase) lines emanating from three quintuple (five-phase) points. Experimental evidence validating the approximate phase diagram is also provided. The use of Schreinemakers' rules for the development of the phase diagram is novel for hydrates, but these rules may be extended to resolve the phase space of other more complex systems commonly encountered in chemical engineering.

  15. Prediction of the phase equilibria of methane hydrates using the direct phase coexistence methodology

    SciTech Connect

    Michalis, Vasileios K.; Costandy, Joseph; Economou, Ioannis G.; Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K.

    2015-01-28

    The direct phase coexistence method is used for the determination of the three-phase coexistence line of sI methane hydrates. Molecular dynamics (MD) simulations are carried out in the isothermal–isobaric ensemble in order to determine the coexistence temperature (T{sub 3}) at four different pressures, namely, 40, 100, 400, and 600 bar. Methane bubble formation that results in supersaturation of water with methane is generally avoided. The observed stochasticity of the hydrate growth and dissociation processes, which can be misleading in the determination of T{sub 3}, is treated with long simulations in the range of 1000–4000 ns and a relatively large number of independent runs. Statistical averaging of 25 runs per pressure results in T{sub 3} predictions that are found to deviate systematically by approximately 3.5 K from the experimental values. This is in good agreement with the deviation of 3.15 K between the prediction of TIP4P/Ice water force field used and the experimental melting temperature of ice Ih. The current results offer the most consistent and accurate predictions from MD simulation for the determination of T{sub 3} of methane hydrates. Methane solubility values are also calculated at the predicted equilibrium conditions and are found in good agreement with continuum-scale models.

  16. The use of gas-phase substrates to study enzyme catalysis at low hydration.

    PubMed Central

    Dunn, Rachel V; Daniel, Roy M

    2004-01-01

    Although there are varying estimates as to the degree of enzyme hydration required for activity, a threshold value of ca. 0.2 g of water per gram of protein has been widely accepted. The evidence upon which this is based is reviewed here. In particular, results from the use of gas-phase substrates are discussed. Results using solid-phase enzyme-substrate mixtures are not altogether in accord with those obtained using gas-phase substrates. The use of gaseous substrates and products provides an experimental system in which the hydration of the enzyme can be easily controlled, but which is not limited by diffusion. All the results show that increasing hydration enhances activity. The results using gas-phase substrates do not support the existence of a critical hydration value below which enzymatic activity is absent, and suggest that enzyme activity is possible at much lower hydrations than previously thought; they do not support the notion that significant hydration of the surface polar groups is required for activity. However, the marked improvement of activity as hydration is increased suggests that water does play a role, perhaps in optimizing the structure or facilitating the flexibility required for maximal activity. PMID:15306385

  17. Phase boundary of hot dense fluid hydrogen

    PubMed Central

    Ohta, Kenji; Ichimaru, Kota; Einaga, Mari; Kawaguchi, Sho; Shimizu, Katsuya; Matsuoka, Takahiro; Hirao, Naohisa; Ohishi, Yasuo

    2015-01-01

    We investigated the phase transformation of hot dense fluid hydrogen using static high-pressure laser-heating experiments in a laser-heated diamond anvil cell. The results show anomalies in the heating efficiency that are likely to be attributed to the phase transition from a diatomic to monoatomic fluid hydrogen (plasma phase transition) in the pressure range between 82 and 106 GPa. This study imposes tighter constraints on the location of the hydrogen plasma phase transition boundary and suggests higher critical point than that predicted by the theoretical calculations. PMID:26548442

  18. Hydration-Responsive Folding and Unfolding in Graphene Oxide Liquid Crystal Phases

    PubMed Central

    Guo, Fei; Kim, Franklin; Han, Tae Hee; Shenoy, Vivek B.; Huang, Jiaxing; Hurt, Robert H.

    2011-01-01

    Graphene oxide is promising as a plate-like giant molecular building block for the assembly of new carbon materials. Its water dispersibility, liquid crystallinity, and ease of reduction offer advantages over other carbon precursors if its fundamental assembly rules can be identified. This article shows that graphene oxide sheets of known lateral dimension form nematic liquid crystal phases with transition points in agreement with the Onsager hard-plate theory. The liquid crystal phases can be systematic ordered into defined supramolecular patterns using surface anchoring, complex fluid flow, and micro-confinement. Graphene oxide is seen to exhibit homeotropic surface anchoring at interfaces driven by excluded volume entropy and by adsorption enthalpy associated with its partially hydrophobic basal planes. Surprisingly, some of the surface-ordered graphene oxide phases dry into graphene oxide solids that undergo a dramatic anisotropic swelling upon rehydration to recover their initial size and shape. This behavior is shown to be a unique hydration-responsive folding and unfolding transition. During drying, surface tension forces acting parallel to the layer planes cause a buckling instability that stores elastic energy in accordion-folded structures in the dry solid. Subsequent water infiltration reduces interlayer frictional forces and triggers release of the stored elastic energy in the form of dramatic unidirectional expansion. We explain the folding/unfolding phenomena by quantitative nanomechanics, and introduce the potential of liquid crystal-derived graphene oxide phases as new stimuli-response materials. PMID:21877716

  19. Hydration-responsive folding and unfolding in graphene oxide liquid crystal phases.

    PubMed

    Guo, Fei; Kim, Franklin; Han, Tae Hee; Shenoy, Vivek B; Huang, Jiaxing; Hurt, Robert H

    2011-10-25

    Graphene oxide is promising as a plate-like giant molecular building block for the assembly of new carbon materials. Its water dispersibility, liquid crystallinity, and ease of reduction offer advantages over other carbon precursors if its fundamental assembly rules can be identified. This article shows that graphene oxide sheets of known lateral dimension form nematic liquid crystal phases with transition points in agreement with the Onsager hard-plate theory. The liquid crystal phases can be systematically ordered into defined supramolecular patterns using surface anchoring, complex fluid flow, and microconfinement. Graphene oxide is seen to exhibit homeotropic surface anchoring at interfaces driven by excluded volume entropy and by adsorption enthalpy associated with its partially hydrophobic basal planes. Surprisingly, some of the surface-ordered graphene oxide phases dry into graphene oxide solids that undergo a dramatic anisotropic swelling upon rehydration to recover their initial size and shape. This behavior is shown to be a unique hydration-responsive folding and unfolding transition. During drying, surface tension forces acting parallel to the layer planes cause a buckling instability that stores elastic energy in accordion-folded structures in the dry solid. Subsequent water infiltration reduces interlayer frictional forces and triggers release of the stored elastic energy in the form of dramatic unidirectional expansion. We explain the folding/unfolding phenomena by quantitative nanomechanics and introduce the potential of liquid crystal-derived graphene oxide phases as new stimuli-response materials. PMID:21877716

  20. The influence of hydrous phases on the microstructure and seismic properties of a hydrated mantle rock

    NASA Astrophysics Data System (ADS)

    Morales, Luiz F. G.; Mainprice, David; Boudier, Françoise

    2013-05-01

    To better understand the microstructural evolution of a “serpentinized” mantle rock and the influence of various hydrous phases on the seismic properties of the mantle wedge, we have conducted the detailed microstructural analyses of a sample of tremolite-chlorite-antigorite schist collected from the Moses Rock dike (central part of the Colorado Plateau). We performed differential effective media (DEM) modelling to study the effect of three hydrous phases forming two-phase aggregates with olivine, considering the crystallographic preferred orientation (CPO) of each phase and the shape ratio of the hydrous phases. We have demonstrated that in a partially serpentinized peridotite, the olivine CPO characteristic of [100](010) dislocation glide is still preserved, and the high-temperature asthenospheric flow is preserved with a foliation normal to that of antigorite schist. The transformation of olivine into antigorite occurs predominantly (~ 75%) by the relationship (100)ol || (001)atg with [001]ol || [010]atg, with the (010)ol || (001)atg and [001]ol || [010]atg relationship observed in areas of weak antigorite CPO. Chlorite results from the phase transformation of olivine in a relatively static environment, as shown by the correlation between the olivine-chlorite CPOs with (100)ol || (100)ch, (010)ol || (001)ch and (001)ol || (010)ch. The fluid percolation that caused the localized metasomatism and partial hydration of the mantle occurred possibly along trans-lithospheric shear zones. The presence of chlorite induces the most important drop on the P-wave velocities and may help to explain some local low velocities in the fore-arc mantle wedges, but is unlikely to be of global importance due to its very high Vp/Vs ratio ~ 1.9. On the other hand, antigorite is the only phase that causes important modification on the propagation directions of P and S-waves, and the only phase to explain the polarization of the fastest shear waves parallel to the subduction trench.

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

    USGS Publications Warehouse

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

    2006-01-01

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

  2. Influence of hydration status and fluid replacement on heat tolerance while wearing NBC protective clothing.

    PubMed

    Cheung, S S; McLellan, T M

    1998-01-01

    The purpose of the present study was to investigate the influence of hypohydration and fluid replacement on tolerance to an uncompensable heat stress. Eight healthy young males completed a matrix of six trials in an environmental chamber, set at 40 degrees C and 30% relative humidity, while wearing nuclear, biological, and chemical protective clothing. Subjects performed either light (3.5 km x h(-1), 0% grade, no wind) or heavy (4.8 km x h(-1), 4% grade, no wind) treadmill exercise combined with three hydration states [euhydration with fluid replacement (EU/F), euhydration without fluid replacement (EU/NF), and hypohydration with fluid replacement (H/F)]. Hypohydration of 2.2% body mass was achieved by exercise and fluid restriction on the day preceding the trials. No differences in the endpoint mean skin temperature (Tsk), sweat rate, or rectal temperature (Tre) were observed among the hydration conditions for either work rate. During light exercise, the change in Tre (deltaTre) was significantly higher with H/F than EU/F after 40 min, and heart rate was greater after 25 min. The heart rate was greater during EU/NF than during EU/F after 60 min. Tolerance times were significantly greater for EU/F than for either EU/NF or H/F. With heavy exercise, no differences in deltaTre were observed across hydration conditions. Compared to EU/F, heart rates were higher after 10 and 30 min for H/F and EU/NF, respectively. Tolerance times were significantly less during H/F than with either of the EU conditions. Stroke volume was significantly decreased in H/F trials compared to EU/F trials for both light and heavy work rates, but no differences in cardiac output were observed. It was concluded that even minor levels of hypohydration significantly impaired exercise tolerance in a severely uncompensable heat stress environment at both light and heavy exercise intensities. PMID:9459534

  3. X-ray structure determination of fully hydrated L alpha phase dipalmitoylphosphatidylcholine bilayers.

    PubMed Central

    Nagle, J F; Zhang, R; Tristram-Nagle, S; Sun, W; Petrache, H I; Suter, R M

    1996-01-01

    Bilayer form factors obtained from x-ray scattering data taken with high instrumental resolution are reported for multilamellar vesicles of L alpha phase lipid bilayers of dipalmitoylphosphatidylcholine at 50 degrees C under varying osmotic pressure. Artifacts in the magnitudes of the form factors due to liquid crystalline fluctuations have been eliminated by using modified Caillé theory. The Caillé fluctuation parameter eta 1 increases systematically with increasing lamellar D spacing and this explains why some higher order peaks are unobservable for the larger D spacings. The corrected form factors fall on one smooth continuous transform F(q); this shows that the bilayer does not change shape as D decreases from 67.2 A (fully hydrated) to 60.9 A. The distance between headgroup peaks is obtained from Fourier reconstruction of samples with four orders of diffraction and from electron density models that use 38 independent form factors. By combining these results with previous gel phase results, area AF per lipid molecule and other structural quantities are obtained for the fluid L alpha phase. Comparison with results that we derived from previous neutron diffraction data is excellent, and we conclude from diffraction studies that AF = 62.9 +/- 1.3 A2, which is in excellent agreement with a previous estimate from NMR data. PMID:8785298

  4. Fluid Phases of Carbon Nanotubes and Graphene

    NASA Astrophysics Data System (ADS)

    Pasquali, Matteo

    2013-03-01

    Nanoscale carbon--including Carbon Nanotubes (CNTs) as well as graphene, i.e., graphite in its single layered form--has remarkable electrical, thermal, and mechanical properties, more so than previously known polymer molecules or colloidal particles. Realizing these properties in applications requires understanding and controlling the behavior of fluid phases of CNTs and graphene. Biological and environmental applications are likely to require dilute phases of CNTs and graphene; material processing, e.g., production of coatings and fibers, will require more concentrated phases. Fluid processing is one of the most important frontiers of applied research in CNTs and graphene. Nano-carbon fluids are almost considered an oxymoron because dispersing or dissolving CNTs and graphene into fluid phases is exceedingly difficult. This talk reviews advances in understanding and controlling fluid phases of CNTs and graphene, with specific focus on single-object properties and true solutions. The dynamics of individual CNTs can be studied by fluorescence microscopy, revealing that their translational and rotational motion and bending stiffness can be described well by the semiflexible chain model. Even at low concentrations (few parts per million), CNTs form complex fluid phases with intriguing properties. In strong acids, CNTs as well as graphene dissolve spontaneously. At low concentration, these fluids can be used for making transparent, conducting films and coatings. In crowded environments, CNTs reptate like stiff polymers. At sufficiently high concentrations, CNTs and graphene form liquid crystals that can be spun into well-aligned, macroscopic fibers. Like in polymeric systems, the properties of macroscopic CNT materials depend on the length (molecular weight) of the constituent CNT macromolecules.

  5. Identification of the hydrate gel phases present in phosphate-modified calcium aluminate binders

    SciTech Connect

    Chavda, Mehul A.; Bernal, Susan A.; Apperley, David C.; Kinoshita, Hajime; Provis, John L.

    2015-04-15

    The conversion of hexagonal calcium aluminate hydrates to cubic phases in hydrated calcium aluminate cements (CAC) can involve undesirable porosity changes and loss of strength. Modification of CAC by phosphate addition avoids conversion, by altering the nature of the reaction products, yielding a stable amorphous gel instead of the usual crystalline hydrate products. Here, details of the environments of aluminium and phosphorus in this gel were elucidated using solid-state NMR and complementary techniques. Aluminium is identified in both octahedral and tetrahedral coordination states, and phosphorus is present in hydrous environments with varying, but mostly low, degrees of crosslinking. A {sup 31}P/{sup 27}Al rotational echo adiabatic passage double resonance (REAPDOR) experiment showed the existence of aluminium–phosphorus interactions, confirming the formation of a hydrated calcium aluminophosphate gel as a key component of the binding phase. This resolves previous disagreements in the literature regarding the nature of the disordered products forming in this system.

  6. Phase equilibria of H2SO4, HNO3, and HCl hydrates and the composition of polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  7. Phase Equilibria of H2SO4, HNO3, and HCl Hydrates and the Composition of Polar Stratospheric Clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  8. The nature of carbon-bearing phases in hydrated interplanetary dust particles. [Abstract only

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Thomas, K. L.; Mckay, D. S.

    1994-01-01

    We have been quantitatively measuring C abundances in hydrated interplanetary dust particles for the past few years, but in general, we have had to infer the distribution and nature of the C-bearing materials within these particles because of the complex microtextures of hydrated IDPs. Aside from rare carbonate grains, other C-bearing phases are difficult to distinguish from the fine-grained, poorly crystalline phyllosilicates that comprise the bulk of these particles. We know that carbonates alone cannot account for the high C abundances observed in most hydrated IDPs and that additional C-bearing phases must be present. We have recently applied the technique of electron energy-loss spectroscopy (EELS) in the transmission electron microscope (TEM) to identify and form the distribution of C-bearing phases in hydrated IDPs. These preliminary data show that several C-rich hydrated IDPs contain a mixture of two major forms of C, Mg-Fe carbonate and amorphous C. The near-edge structure in the C k-edges from these IDPs shows no evidence for the development of graphite or even poorly graphitized C. We conclude that the 'elemental' C in these IDPs is either very poorly ordered or is exceedingly fine-grained (we refer to this C as 'amorphous C'). The amorphous C is intimately intergrown with the fine-grained phyllosilicates and is evenly distributed within three of the four IDPs analyzed (only G1 contains discrete 'hot spots' of amorphous C). Not all hydrated IDPs contain carbonates.

  9. A combined QXRD/TG method to quantify the phase composition of hydrated Portland cements

    SciTech Connect

    Soin, Alexander V.; Catalan, Lionel J.J.; Kinrade, Stephen D.

    2013-06-15

    A new method is reported for quantifying the mineral phases in hydrated cement pastes that is based on a combination of quantitative X-ray diffractometry (QXRD) and thermogravimetry (TG). It differs from previous methods in that it gives a precise measure of the amorphous phase content without relying on an assumed stoichiometric relationship between the principal hydration products, calcium hydroxide (CH) and calcium silicate hydrate (C–S–H). The method was successfully applied to gray and white ordinary Portland cements (GOPC and WOPC, respectively) that were cured for up to 56 days. Phase distributions determined by QXRD/TG closely matched those from gray-level analysis of backscattered scanning electron microscope (BSEM) images, whereas elemental compositions obtained for the amorphous phase by QXRD/TG agreed well with those measured by quantitative energy dispersive X-ray spectroscopy (EDS)

  10. Endurance Cyclist Fluid Intake, Hydration Status, Thirst, and Thermal Sensations: Gender Differences.

    PubMed

    Armstrong, Lawrence E; Johnson, Evan C; McKenzie, Amy L; Ellis, Lindsay A; Williamson, Keith H

    2016-04-01

    This field investigation assessed differences (e.g., drinking behavior, hydration status, perceptual ratings) between female and male endurance cyclists who completed a 164-km event in a hot environment (35 °C mean dry bulb) to inform rehydration recommendations for athletes. Three years of data were pooled to create 2 groups of cyclists: women (n = 15) and men (n = 88). Women were significantly smaller (p < .001) than men in height (166 ± 5 vs. 179 ± 7 cm), body mass (64.6 ± 7.3 vs. 86.4 ± 12.3 kg), and body mass index (BMI; 23.3 ± 1.8 vs. 26.9 ± 3.4) and had lower preevent urinary indices of hydration status, but were similar to men in age (43 ± 7 years vs. 44 ± 9 years) and exercise time (7.77 ± 1.24 hr vs. 7.23 ± 1.75 hr). During the 164-km ride, women lost less body mass (-0.7 ± 1.0 vs. -1.7 ± 1.5 kg; -1.1 ± 1.6% vs. -1.9 ± 1.8% of body weight; p < .005) and consumed less fluid than men (4.80 ± 1.28 L vs. 5.59 ± 2.13 L; p < .005). Women consumed a similar volume of fluid as men, relative to body mass (milliliters/kilogram). To control for performance and anthropomorphic characteristics, 15 women were pair-matched with 15 men on the basis of exercise time on the course and BMI; urine-specific gravity, urine color, and body mass change (kilograms and percentage) were different (p < .05) in 4 of 6 comparisons. No gender differences were observed for ratings of thirst, thermal sensation, or perceived exertion. In conclusion, differences in relative fluid volume consumed and hydration indices suggest that professional sports medicine organizations should consider gender and individualized drinking plans when formulating pronouncements regarding rehydration during exercise. PMID:26479401

  11. A Descriptive Study of the Fluid Intake, Hydration, and Health Status of Rehabilitation Inpatients without Dysphagia Following Stroke.

    PubMed

    Murray, Jo; Doeltgen, Sebastian; Miller, Michelle; Scholten, Ingrid

    2015-01-01

    Adequate hydration is important for all people, particularly when hospitalized with illness. Individuals with dysphagia following stroke are considered to be at risk of inadequate fluid intake and, therefore, dehydration, but there is little information about the fluid intake or hydration of individuals without dysphagia poststroke. This cohort study measured the average beverage intake, calculated the urea/creatinine ratio as a measure of hydration, and documented specific health outcomes of 86 people without dysphagia poststroke who were inpatients in rehabilitation centers. Participants drank on average 1504 ml per day (SD 359 ml), which typically represented 67% of their estimated daily requirement. Approximately 44% of the participants in the sample were dehydrated based on a blood urea nitrogen/creatinine ratio >20:1. Sixteen percent of participants were diagnosed with one or more of the health outcomes of dehydration/hypernatremia, urinary tract infection, or constipation. A greater level of dependence was associated with poorer beverage intake and higher risk of an adverse health outcome. Those in the older/elderly age range (particularly older women) and those with poor mobility were most at risk of poor hydration. This study highlights that patients in rehabilitation facilities poststroke, even without dysphagia, may be at risk of suboptimal fluid intake and hydration. PMID:26267442

  12. Phase diagrams for clathrate hydrates of methane, ethane, and propane from first-principles thermodynamics.

    PubMed

    Cao, Xiaoxiao; Huang, Yingying; Li, Wenbo; Zheng, Zhaoyang; Jiang, Xue; Su, Yan; Zhao, Jijun; Liu, Changling

    2016-01-28

    Natural gas hydrates are inclusion compounds composed of major light hydrocarbon gaseous molecules (CH4, C2H6, and C3H8) and a water clathrate framework. Understanding the phase stability and formation conditions of natural gas hydrates is crucial for their future exploitation and applications and requires an accurate description of intermolecular interactions. Previous ab initio calculations on gas hydrates were mainly limited by the cluster models, whereas the phase diagram and equilibrium conditions of hydrate formation were usually investigated using the thermodynamic models or empirical molecular simulations. For the first time, we construct the chemical potential phase diagrams of type II clathrate hydrates encapsulated with methane/ethane/propane guest molecules using first-principles thermodynamics. We find that the partially occupied structures (136H2O·1CH4, 136H2O·16CH4, 136H2O·20CH4, 136H2O·1C2H6, and 136H2O·1C3H8) and fully occupied structures (136H2O·24CH4, 136H2O·8C2H6, and 136H2O·8C3H8) are thermodynamically favorable under given pressure-temperature (p-T) conditions. The theoretically predicted equilibrium pressures for pure CH4, C2H6 and C3H8 hydrates at the phase transition point are consistent with the experimental data. These results provide valuable guidance for establishing the relationship between the accurate description of intermolecular noncovalent interactions and the p-T equilibrium conditions of clathrate hydrates and other molecular crystals. PMID:26745181

  13. Hydration of an apolar solute in a two-dimensional waterlike lattice fluid.

    PubMed

    Buzano, C; De Stefanis, E; Pretti, M

    2005-05-01

    In a previous work, we investigated a two-dimensional lattice-fluid model, displaying some waterlike thermodynamic anomalies. The model, defined on a triangular lattice, is now extended to aqueous solutions with apolar species. Water molecules are of the "Mercedes Benz" type, i.e., they possess a D3 (equilateral triangle) symmetry, with three equivalent bonding arms. Bond formation depends both on orientation and local density. The insertion of inert molecules displays typical signatures of hydrophobic hydration: large positive transfer free energy, large negative transfer entropy (at low temperature), strong temperature dependence of the transfer enthalpy and entropy, i.e., large (positive) transfer heat capacity. Model properties are derived by a generalized first order approximation on a triangle cluster. PMID:16089537

  14. Hydration of an apolar solute in a two-dimensional waterlike lattice fluid

    NASA Astrophysics Data System (ADS)

    Buzano, C.; de Stefanis, E.; Pretti, M.

    2005-05-01

    In a previous work, we investigated a two-dimensional lattice-fluid model, displaying some waterlike thermodynamic anomalies. The model, defined on a triangular lattice, is now extended to aqueous solutions with apolar species. Water molecules are of the “Mercedes Benz” type, i.e., they possess a D3 (equilateral triangle) symmetry, with three equivalent bonding arms. Bond formation depends both on orientation and local density. The insertion of inert molecules displays typical signatures of hydrophobic hydration: large positive transfer free energy, large negative transfer entropy (at low temperature), strong temperature dependence of the transfer enthalpy and entropy, i.e., large (positive) transfer heat capacity. Model properties are derived by a generalized first order approximation on a triangle cluster.

  15. Dynamic fluid flow and chemical fluxes associated with a seafloor gas hydrate deposit on the northern Gulf of Mexico slope

    NASA Astrophysics Data System (ADS)

    Solomon, Evan A.; Kastner, Miriam; Jannasch, Hans; Robertson, Gretchen; Weinstein, Yishai

    2008-06-01

    Gas hydrates outcrop on the seafloor at the Bush Hill hydrocarbon seep site in the northern Gulf of Mexico. Four newly designed fluid flux meters/chemical samplers, called the MOSQUITO, were deployed for 430 days at Bush Hill to determine how dynamic subsurface fluid flow influences gas hydrate stability and to quantify the associated methane fluxes into the ocean. Three of the flux meters were deployed adjacent to an outcropping gas hydrate mound, while the fourth monitored background conditions. The flux meter measurements reveal that the subsurface hydrology in the vicinity of the mound is complex and variable with frequent changes from downward to upward flow ranging from - 161 to 273 cm/yr, and with temporal variations in the horizontal component of flow. The continuous record of fluid chemistry indicates that gas hydrate actively formed in the sediments. We propose that long periods of downward flow of seawater adjacent to gas vents (up to 4 months) are driven by local sub-pressure resulting from gas ebullition through faults and fractures due to overpressure at depth. High frequency variations in flow rates (days to weeks) are likely due to temporal changes in sediment permeability and the 3-D fluid flow field as a result of active gas hydrate and authigenic carbonate precipitation, as well as the presence of free gas. Gas hydrate formation occurred as a result of long-term emanation of CH4 at focused gas vents followed by a more diffuse intergranular methane flux. The estimated CH4 flux to the water column from focused gas vents across the Bush Hill seep is ~ 5•106 mol/yr. This significant flux suggests that Bush Hill and similar hydrocarbon seeps in the northwestern Gulf of Mexico may be important natural sources of methane to the ocean and possibly the atmosphere.

  16. Effect of fatty acids on phase behavior of hydrated dipalmitoylphosphatidylcholine bilayer: saturated versus unsaturated fatty acids.

    PubMed

    Inoue, T; Yanagihara, S; Misono, Y; Suzuki, M

    2001-02-01

    The effect of some fatty acids on the phase behavior of hydrated dipalmitoylphosphatidylcholine (DPPC) bilayer was investigated with special interest in possible difference between saturated and unsaturated fatty acids. The phase behavior of hydrated DPPC bilayer was followed by a differential scanning calorimetry and a Fourier transform infrared spectroscopy. The addition of palmitic acid (PA) increased the bilayer phase transition temperature with the increase of the PA content in the mixture. In addition, DPPC molecules in gel phase bilayer became more rigid in the presence of PA compared with those in the absence of PA. This effect of PA on the phase behavior of hydrated DPPC bilayer is common to other saturated fatty acids, stearic acid, myristic acid, and also to unsaturated fatty acid with trans double bond, elaidic acid. Contrary to these fatty acids, oleic acid (OA), the unsaturated fatty acid with cis double bond in the acyl chain, exhibited quite different behavior. The effect of OA on the bilayer phase transition temperature was rather small, although a slight decrease in the temperature was appreciable. Furthermore, the IR spectral results demonstrated that the perturbing effect of OA on the gel phase bilayer of DPPC was quite small. These results mean that OA does not disturb the hydrated DPPC bilayer significantly. PMID:11269932

  17. Pore-Scale Controls on Permeability, Fluid Flow, and Methane Hydrate Distribution in Fine-Grained Sediments

    NASA Astrophysics Data System (ADS)

    Daigle, Hugh Callahan

    2011-12-01

    Permeability in fine-grained sediments is governed by the surface area exposed to fluid flow and tortuosity of the pore network. I modify an existing technique of computing permeability from nuclear magnetic resonance (NMR) data to extend its applicability beyond reservoir-quality rocks to the fine-grained sediments that comprise the majority of the sedimentary column. This modification involves correcting the NMR data to account for the large surface areas and disparate mineralogies typically exhibited by fine-grained sediments. Through measurements on resedimented samples composed of controlled mineralogies, I show that this modified NMR permeability algorithm accurately predicts permeability over 5 orders of magnitude. This work highlights the importance of pore system surface area and geometry in determining transport properties of porous media. I use these insights to probe the pore-scale controls on methane hydrate distribution and hydraulic fracturing behavior, both of which are controlled by flux and permeability. To do this I employ coupled poromechanical models of hydrate formation in marine sediments. Fracture-hosted methane hydrate deposits are found at many sites worldwide, and I investigate whether pore occlusion and permeability reduction due to hydrate formation can drive port fluid pressures to the point at which the sediments fracture hydraulically. I find that hydraulic fractures may form in systems with high flux and/or low permeability; that low-permeability layers can influence the location of fracture initiation if they are thicker than a critical value that is a function of flux and layer permeability; that capillary-driven depression of the triple point of methane in fine-gained sediments causes hydrate to form preferentially in coarse-grained layers; that the relative fluxes of gas and water in multiphase systems controls hydrate distribution and the location of fracture initiation; and that methane hydrate systems are dynamic systems in

  18. Hydration profile and influence of beverage contents on fluid intake by women during outdoor recreational walking.

    PubMed

    O'Neal, E K; Poulos, S P; Bishop, P A

    2012-12-01

    This study examined hydration status, sweat losses, and the effects of flavoring and electrolytes on fluid intake for women (n = 27, age = 24 ± 4 years) walking at a self-selected pace for ~1 h on a 1 km outdoor path during summer mornings or evenings. Over five consecutive days, participants consumed ad libitum one non-caloric beverage containing: (1) water (W), (2) acidified water (AW), (3) acidified water with electrolytes (AWE), (4) acidified water with flavor (AWF), and (5) acidified water with flavor and electrolytes (AWFE) in a counter-balanced order during walks and a 1-h recovery period. Walk Wet bulb globe temperature (26.2 ± 1.8 °C) and pace (6.0 ± 0.5 km/h) did not differ among beverages (P > 0.05). Thirty-four percent of pre-walk urine specific gravity samples exceeded 1.020. Flavoring (AWF 700 ± 393 mL; AWFE 719 ± 405 mL) did not result in greater consumption (P > 0.05) over W (560 ± 315 mL), with all three beverages exceeding grand mean sweat losses (528 ± 208 mL). Addition of electrolytes did not influence (P > 0.05) the intake between AW versus AWE or AWF versus AWFE. The results of this study indicate that the majority of women will consume fluids in excess of their sweat losses within 1 h post-walk. Over half of consumption took place during walks, highlighting the importance of fluid availability during exercise. Great among-subjects variability in sweat losses and fluid intake support the need for promoting individualized hydration strategies based on the changes in body mass for athletic populations. PMID:22434252

  19. 2-Phase Fluid Flow & Heat Transport

    Energy Science and Technology Software Center (ESTSC)

    1993-03-13

    GEOTHER is a three-dimensional, geothermal reservoir simulation code. The model describes heat transport and flow of a single component, two-phase fluid in porous media. It is based on the continuity equations for steam and water, which are reduced to two nonlinear partial differential equations in which the dependent variables are fluid pressure and enthalpy. GEOTHER can be used to simulate the fluid-thermal interaction in rock that can be approximated by a porous media representation. Itmore » can simulate heat transport and the flow of compressed water, two-phase mixtures, and superheated steam in porous media over a temperature range of 10 to 300 degrees C. In addition, it can treat the conversion from single to two-phase flow, and vice versa. It can be used for evaluation of a near repository spatial scale and a time scale of a few years to thousands of years. The model can be used to investigate temperature and fluid pressure changes in response to thermal loading by waste materials.« less

  20. Ammonia clathrate hydrates as new solid phases for Titan, Enceladus, and other planetary systems.

    PubMed

    Shin, Kyuchul; Kumar, Rajnish; Udachin, Konstantin A; Alavi, Saman; Ripmeester, John A

    2012-09-11

    There is interest in the role of ammonia on Saturn's moons Titan and Enceladus as the presence of water, methane, and ammonia under temperature and pressure conditions of the surface and interior make these moons rich environments for the study of phases formed by these materials. Ammonia is known to form solid hemi-, mono-, and dihydrate crystal phases under conditions consistent with the surface of Titan and Enceladus, but has also been assigned a role as water-ice antifreeze and methane hydrate inhibitor which is thought to contribute to the outgassing of methane clathrate hydrates into these moons' atmospheres. Here we show, through direct synthesis from solution and vapor deposition experiments under conditions consistent with extraterrestrial planetary atmospheres, that ammonia forms clathrate hydrates and participates synergistically in clathrate hydrate formation in the presence of methane gas at low temperatures. The binary structure II tetrahydrofuran + ammonia, structure I ammonia, and binary structure I ammonia + methane clathrate hydrate phases synthesized have been characterized by X-ray diffraction, molecular dynamics simulation, and Raman spectroscopy methods. PMID:22908239

  1. Molecular Modeling of Solid Fluid Phase Behavior

    SciTech Connect

    Peter A. Monson

    2007-12-20

    This report gives a summary of the achievements under DOE contract No. DOE/ER/14150 during the period September 1, 1990 to December 31, 2007. This project was concerned with the molecular modeling of solid-fluid equilibrium. The focus was on understanding how solid-fluid and solid-solid phase behavior are related to molecular structure, and the research program made a seminal contribution in this area. The project led to 34 journal articles, including a comprehensive review article published in Advances in Chemical Physics. The DOE funding supported the work of 5 Ph.D. students, 2 M.S. students and 5 postdoctoral researchers.

  2. Accurate description of phase diagram of clathrate hydrates at the molecular level

    NASA Astrophysics Data System (ADS)

    Belosludov, Rodion V.; Subbotin, Oleg S.; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki; Belosludov, Vladimir R.

    2009-12-01

    In order to accurately estimate the thermodynamic properties of hydrogen clathrate hydrates, we developed a method based on the solid solution theory of van der Waals and Platteeuw. This model allows one to take into account the influence of guest molecules on the host lattice and guest-guest interactions—especially when more than one guest molecule occupies a cage. The free energies, equations of state, and chemical potentials of hydrogen and mixed propane-hydrogen clathrate hydrates of cubic structure II with different cage fillings have been estimated using this approach. Moreover, the proposed theory has been used for construction p -T phase diagrams of hydrogen hydrate and mixed hydrogen-propane hydrates in a wide range of pressures and temperatures. For the systems with well defined interactions the calculated curves of "guest gas-hydrate-ice Ih" equilibrium agree with the available experimental data. We also believe that the present model allows one not only to calculate the hydrogen storage ability of known hydrogen hydrate but also predict this value for structures that have not yet been realized by experiment.

  3. The mechanism of vapor phase hydration of calcium oxide: implications for CO2 capture.

    PubMed

    Kudłacz, Krzysztof; Rodriguez-Navarro, Carlos

    2014-10-21

    Lime-based sorbents are used for fuel- and flue-gas capture, thereby representing an economic and effective way to reduce CO2 emissions. Their use involves cyclic carbonation/calcination which results in a significant conversion reduction with increasing number of cycles. To reactivate spent CaO, vapor phase hydration is typically performed. However, little is known about the ultimate mechanism of such a hydration process. Here, we show that the vapor phase hydration of CaO formed after calcination of calcite (CaCO3) single crystals is a pseudomorphic, topotactic process, which progresses via an intermediate disordered phase prior to the final formation of oriented Ca(OH)2 nanocrystals. The strong structural control during this solid-state phase transition implies that the microstructural features of the CaO parent phase predetermine the final structural and physicochemical (reactivity and attrition) features of the product hydroxide. The higher molar volume of the product can create an impervious shell around unreacted CaO, thereby limiting the efficiency of the reactivation process. However, in the case of compact, sintered CaO structures, volume expansion cannot be accommodated in the reduced pore volume, and stress generation leads to pervasive cracking. This favors complete hydration but also detrimental attrition. Implications of these results in carbon capture and storage (CCS) are discussed. PMID:25233236

  4. Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases

    NASA Astrophysics Data System (ADS)

    Dureckova, Hana; Woo, Tom K.; Alavi, Saman

    2016-01-01

    Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br2 and Cl2 in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water-oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formation of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br2 and Cl2 clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br2 and Cl2 guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br2 and Cl2 guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br2 and Cl2 guests in the hydrate cages may explain why bromine forms the unique TS-I phase.

  5. Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases.

    PubMed

    Dureckova, Hana; Woo, Tom K; Alavi, Saman

    2016-01-28

    Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br2 and Cl2 in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water-oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formation of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br2 and Cl2 clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br2 and Cl2 guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br2 and Cl2 guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br2 and Cl2 guests in the hydrate cages may explain why bromine forms the unique TS-I phase. PMID:26827220

  6. The void in using urine concentration to assess population fluid intake adequacy or hydration status.

    PubMed

    Cheuvront, Samuel N; Muñoz, Colleen X; Kenefick, Robert W

    2016-09-01

    Urine concentration can be used to assess fluid intake adequacy or to diagnose dehydration. However, too often urine concentration is used inappropriately to draw dubious conclusions that could have harmful health and economic consequences. Inappropriate uses of urine concentration relate primarily to convenience sampling (timing) and problems related to convenience sampling (misapplication of thresholds), but a conceptual problem also exists with using urine concentration in isolation. The purpose of this Perspective article is to briefly explain the problematic nature of current practices and to offer a possible solution to improve practice with minimal added complication. When urine is used exclusively to assess fluid intake adequacy and hydration status in adults, we propose that only when urine concentration is high (>850 mmol/kg) and urine excretion rate is low (<850 mL/24 h) should suspicion of inadequate drinking or impending dehydration be considered. Prospective tests of the 850 × 850 thresholds will provide supporting evidence and/or help refine the best thresholds for men and women, young and old. PMID:27465376

  7. Hydration and phase separation of polyethylene glycol in copolymers of tyrosine derived carbonates.

    NASA Astrophysics Data System (ADS)

    Sanjeeva Murthy, N.; Wang, Wenjie; Kohn, Joachim

    2009-03-01

    Effect of PEG fraction and its block size on the temperature-induced phase transitions and the hydration-induced phase separation were investigated in a copolymer of desaminotyrosyl tyrosine ethyl ester (DTE) and PEG using simultaneous SAXS/WAXS/DSC. The PEG segments crystallized when the block size was at least 2000 Daltons and present at ˜ 40 wt%, and raised the Tg of the polymer by ˜ 15 ^oC. The PEG blocks in dry polymers with up to 50 wt% PEG, even when crystalline, were found to be uniformly distributed with no evidence of phase separation at 10 nm length scales. The non-iodinated PEG-rich sample with 30 mole% PEG2k showed the lower critical solution temperature (LCST) behavior with PEG blocks forming a separate phase above -21 ^oC. In the iodinated version of this polymer, the PEG2k blocks were phase separated in the solid phase. In all samples, whether PEG was crystalline or not, hydration induced PEG to separate into 15 nm hydrated domains. Phase behavior was dependent on whether poly(DTE) or the PEG was the major (matrix) phase. Changes in the mobility of the chains brought about by water-mediated hydrogen-bonding, and modulated by heat, appear to be the common underlying explanation for the range of observed phase behavior.

  8. Pathways through equilibrated states with coexisting phases for gas hydrate formation

    SciTech Connect

    Malolepsza, Edyta; Keyes, Tom

    2015-12-01

    Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces the initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Furthermore, free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation.

  9. Pathways through Equilibrated States with Coexisting Phases for Gas Hydrate Formation.

    PubMed

    Małolepsza, Edyta; Keyes, Tom

    2015-12-31

    Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces the initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation. PMID:26624929

  10. Pathways through equilibrated states with coexisting phases for gas hydrate formation

    DOE PAGESBeta

    Malolepsza, Edyta; Keyes, Tom

    2015-12-01

    Under ambient conditions, water freezes to either hexagonal ice or a hexagonal/cubic composite ice. The presence of hydrophobic guest molecules introduces a competing pathway: gas hydrate formation, with the guests in clathrate cages. Here, the pathways of the phase transitions are sought as sequences of states with coexisting phases, using a generalized replica exchange algorithm designed to sample them in equilibrium, avoiding nonequilibrium processes. For a dilute solution of methane in water under 200 atm, initializing the simulation with the full set of replicas leads to methane trapped in hexagonal/cubic ice, while gradually adding replicas with decreasing enthalpy produces themore » initial steps of hydrate growth. Once a small amount of hydrate is formed, water rearranges to form empty cages, eventually transforming the remainder of the system to metastable β ice, a scaffolding for hydrates. It is suggested that configurations with empty cages are reaction intermediates in hydrate formation when more guest molecules are available. Furthermore, free energy profiles show that methane acts as a catalyst reducing the barrier for β ice versus hexagonal/cubic ice formation.« less

  11. Direct Measurement of the Fluid Phase Diagram.

    PubMed

    Bao, Bo; Riordon, Jason; Xu, Yi; Li, Huawei; Sinton, David

    2016-07-19

    The thermodynamic phase of a fluid (liquid, vapor or supercritical) is fundamental to all chemical processes, and the critical point is particularly important for supercritical chemical extraction. Conventional phase measurement methods require hours to obtain a single datum on the pressure and temperature diagram. Here, we present the direct measurement of the full pressure-temperature phase diagram, with 10 000 microwells. Orthogonal, linear, pressure and temperature gradients are obtained with 100 parallel microchannels (spanning the pressure range), each with 100 microwells (spanning the temperature range). The phase-mapping approach is demonstrated with both a pure substance (CO2) and a mixture (95% CO2 + 5% N2). Liquid, vapor, and supercritical regions are clearly differentiated, and the critical pressure is measured at 1.2% error with respect to the NIST standard. This approach provides over 100-fold improvement in measurement speed over conventional methods. PMID:27331613

  12. Phase behavior of an amphiphilic fluid.

    PubMed

    Schoen, Martin; Giura, Stefano; Klapp, Sabine H L

    2014-01-01

    We invoke mean-field density functional theory (DFT) to investigate the phase behavior of an amphiphilic fluid composed of a hard-sphere core plus a superimposed anisometric Lennard-Jones perturbation. The orientation dependence of the interactions consists of a contribution analogous to the interaction potential between a pair of "spins" in the classical, three-dimensional Heisenberg fluid and another one reminiscent of the interaction between (electric or magnetic) point dipoles. At fixed orientation both contributions are short-range in nature decaying as r-6 (r being the separation between the centers of mass of a pair of amphiphiles). Based upon two mean-field-like approximations for the pair correlation function that differ in the degree of sophistication we derive expressions for the phase boundaries between various isotropic and polar phases that we solve numerically by the Newton-Raphson method. For sufficiently strong coupling between the Heisenberg "spins" both mean-field approximations generate three topologically different and generic types of phase diagrams that are observed in agreement with earlier work [see, for example, Tavares et al., Phys. Rev. E 52, 1915 (1995)]. Whereas the dipolar contribution alone is incapable of stabilizing polar phases on account of its short-range nature it is nevertheless important for details of the phase diagram such as location of the gas-isotropic liquid critical point, triple, and tricritical points. By tuning the dipolar coupling constant suitably one may, in fact, switch between topologically different phase diagrams. Employing also Monte Carlo simulations in the isothermal-isobaric ensemble the general topology of the DFT phase diagrams is confirmed. PMID:24580230

  13. Phase behavior of an amphiphilic fluid

    NASA Astrophysics Data System (ADS)

    Schoen, Martin; Giura, Stefano; Klapp, Sabine H. L.

    2014-01-01

    We invoke mean-field density functional theory (DFT) to investigate the phase behavior of an amphiphilic fluid composed of a hard-sphere core plus a superimposed anisometric Lennard-Jones perturbation. The orientation dependence of the interactions consists of a contribution analogous to the interaction potential between a pair of "spins" in the classical, three-dimensional Heisenberg fluid and another one reminiscent of the interaction between (electric or magnetic) point dipoles. At fixed orientation both contributions are short-range in nature decaying as r-6 (r being the separation between the centers of mass of a pair of amphiphiles). Based upon two mean-field-like approximations for the pair correlation function that differ in the degree of sophistication we derive expressions for the phase boundaries between various isotropic and polar phases that we solve numerically by the Newton-Raphson method. For sufficiently strong coupling between the Heisenberg "spins" both mean-field approximations generate three topologically different and generic types of phase diagrams that are observed in agreement with earlier work [see, for example, Tavares et al., Phys. Rev. E 52, 1915 (1995), 10.1103/PhysRevE.52.1915]. Whereas the dipolar contribution alone is incapable of stabilizing polar phases on account of its short-range nature it is nevertheless important for details of the phase diagram such as location of the gas-isotropic liquid critical point, triple, and tricritical points. By tuning the dipolar coupling constant suitably one may, in fact, switch between topologically different phase diagrams. Employing also Monte Carlo simulations in the isothermal-isobaric ensemble the general topology of the DFT phase diagrams is confirmed.

  14. Calcium silicate hydrates: Solid and liquid phase composition

    SciTech Connect

    Lothenbach, Barbara; Nonat, André

    2015-12-15

    This paper presents a review on the relationship between the composition, the structure and the solution in which calcium silicate hydrate (C–S–H) is equilibrated. The silica chain length in C–S–H increases with the silicon concentration and the calcium content in the interlayer space with the calcium concentrations. Sodium and potassium are taken up in the interlayer space, preferentially at low calcium concentrations and thus by low Ca/Si C–S–H. Aluminium uptake in C–S–H increases strongly at higher aluminium concentrations in the solution. At low Ca/Si, aluminium substitutes silica in the bridging position, at Ca/Si > 1 aluminium is bound in TAH. Recently developed thermodynamic models are closely related to the structure of C–S–H and tobermorite, and able to model not only the solubility and the chemical composition of the C–S–H, but also to predict the mean silica chain length and the uptake of aluminium.

  15. Fluid Leakages in Gas-Hydrate Systems at the Storegga Slide of the Mid-Norwegian Margin

    NASA Astrophysics Data System (ADS)

    Hustoft, S.; Mienert, J.; Buenz, S.

    2005-12-01

    High-resolution 3D-seismic data has given new insight to the fluid flow regime at the well-documented gas-hydrate system along the northern flank of the Storegga Slide of the passive mid-Norwegian continental margin. Fluids are expelled from a widespread polygonal fault system of fine-grained, Miocene sediments of the lower Kai Formation that contribute to formation of gas hydrates in the study area. Previous work has mainly presumed a diffusive fluid flow regime above the polygonal fault system into the gas hydrate stability zone. However, 3D-seismic data indicates that migrating fluids above the polygonal fault system are focused trough imbricated small-offset fault zones in the upper stratigraphic level of the Kai Formation. Fluids seems to accumulate laterally within the lower level of the overlying Plio-Pleistocene Naust Formation, causing a small-scale dome structure with low frequency content, above the imbricated fault zones. Vertical fluid leakage originates from the extended dome structure causing fracturing in sediments throughout a ~200 m sedimentary sequence. The fluid leakage terminates within strata represented by negative amplitude anomalies located beneath a bottom-simulating reflector (BSR). Free gas in relatively porous media is deflected laterally by impermeable hydrated sediments occurring down-slope, and less permeable glacigenic sediments up-slope. At the upper termination of the fractured sediments within the Plio-Pleistocene formation, a 3 km long channel is recognized showing a geometric shape opposite to the stratigraphic deep-seated dome structure, but having the same lateral extension. The presence of vertical blowout pipes in direct proximity to the channel, indicate high pore pressure build-up. Adding to the complexity of the fluid flow system in gas hydrate settings, the channel might be a seismic artefact due to the presence of gas (pushdown), rather than a morphological feature. Due to the low organic matter content (< 1 %) of

  16. Feasibility of Using Phase Change Materials to Control the Heat of Hydration in Massive Concrete Structures

    PubMed Central

    Choi, Won-Chang; Khil, Bae-Soo; Chae, Young-Seok; Liang, Qi-Bo; Yun, Hyun-Do

    2014-01-01

    This paper presents experimental results that can be applied to select a possible phase change material (PCM), such as a latent heat material (LHM), to control the hydration heat in mass concrete structures. Five experimental tests (microconduction, simplified adiabatic temperature rise, heat, and compressive strength tests) were conducted to select the most desirable LHM out of seven types of inorganic PCM used in cement mortar and to determine the most suitable mix design. The results of these experimental tests were used to assess the feasibility of using PCM to reduce hydration heat in mass concrete that was examined. The experimental results show that cement mortar containing barium- [Ba(OH)2·8H2O] based PCM has the lowest amount of total hydration heat of the cement pastes. The barium-based PCM provides good latent heat properties that help to prevent volume change and microcracks caused by thermal stress in mass concrete. PMID:25133259

  17. Feasibility of using phase change materials to control the heat of hydration in massive concrete structures.

    PubMed

    Choi, Won-Chang; Khil, Bae-Soo; Chae, Young-Seok; Liang, Qi-Bo; Yun, Hyun-Do

    2014-01-01

    This paper presents experimental results that can be applied to select a possible phase change material (PCM), such as a latent heat material (LHM), to control the hydration heat in mass concrete structures. Five experimental tests (microconduction, simplified adiabatic temperature rise, heat, and compressive strength tests) were conducted to select the most desirable LHM out of seven types of inorganic PCM used in cement mortar and to determine the most suitable mix design. The results of these experimental tests were used to assess the feasibility of using PCM to reduce hydration heat in mass concrete that was examined. The experimental results show that cement mortar containing barium- [Ba(OH)2 · 8H2O] based PCM has the lowest amount of total hydration heat of the cement pastes. The barium-based PCM provides good latent heat properties that help to prevent volume change and microcracks caused by thermal stress in mass concrete. PMID:25133259

  18. Ecological and climatic consequences of phase instability of gas hydrates on the ocean bed

    NASA Astrophysics Data System (ADS)

    Balanyuk, I.; Dmitrievsky, A.; Akivis, T.; Chaikina, O.

    2009-04-01

    energy and gas that leads to explosion. Methane is the main natural source for power engineering specialists. It is transported by pipelines, and gas hydrate is dangerous in this case too. It can block the gas pipeline system forming the so-called "trombus" of "thermal ice". After that the pipes have to be opened. The mess of this strange ice discovered melts immediately releasing methane and water vapor. The trombus formation can be prevented by the temperature increase or the pressure decrease. Both methods are very uncomfortable under the conditions the pipelines work. The better method is thorough drying up of the gas because gas hydrate obviously cannot be formed without water. Gas hydrates attract attention not only as a fuel and chemical stuff but in relation to a serious anxiety of strong ecological and climatic problems that can occur as a result of methane release to the atmosphere due to both gas hydrate deposits development and minor changes in thermodynamic conditions in the vicinity of a threshold of gas hydrate phase stability. One of the most probable causes is the global warming of the Earth due to the hothouse effect because the specific absorption of the Earth heat radiation by methane (radiation effectivity) is 21 times higher than its absorption by carbonic gas. Analysis of the air trapped by polar ice show that contemporary increase of methane concentration in the atmosphere is unexampled for the last 160 thousands of years. The sources of this increase are not clear. Observer and latent methane bursts during natural gas hydrates decomposition can be considered as a probable source. Amount of methane hided in natural gas hydrates is 3000 times higher its amount in the atmosphere. Release of this hothouse potential would have terrible consequences for the humanity. The warming can cause further gas hydrates decomposition and released methane will cause the following warming. Thus, self-accelerating process can start. The most vulnerable for the

  19. Reentrant Phase Diagram of Network Fluids

    NASA Astrophysics Data System (ADS)

    Russo, J.; Tavares, J. M.; Teixeira, P. I. C.; Telo da Gama, M. M.; Sciortino, F.

    2011-02-01

    We introduce a microscopic model for particles with dissimilar patches which displays an unconventional “pinched” phase diagram, similar to the one predicted by Tlusty and Safran in the context of dipolar fluids [Science 290, 1328 (2000)SCIEAS0036-807510.1126/science.290.5495.1328]. The model—based on two types of patch interactions, which account, respectively, for chaining and branching of the self-assembled networks—is studied both numerically via Monte Carlo simulations and theoretically via first-order perturbation theory. The dense phase is rich in junctions, while the less-dense phase is rich in chain ends. The model provides a reference system for a deep understanding of the competition between condensation and self-assembly into equilibrium-polymer chains.

  20. Controls on mound formation and effects of fluid ascent on the gas hydrate system of mound structures offshore Costa Rica

    NASA Astrophysics Data System (ADS)

    Planert, L.; Klaeschen, D.; Berndt, C.; Hensen, C.; Brueckmann, W.

    2010-12-01

    Our analysis of 2D MCS seismic data from the Middle America margin provides an insight into the buildup and formation mechanisms of mound structures and the effects of fluid ascent on the gas hydrate system observed on the continental slope offshore Costa Rica. Our targets, Mounds 11&12, are the sites of IODP drilling proposal 633-Full2, which aims to enhance the general understanding of complex forearc dewatering processes of the erosive subduction system off Costa Rica. Major sites of dewatering planned for drilling are mounds, related to mud diapirism/volcanism and precipitation of authigenic carbonates, and large-scale slides related to the subduction of seamounts. Geochemical analysis of methane hydrate and chloride anomalies as well as heat flow modeling of the mounds indicate deeply sourced fluids discharged by clay dehydration at the decollement. Hence, the hydrogeological system at this margin appears to be dominated by the fracture porosity of faults which extend through the overriding plate and provide the paths for fluids liberated by early dehydration reactions from the plate boundary. In order to test the hypothesis of deeply sourced and fault-controlled dewatering sites and to better understand the interactions between gas hydrate formation and dissociation with the fluid ascent from the deep sources, new pre-site survey seismic profiles were acquired using the 36-gun, four-string linear gun array of R/V Marcus Langseth, and a 240 channel streamer with 3000 m of active length. The seismic lines were prestack depth migrated, in which the velocity model is iteratively improved using depth focusing analysis and residual moveout correction on common image point gathers. Improvement of the deep imaging involved multiple attenuation and detailed velocity analysis of the lower sedimentary portions and beneath the basement down to the plate boundary. Our results reveal an upward bending of the bottom simulating reflection (BSR) directly beneath the mounds

  1. Non-equilibrium Simulation of CO­2-hydrate Phase Transitions from Mixtures of CO2 and N2 Gases

    NASA Astrophysics Data System (ADS)

    Qorbani Nashaqi, K.

    2015-12-01

    Storage of CO2 in aquifers is one of several options for reducing the emissions of CO2 to the atmosphere. Generally this option requires sealing integrity through layers of clay or shale. Many reservoirs have regions of temperature and pressure inside hydrate formation conditions. Whether hydrate formation can provide long term extra sealing still remains unverified in view of all co-existing phases that affect hydrate stability. Yet another storage option for CO2 is in the form of hydrate through exchange of in situ CH4 hydrate. Injection of CO2 into hydrate filled sediments is challenging due to the partial filling of pores with hydrate which results in low porosity and low permeability. Formation of new hydrate from injected CO2 will enhance these problems, Mixing N2 gas with the CO2 will increase permeability and will reduce driving forces for formation of new hydrate from pore water and injection gas. Hydrate can generally not reach thermodynamic equilibrium due to Gibbs' phase rule and the combined first and second laws of thermodynamics. These thermodynamic constraints on distribution of masses over co-existing phases are dynamically coupled to local mass- and heat-transport. Reservoir simulations are one possible method for investigation of possible scenarios related to injection of CO2 with N2 into aquifers containing CH4 hydrate. In this work we have developed prevoiusly modified RetrasoCodeBrite (RCB) simulator to handle injection of CO2/N2 gas mixtures. Hydrate formation and dissociation were determined by investigating Gibbs free energy differences between hydrate and hydrate formers. Gibbs free energy differences were calculated from changes in chemical potentials, which were obtained using non-equilibrium thermodynamic approach. Further extension of RCB has been implemented in this work through adding on-the-fly thermodynamic calculations. Correspondingly, hydrate phase transitions are calculated directly inside the code as a result of super

  2. Molecular dynamics simulation of CO2 hydrates: Prediction of three phase coexistence line.

    PubMed

    Míguez, J M; Conde, M M; Torré, J-P; Blas, F J; Piñeiro, M M; Vega, C

    2015-03-28

    The three phase equilibrium line (hydrate-liquid water-liquid carbon dioxide) has been estimated for the water + carbon dioxide binary mixture using molecular dynamics simulation and the direct coexistence technique. Both molecules have been represented using rigid nonpolarizable models. TIP4P/2005 and TIP4P/Ice were used for the case of water, while carbon dioxide was considered as a three center linear molecule with the parameterizations of MSM, EPM2, TraPPE, and ZD. The influence of the initial guest occupancy fraction on the hydrate stability has been analyzed first in order to determine the optimal starting configuration for the simulations, paying attention to the influence of the two different cells existing in the sI hydrate structure. The three phase coexistence temperature was then determined for a pressure range from 2 to 500 MPa. The qualitative shape of the equilibrium curve estimated is correct, including the high pressure temperature maximum that determines the hydrate re-entrant behaviour. However, in order to obtain quantitative agreement with experimental results, a positive deviation from the classical Lorentz-Berthelot combining rules must be considered. PMID:25833594

  3. Molecular dynamics simulation of CO2 hydrates: Prediction of three phase coexistence line

    NASA Astrophysics Data System (ADS)

    Míguez, J. M.; Conde, M. M.; Torré, J.-P.; Blas, F. J.; Piñeiro, M. M.; Vega, C.

    2015-03-01

    The three phase equilibrium line (hydrate-liquid water-liquid carbon dioxide) has been estimated for the water + carbon dioxide binary mixture using molecular dynamics simulation and the direct coexistence technique. Both molecules have been represented using rigid nonpolarizable models. TIP4P/2005 and TIP4P/Ice were used for the case of water, while carbon dioxide was considered as a three center linear molecule with the parameterizations of MSM, EPM2, TraPPE, and ZD. The influence of the initial guest occupancy fraction on the hydrate stability has been analyzed first in order to determine the optimal starting configuration for the simulations, paying attention to the influence of the two different cells existing in the sI hydrate structure. The three phase coexistence temperature was then determined for a pressure range from 2 to 500 MPa. The qualitative shape of the equilibrium curve estimated is correct, including the high pressure temperature maximum that determines the hydrate re-entrant behaviour. However, in order to obtain quantitative agreement with experimental results, a positive deviation from the classical Lorentz-Berthelot combining rules must be considered.

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

    USGS Publications Warehouse

    Chou, I.-Ming; Sharma, A.; Burruss, R.C.; Hemley, R.J.; Goncharov, A.F.; Stern, L.A.; Kirby, S.H.

    2001-01-01

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

  5. Stable isotopic (O, H) evidence for hydration of the central Colorado Plateau lithospheric mantle by slab-derived fluids

    NASA Astrophysics Data System (ADS)

    Marshall, E. W.; Barnes, J.; Lassiter, J. C.

    2013-12-01

    The Colorado Plateau is a tectonically stable, relatively undeformed Proterozoic lithospheric province in the North America Cordillera. Although the stability of the Colorado Plateau suggests that it is rheologically strong, evidence from xenoliths show that the lithospheric mantle is extensively hydrated (e.g., presence of hydrous minerals, 'high' water contents in nominally anhydrous minerals), and therefore weakened. In addition, LREE enrichments in clinopyroxene (cpx) imply that the lithospheric mantle has been metasomatized ([1],[2]). Here we analyze mineral separates from spinel and garnet peridotite xenoliths from the Navajo Volcanic Field (NVF), located in the center of the Plateau, for their oxygen and hydrogen isotope compositions. These compositions are compared to those of xenoliths at the margins of the Plateau: spinel peridotites from the Grand Canyon Volcanic Field (GCVF) in the west and Zuni-Bandera Volcanic Field (ZBVF) in the east. NVF xenoliths are significantly more hydrous than the xenoliths on the margins of the Colorado Plateau based on modal abundances of hydrous minerals and structural water in olivine (e.g. [3]). All hydrous phases have high δD values (antigorite = -71 to -46‰ (n = 6 xenoliths); chlorite = -49 to -31‰ (n=3); amphibole = -47‰ (n=1)) compared to normal mantle (~-80‰), suggesting the addition of a fluid that is enriched in D compared to typical mantle. δ18O values for the same hydrous minerals range from 6.0 to 6.6‰ (n=6). δ18O values of olivine from NVF spinel peridotites have a narrow range, 5.0 to 5.4‰ (n = 4), near mantle olivine values (~5.2‰). Olivines from spinel peridotites from the GCVF and ZBVF also have mantle-like δ18O values (5.1 to 5.2‰ (n=3) and 5.1 to 5.4‰ (n=7), respectively). However, olivines and orthopyroxenes (opx) from NVF garnet peridotites have a slightly larger range and some record 18O enrichment (olivine = 5.1 to 5.6‰ (n = 3); opx = 5.9‰ (n=1)). The high δ18O values of

  6. Seismic and seafloor evidence for free gas, gas hydrates, and fluid seeps on the transform margin offshore Cape Mendocino

    NASA Astrophysics Data System (ADS)

    TréHu, Anne M.; Stakes, Debra S.; Bartlett, Cindy D.; Chevallier, Johanna; Duncan, Robert A.; Goffredi, Shana K.; Potter, Susan M.; Salamy, Karen A.

    2003-05-01

    Seismic data and seafloor samples indicate the presence of free gas, gas hydrate, and fluid seeps south of the Gorda Escarpment, a topographic feature that marks the eastern end of the Gorda/Pacific transform plate boundary southwest of Cape Mendocino, California. In spite of high sedimentation rates and high biological productivity, direct or indirect indicators of gas hydrate presence had not previously been recognized in this region, or along transform margins in general. Gas is indicated by a bottom simulating reflection (BSR) observed near the Gorda Escarpment, by "bright spots" and "gas curtains" scattered throughout the sedimentary basin to the south, and by δ13C and δ18O isotopes of carbonates, which are similar to those recovered from other hydrate-bearing regions. The BSR reflection coefficient of -0.13 ± 0.04 and interval velocities as low as 1.38 km/s indicate that free gas is present beneath the BSR. Local shallowing of the BSR toward the north facing Gorda Escarpment and beneath a channel near the crest suggests fluid flow toward the seafloor. Integrating these various observations, we suggest a scenario in which methane is formed in thick Miocene and Pliocene deposits of organic-rich sediments that fill the marginal basin south of the transform fault. Dissolved and free gas migrates toward the escarpment along stratigraphic horizons, resulting in hydrate formation and in channels, slumps and chemosynthetic communities on the face of the escarpment. We conclude that the BSR appears where hydrate-bearing sediments are uplifted because of current triple junction tectonics.

  7. Fluid flow and methane occurrences in the Disko Bugt area offshore West Greenland: indications for gas hydrates?

    NASA Astrophysics Data System (ADS)

    Nielsen, Tove; Laier, Troels; Kuijpers, Antoon; Rasmussen, Tine L.; Mikkelsen, Naja E.; Nørgård-Pedersen, Niels

    2014-12-01

    The present study is the first to directly address the issue of gas hydrates offshore West Greenland, where numerous occurrences of shallow hydrocarbons have been documented in the vicinity of Disko Bugt (Bay). Furthermore, decomposing gas hydrate has been implied to explain seabed features in this climate-sensitive area. The study is based on archive data and new (2011, 2012) shallow seismic and sediment core data. Archive seismic records crossing an elongated depression (20×35 km large, 575 m deep) on the inner shelf west of Disko Bugt (Bay) show a bottom simulating reflector (BSR) within faulted Mesozoic strata, consistent with the occurrence of gas hydrates. Moreover, the more recently acquired shallow seismic data reveal gas/fluid-related features in the overlying sediments, and geochemical data point to methane migration from a deeper-lying petroleum system. By contrast, hydrocarbon signatures within faulted Mesozoic strata below the strait known as the Vaigat can be inferred on archive seismics, but no BSR was visible. New seismic data provide evidence of various gas/fluid-releasing features in the overlying sediments. Flares were detected by the echo-sounder in July 2012, and cores contained ikaite and showed gas-releasing cracks and bubbles, all pointing to ongoing methane seepage in the strait. Observed seabed mounds also sustain gas seepages. For areas where crystalline bedrock is covered only by Pleistocene-Holocene deposits, methane was found only in the Egedesminde Dyb (Trough). There was a strong increase in methane concentration with depth, but no free gas. This is likely due to the formation of gas hydrate and the limited thickness of the sediment infill. Seabed depressions off Ilulissat Isfjord (Icefjord) previously inferred to express ongoing gas release from decomposing gas hydrate show no evidence of gas seepage, and are more likely a result of neo-tectonism.

  8. Phase equilibria for complex fluid mixtures

    SciTech Connect

    Prausnitz, J.M.

    1983-04-01

    After defining complex mixtures, attention is given to the canonical procedure used for the thermodynamics of fluid mixtures: first, we establish a suitable, idealized reference system and then we establish a perturbation (or excess function) which corrects the idealized system for real behavior. For complex mixtures containing identified components (e.g. alcohols, ketones, water) discussion is directed at possible techniques for extending to complex mixtures our conventional experience with reference systems and perturbations for simple mixtures. Possible extensions include generalization of the quasi-chemical approximation (local compositions) and superposition of chemical equilibria (association and solvation) on a physical equation of state. For complex mixtures containing unidentified components (e.g. coal-derived fluids), a possible experimental method is suggested for characterization; conventional procedures can then be used to calculate phase equilibria using the concept of pseudocomponents whose properties are given by the characterization data. Finally, as an alternative to the pseudocomponent method, a brief introduction is given to phase-equilibrium calculations using continuous thermodynamics.

  9. Direct visualization of the hydration layer on alumina nanoparticles with the fluid cell STEM in situ

    SciTech Connect

    Firlar, Emre; Çınar, Simge; Kashyap, Sanjay; Akinc, Mufit; Prozorov, Tanya

    2015-05-21

    Rheological behavior of aqueous suspensions containing nanometer-sized powders is of relevance to many branches of industry. Unusually high viscosities observed for suspensions of nanoparticles compared to those of micron size powders cannot be explained by current viscosity models. Formation of so-called hydration layer on alumina nanoparticles in water was hypothesized, but never observed experimentally. We report here on the direct visualization of aqueous suspensions of alumina with the fluid cell in situ. We observe the hydration layer formed over the particle aggregates and show that such hydrated aggregates constitute new particle assemblies and affect the flow behavior of the suspensions. We discuss how these hydrated nanoclusters alter the effective solid content and the viscosity of nanostructured suspensions. As a result, our findings elucidate the source of high viscosity observed for nanoparticle suspensions and are of direct relevance to many industrial sectors including materials, food, cosmetics, pharmaceutical among others employing colloidal slurries with nanometer-scale particles.

  10. Hydration energies of sodiated amino acids from gas-phase equilibria determinations.

    PubMed

    Wincel, Henryk

    2007-07-01

    The sequential hydration of a number of sodiated amino acids is investigated using a high-pressure mass spectrometer. Ions produced continuously by electrospray are injected into the reaction chamber in the pulsed mode where the hydration equilibria, AANa+(H2O)n-1+H2O=AANa+(H2O)n (AA=Val, Pro, Met, Phe, and Gln), and the temperature dependence of the equilibrium constants are measured in the gas phase at 10 mbar (N2 bath gas and known pressure of H2O). The thermochemical properties, DeltaH degrees n, DeltaS degrees n, and DeltaG degrees n, for the hydrated systems are determined and discussed in conjunction with the structural forms. The results show that the binding energies of water to the AANa+ complexes decrease with the increasing number of water molecules. The present results from equilibrium measurements are compared to those from earlier studies obtained by other techniques. A correlation between the free energy changes for the addition of the first and second water molecules to AANa+, and the corresponding sodium ion affinities, is observed. Generally, the hydration free energy becomes weaker as the AA-Na+ bond strength increases. PMID:17559201

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

    PubMed Central

    2014-01-01

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

  12. Phase mixing induced by granular fluid pump during mantle strain localization

    NASA Astrophysics Data System (ADS)

    Précigout, Jacques; Prigent, Cécile; Palasse, Laurie; Pochon, Anthony

    2014-05-01

    Mantle viscous strain localization is often attributed to feedbacks between grain boundary sliding (GBS) and phase mixing, as GBS could promote mixing through grain switching, and phase mixing would enhance grain-size-sensitive granular flow through grain boundary pinning. However, although GBS and phase mixing are intimately related, recent data show that GBS alone cannot end-up with randomly mixed phases. Here we show natural observations of an ultramylonitic shear zone from the Ronda peridotite (Spain) where both GBS and phase mixing occur. Microprobe analyses and coupled EDX/EBSD data first document enrichment in pyroxenes and amphibole concomitant with both phase mixing and complete randomization of the olivine fabric in fine-grained layers (5-20 microns) where strain has been localized. Both the fabric randomization and some microstructural observations indicate that these layers mostly deformed by granular flow, i.e., by GBS. Based on petrological pseudo-sections, we also show that phase enrichment does not result from metamorphic reaction, but instead from dissolution-precipitation phenomena. Finally, we document in adjacent areas a change of olivine fabric geometry that highlights syn-tectonic water draining towards fine-grained layers. While olivine fabric switches from E-type (moderately hydrated fabric) to C-type (highly hydrated fabric) towards fine-grained layers, it changes from E-type to D-type (highly hydrated fabric) in coarse-grained bands between E/C-type layers. Altogether, our findings suggest that water converges as a result of GBS-induced creep cavitation and subsequent granular fluid pump in fine-grained layers. We propose that phase mixing originates here from such a creep cavitation through dissolution-precipitation of secondary phases in newly formed cavities, giving rise to a key process for the relationships between GBS and phase mixing, and hence, for the origin of viscous strain localization in the upper mantle.

  13. Phase behavior and 13C NMR spectroscopic analysis of the mixed methane + ethane + propane hydrates in mesoporous silica gels.

    PubMed

    Lee, Seungmin; Cha, Inuk; Seo, Yongwon

    2010-11-25

    In this study, the phase behavior and quantitative determination of hydrate composition and cage occupancy for the mixed CH(4) + C(2)H(6) + C(3)H(8) hydrates were closely investigated through the experimental measurement of three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria and (13)C NMR spectra. To examine the effect of pore size and salinity, we measured hydrate phase equilibria for the quaternary CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) + water mixtures in silica gel pores of nominal diameters of 6.0, 15.0, and 30.0 nm and for the quinary CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) + NaCl + water mixtures of two different NaCl concentrations (3 and 10 wt %) in silica gel pores of a nominal 30.0 nm diameter. The value of hydrate-water interfacial tension for the CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) hydrate was found to be 47 ± 4 mJ/m(2) from the relation of the dissociation temperature depression with the pore size of silica gels at a given pressure. At a specified temperature, three-phase H-L(W)-V equilibrium curves of pore hydrates were shifted to higher pressure regions depending on pore sizes and NaCl concentrations. From the cage-dependent (13)C NMR chemical shifts of enclathrated guest molecules, the mixed CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) gas hydrate was confirmed to be structure II. The cage occupancies of each guest molecule and the hydration number of the mixed gas hydrates were also estimated from the (13)C NMR spectra. PMID:20964277

  14. Phase changes of filled ice Ih methane hydrate under low temperature and high pressure

    NASA Astrophysics Data System (ADS)

    Tanaka, Takehiko; Hirai, Hisako; Matsuoka, Takahiro; Ohishi, Yasuo; Yagi, Takehiko; Ohtake, Michika; Yamamoto, Yoshitaka; Nakano, Satoshi; Irifune, Tetsuo

    2013-09-01

    Low-temperature and high-pressure experiments were performed with filled ice Ih structure of methane hydrate under 2.0-77.0 GPa and 30-300 K using diamond anvil cells and a helium-refrigeration cryostat. In situ X-ray diffractometry revealed distinct changes in the compressibility of the axial ratios of the host framework with pressure. Raman spectroscopy showed a split in the C-H vibration modes of the guest methane molecules, which was previously explained by the orientational ordering of the guest molecules. The pressure and temperature conditions at the split of the vibration modes agreed well with those of the compressibility change. The results indicate the following: (i) the orientational ordering of the guest methane molecules from an orientationally disordered state occurred at high pressures and low temperatures; and (ii) this guest ordering led to anisotropic contraction in the host framework. Such guest orientational ordering and subsequent anisotropic contraction of the host framework were similar to that reported previously for filled ice Ic hydrogen hydrate. Since phases with different guest-ordering manners were regarded as different phases, existing regions of the guest disordered-phase and the guest ordered-phase were roughly estimated by the X-ray study. In addition, above the pressure of the guest-ordered phase, another high-pressure phase developed in the low-temperature region. The deuterated-water host samples were also examined, and the influence of isotopic effects on guest ordering and phase transformation was observed.

  15. Changes in hydration status of elite Olympic class sailors in different climates and the effects of different fluid replacement beverages

    PubMed Central

    2013-01-01

    Background Olympic class sailing poses physiological challenges similar to other endurance sports such as cycling or running, with sport specific challenges of limited access to nutrition and hydration during competition. As changes in hydration status can impair sports performance, examining fluid consumption patterns and fluid/electrolyte requirements of Olympic class sailors is necessary to develop specific recommendations for these elite athletes. The purpose of this study was to examine if Olympic class sailors could maintain hydration status with self-regulated fluid consumption in cold conditions and the effect of fixed fluid intake on hydration status in warm conditions. Methods In our cold condition study (CCS), 11 elite Olympic class sailors were provided ad libitum access to three different drinks. Crystal Light (control, C); Gatorade (experimental control, G); and customized sailing-specific Infinit (experimental, IN) (1.0:0.22 CHO:PRO), were provided on three separate training days in cold 7.1°C [4.2 – 11.3]. Our warm condition study (WCS) examined the effect of fixed fluid intake (11.5 mL.kg.-1.h-1) of C, G and heat-specific experimental Infinit (INW)(1.0:0.074 CHO:PRO) on the hydration status of eight elite Olympic Laser class sailors in 19.5°C [17.0 - 23.3]. Both studies used a completely random design. Results In CCS, participants consumed 802 ± 91, 924 ± 137 and 707 ± 152 mL of fluid in each group respectively. This did not change urine specific gravity, but did lead to a main effect for time for body mass (p < 0.001), blood sodium, potassium and chloride with all groups lower post-training (p < 0.05). In WCS, fixed fluid intake increased participant’s body mass post-training in all groups (p < 0.01) and decreased urine specific gravity post-training (p < 0.01). There was a main effect for time for blood sodium, potassium and chloride concentration, with lower values observed post-training (p < 0.05). C

  16. X-Ray Structure Determination of Fully Hydrated L_alpha Phase DPPC Lipid Bilayers

    NASA Astrophysics Data System (ADS)

    Nagle, John F.

    1996-03-01

    Accurate and reliable structural information is more difficult to obtain for lipid bilayers in the biologically relevant fully hydrated L_α thermodynamic phase than for bilayers at lower hydration or for phases that occur at lower temperature because there are fewer x-ray or neutron reflections. There have been many studies of the benchmark lipid DPPC, but these have yielded unacceptably large discrepancies ranging from 58 to 71 Åfor interfacial area A^F per lipid molecule. We have resolved this uncertainty using X-ray scattering with high instrumental resolution at CHESS for multilamellar vesicles of L_α phase lipid bilayers of DPPC at 50^circC under varying osmotic pressure.(This work was performed by the authors of ref. 3 and Horia Petrache. This research is supported by NIH grant GM-44976.) Artifacts in the magnitudes of the form factors due to liquid crystalline fluctuations have been eliminated by using modified Caillé theory (R. Zhang, R. M. Suter and J. F. Nagle, Phys. Rev. E50, 5047 (1994)), which we have shown to provide an excellent fit to the data (R. Zhang, S. Tristram-Nagle, W. Sun, R. Headrick, T. Irving, R. Suter and J. Nagle, Biophys. J., in press for 1/96). The Caillé fluctuation parameter η1 increases systematically with increasing D spacing and this explains why some higher order peaks are unobservable for the larger D spacings. The corrected form factors fall on one smooth continuous transform F(q); this shows that the bilayer does not change shape as D decreases from 67.2 Åfully hydrated) to 53.9 Åthereby validating the biological relevance of older neutron diffraction data taken on less than fully hydrated samples. We obtain the distance between headgroup peaks from Fourier reconstruction of electron density profiles for samples with four orders of diffraction and also from electron density models that use 38 independent form factors. By combining these results with our previous gel phase results, we obtain the area A^F = 62.9±1.3

  17. Controlled-source electromagnetic and seismic delineation of sub-seafloor fluid flow structures in a gas hydrate province, offshore Norway

    NASA Astrophysics Data System (ADS)

    Attias, Eric; Weitemeyer, Karen; Minshull, Tim A.; Best, Angus I.; Sinha, Martin; Jegen-Kulcsar, Marion; Hölz, Sebastian; Berndt, Christian

    2016-05-01

    Deep sea pockmarks underlain by chimney-like or pipe structures that contain methane hydrate are abundant along the Norwegian continental margin. In such hydrate provinces the interaction between hydrate formation and fluid flow has significance for benthic ecosystems and possibly climate change. The Nyegga region, situated on the western Norwegian continental slope, is characterized by an extensive pockmark field known to accommodate substantial methane gas hydrate deposits. The aim of this study is to detect and delineate both the gas hydrate and free gas reservoirs at one of Nyegga's pockmarks. In 2012, a marine controlled-source electromagnetic (CSEM) survey was performed at a pockmark in this region, where high-resolution three-dimensional seismic data were previously collected in 2006. Two-dimensional CSEM inversions were computed using the data acquired by ocean bottom electrical field receivers. Our results, derived from unconstrained and seismically constrained CSEM inversions, suggest the presence of two distinctive resistivity anomalies beneath the pockmark: a shallow vertical anomaly at the underlying pipe structure, likely due to gas hydrate accumulation, and a laterally extensive anomaly attributed to a free gas zone below the base of the gas hydrate stability zone. This work contributes to a robust characterization of gas hydrate deposits within sub-seafloor fluid flow pipe structures.

  18. The 10Å phase: a high-pressure expandable sheet silicate stable during subduction of hydrated lithosphere

    NASA Astrophysics Data System (ADS)

    Fumagalli, Patrizia; Stixrude, Lars; Poli, Stefano; Snyder, Don

    2001-03-01

    H 2O storage and release in deep subducting lithosphere is controlled by complex reaction suites involving a variety of hydrous phases. As a result of its relatively large thermal stability and intermediate composition, the 10Å phase (Mg 3Si 4O 10(OH) 2· nH 2O) has been regarded as a relevant H 2O reservoir in a wide range of rock compositions and mineral assemblages. High-pressure syntheses of the 10Å phase were carried out at 6.7 GPa and 650°C under fluid-saturated conditions in a Walker-type multi-anvil apparatus, from 5 min to 430 h. X-ray powder diffraction of large platy hexagonal crystals of the 10Å phase (up to 100 μm) were indexed on the basis of a trioctahedral-type structure. Long-term run products (>110 h) reveal sensitivity of the 10Å phase to treatment with acetone leading to the appearance of diffractions at greater d-spacings (10.2-11.6 Å) with respect to the basal peak of the 10Å phase (9.64-10.07 Å). This swelling behavior is strongly related to synthesis run duration. The Raman spectrum of the 10Å phase at frequencies less than 800 cm -1 shows a strong similarity to talc. In the Si-O stretching region (800-1100 cm -1), the 10Å phase exhibits three modes (909, 992 and 1058 cm -1), as compared to two in talc. The bending mode of water (ν 2) is found at 1593 cm -1. In the OH stretching region, peaks at 3593, 3622 and 3668 cm -1 were observed. The acetone treated sample shows a C-H stretching mode at 2923 cm -1 while the double bond CO signal is absent. The swelling behavior of the 10Å phase is interpreted as due to intercalation of acetone with pre-existing interlayer water. The efficiency of this process is dependent on the amount of the interlayer water which in turn depends on run duration. The relation between the response to acetone treatment and run duration is therefore interpreted as a time-dependent hydration of the 10Å phase. The fractions transformed from non-expandable to expandable fractions was fitted to the Avrami

  19. The infrared spectrum of ammonia hydrate - Explanation for a reported ammonia phase

    NASA Technical Reports Server (NTRS)

    Still, G.; Fink, U.; Ferraro, J. R.

    1981-01-01

    A number of anomalous spectra of solid NH3 deposited from the vapor phase have appeared in the literature. These spectra have been ascribed to a new phase of NH3. In the experiment reported here these anomalous spectra were reproduced by depositing a thin film from a mixture of gaseous NH3 and H2O and annealing this film at a temperature of 162 K. The thin film spectra showed excellent agreement with recent data on NH3.H2O. The anomalous 'NH3' spectra are, therefore, seen to be caused by H2O contamination of solid NH3 with formation of NH3 hydrate.

  20. Use of cosmogenic 129I to constrain numerical models of fluid flow in marine sediments: Application to the Blake Ridge Hydrate Province

    NASA Astrophysics Data System (ADS)

    Frederick, Jennifer M.; Buffett, Bruce A.

    2013-05-01

    of cosmogenic iodine, 129I, in the pore fluid of marine sediments often indicate that the pore fluid is much older than the host sediment, even when vertical flow due to sediment compaction is taken into account. Old pore fluid has been used in previous studies to argue for pervasive upward fluid flow and a deep methane source for hydrate deposits. Alternatively, old pore fluid age may reflect more complex flow patterns. We use a two-dimensional numerical transport model to account for the effects of topography and fractures on pore fluid pathlines when sediment permeability is anisotropic. We find that fluid focusing can cause significant lateral migration as well as regions where downward flow reverses direction and returns toward the seafloor. Longer pathlines can produce pore fluid ages much older than that expected with a one-dimensional compaction model. For steady-state models with geometry representative of Blake Ridge (USA), a well-studied hydrate province, we find pore fluid ages beneath regions of topography and within fractured zones that are up to 70 Ma old. Our results suggest that the measurements of 129I/127I reflect a mixture of new and old pore fluid. However, old pore fluid need not originate at great depths. Methane within pore fluids can travel laterally several kilometers, implying an extensive source region around the deposit. This type of focusing should aid hydrate formation beneath topographic highs.

  1. Multiscale approach to CO2 hydrate formation in aqueous solution: phase field theory and molecular dynamics. Nucleation and growth.

    PubMed

    Tegze, György; Pusztai, Tamás; Tóth, Gyula; Gránásy, László; Svandal, Atle; Buanes, Trygve; Kuznetsova, Tatyana; Kvamme, Bjorn

    2006-06-21

    A phase field theory with model parameters evaluated from atomistic simulations/experiments is applied to predict the nucleation and growth rates of solid CO(2) hydrate in aqueous solutions under conditions typical to underwater natural gas hydrate reservoirs. It is shown that under practical conditions a homogeneous nucleation of the hydrate phase can be ruled out. The growth rate of CO(2) hydrate dendrites has been determined from phase field simulations as a function of composition while using a physical interface thickness (0.85+/-0.07 nm) evaluated from molecular dynamics simulations. The growth rate extrapolated to realistic supersaturations is about three orders of magnitude larger than the respective experimental observation. A possible origin of the discrepancy is discussed. It is suggested that a kinetic barrier reflecting the difficulties in building the complex crystal structure is the most probable source of the deviations. PMID:16821944

  2. Gas-phase uranyl, neptunyl, and plutonyl: hydration and oxidation studied by experiment and theory.

    PubMed

    Rios, Daniel; Michelini, Maria C; Lucena, Ana F; Marçalo, Joaquim; Bray, Travis H; Gibson, John K

    2012-06-18

    The following monopositive actinyl ions were produced by electrospray ionization of aqueous solutions of An(VI)O(2)(ClO(4))(2) (An = U, Np, Pu): U(V)O(2)(+), Np(V)O(2)(+), Pu(V)O(2)(+), U(VI)O(2)(OH)(+), and Pu(VI)O(2)(OH)(+); abundances of the actinyl ions reflect the relative stabilities of the An(VI) and An(V) oxidation states. Gas-phase reactions with water in an ion trap revealed that water addition terminates at AnO(2)(+)·(H(2)O)(4) (An = U, Np, Pu) and AnO(2)(OH)(+)·(H(2)O)(3) (An = U, Pu), each with four equatorial ligands. These terminal hydrates evidently correspond to the maximum inner-sphere water coordination in the gas phase, as substantiated by density functional theory (DFT) computations of the hydrate structures and energetics. Measured hydration rates for the AnO(2)(OH)(+) were substantially faster than for the AnO(2)(+), reflecting additional vibrational degrees of freedom in the hydroxide ions for stabilization of hot adducts. Dioxygen addition resulted in UO(2)(+)(O(2))(H(2)O)(n) (n = 2, 3), whereas O(2) addition was not observed for NpO(2)(+) or PuO(2)(+) hydrates. DFT suggests that two-electron three-centered bonds form between UO(2)(+) and O(2), but not between NpO(2)(+) and O(2). As formation of the UO(2)(+)-O(2) bonds formally corresponds to the oxidation of U(V) to U(VI), the absence of this bonding with NpO(2)(+) can be considered a manifestation of the lower relative stability of Np(VI). PMID:22656318

  3. Phase transitions in fluids and biological systems

    NASA Astrophysics Data System (ADS)

    Sipos, Maksim

    In this thesis, I consider systems from two seemingly different fields: fluid dynamics and microbial ecology. In these systems, the unifying features are the existences of global non-equilibrium steady states. I consider generic and statistical models for transitions between these global states, and I relate the model results with experimental data. A theme of this thesis is that these rather simple, minimal models are able to capture a lot of functional detail about complex dynamical systems. In Part I, I consider the transition between laminar and turbulent flow. I find that quantitative and qualitative features of pipe flow experiments, the superexponential lifetime and the splitting of turbulent puffs, and the growth rate of turbulent slugs, can all be explained by a coarse-grained, phenomenological model in the directed percolation universality class. To relate this critical phenomena approach closer to the fluid dynamics, I consider the transition to turbulence in the Burgers equation, a simplified model for Navier-Stokes equations. Via a transformation to a model of directed polymers in a random medium, I find that the transition to Burgers turbulence may also be in the directed percolation universality class. This evidence implies that the turbulent-to-laminar transition is statistical in nature and does not depend on details of the Navier-Stokes equations describing the fluid flow. In Part II, I consider the disparate subject of microbial ecology where the complex interactions within microbial ecosystems produce observable patterns in microbe abundance, diversity and genotype. In order to be able to study these patterns, I develop a bioinformatics pipeline to multiply align and quickly cluster large microbial metagenomics datasets. I also develop a novel metric that quantifies the degree of interactions underlying the assembly of a microbial ecosystem, particularly the transition between neutral (random) and niche (deterministic) assembly. I apply this

  4. Properties of nuclear waste melts and glasses: Contact-refractory corrosion and vapor phase hydration

    NASA Astrophysics Data System (ADS)

    Lu, Xiaodong

    Control of refractory corrosion in waste glass melts and meeting vapor phase hydration test (VHT) requirement for Hanford low-activity waste (LAW) glass product are two critical issues among many technical challenges of nuclear waste vitrification. In this study, refractory corrosion was treated as a complex non-equilibrium, multi-component and multi-phase reactive transport process and studied both thermodynamically and kinetically. Dissolution tests of granular refractory materials into under-saturated melts coupled with crystallization tests from supersaturated melts were used to determine the possible equilibrium points. The test results show that spinet phase is the most stable phase of K-3 refractory. Solubility of glass-refractory interface material controls the long term refractory corrosion rate and protects refractory from further corrosion. Therefore, refractory corrosion rate can be possibly adjusted by controlling the underlying solubility of the interface material. A set of monolithic refractory corrosion and dissolution tests was carried out to study the kinetic effects of refractory porosity and glass melt viscosity, the two major kinetic factors associated with reactive transport process. The test results show that temperature and glass melt viscosity have intensive effects on refractory material dissolution rate. Fast closure of channels near the glass-refractory interface during corrosion reaction by fast transformation of solid solution to spinel and spinel re-crystallization helps stop further corrosion reaction. Glass composition can be "passivated" by engineering the formulation to maximizing the beneficial alteration process. For the study of VHT kinetics, data from simulated LAW glasses studied previously at Pacific Northwest National Laboratory and Vitreous State Laboratory was modeled based on Avrami equation and its variant, the so-called generalized Avrami equation for better modeling of the VHT data. The results show that the kinetics

  5. Thermal conductivity of hydrate-bearing sediments

    USGS Publications Warehouse

    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.

  6. Desalination utilizing clathrate hydrates (LDRD final report).

    SciTech Connect

    Simmons, Blake Alexander; Bradshaw, Robert W.; Dedrick, Daniel E.; Cygan, Randall Timothy; Greathouse, Jeffery A.; Majzoub, Eric H.

    2008-01-01

    Advances are reported in several aspects of clathrate hydrate desalination fundamentals necessary to develop an economical means to produce municipal quantities of potable water from seawater or brackish feedstock. These aspects include the following, (1) advances in defining the most promising systems design based on new types of hydrate guest molecules, (2) selection of optimal multi-phase reactors and separation arrangements, and, (3) applicability of an inert heat exchange fluid to moderate hydrate growth, control the morphology of the solid hydrate material formed, and facilitate separation of hydrate solids from concentrated brine. The rate of R141b hydrate formation was determined and found to depend only on the degree of supercooling. The rate of R141b hydrate formation in the presence of a heat exchange fluid depended on the degree of supercooling according to the same rate equation as pure R141b with secondary dependence on salinity. Experiments demonstrated that a perfluorocarbon heat exchange fluid assisted separation of R141b hydrates from brine. Preliminary experiments using the guest species, difluoromethane, showed that hydrate formation rates were substantial at temperatures up to at least 12 C and demonstrated partial separation of water from brine. We present a detailed molecular picture of the structure and dynamics of R141b guest molecules within water cages, obtained from ab initio calculations, molecular dynamics simulations, and Raman spectroscopy. Density functional theory calculations were used to provide an energetic and molecular orbital description of R141b stability in both large and small cages in a structure II hydrate. Additionally, the hydrate of an isomer, 1,2-dichloro-1-fluoroethane, does not form at ambient conditions because of extensive overlap of electron density between guest and host. Classical molecular dynamics simulations and laboratory trials support the results for the isomer hydrate. Molecular dynamics simulations

  7. Application of the cell potential method to predict phase equilibria of multicomponent gas hydrate systems.

    PubMed

    Anderson, Brian J; Bazant, Martin Z; Tester, Jefferson W; Trout, Bernhardt L

    2005-04-28

    We present the application of a mathematical method reported earlier by which the van der Waals-Platteeuw statistical mechanical model with the Lennard-Jones and Devonshire approximation can be posed as an integral equation with the unknown function being the intermolecular potential between the guest molecules and the host molecules. This method allows us to solve for the potential directly for hydrates for which the Langmuir constants are computed, either from experimental data or from ab initio data. Given the assumptions made in the van der Waals-Platteeuw model with the spherical-cell approximation, there are an infinite number of solutions; however, the only solution without cusps is a unique central-well solution in which the potential is at a finite minimum at the center to the cage. From this central-well solution, we have found the potential well depths and volumes of negative energy for 16 single-component hydrate systems: ethane (C2H6), cyclopropane (C3H6), methane (CH4), argon (Ar), and chlorodifluoromethane (R-22) in structure I; and ethane (C2H6), cyclopropane (C3H6), propane (C3H8), isobutane (C4H10), methane (CH4), argon (Ar), trichlorofluoromethane (R-11), dichlorodifluoromethane (R-12), bromotrifluoromethane (R-13B1), chloroform (CHCl3), and 1,1,1,2-tetrafluoroethane (R-134a) in structure II. This method and the calculated cell potentials were validated by predicting existing mixed hydrate phase equilibrium data without any fitting parameters and calculating mixture phase diagrams for methane, ethane, isobutane, and cyclopropane mixtures. Several structural transitions that have been determined experimentally as well as some structural transitions that have not been examined experimentally were also predicted. In the methane-cyclopropane hydrate system, a structural transition from structure I to structure II and back to structure I is predicted to occur outside of the known structure II range for the cyclopropane hydrate. Quintuple (L

  8. A phylogenetic analysis of microbial communities associated with methane hydrate containing marine fluids and sediments in the Cascadia margin (ODP site 892B).

    PubMed

    Bidle, K A; Kastner, M; Bartlett, D H

    1999-08-01

    Methane hydrates represent an enormous carbon and energy source in many low temperature deep marine sediments. However, little information is available concerning the nature of the microbial communities associated with these structures. Here, we describe a phylogenetic analysis based on ribosomal DNA (rDNA) sequences obtained from sediment and fluid samples present in a region of gas hydrate formation in shallow sediments within the Cascadia margin in and around Ocean Drilling Program (ODP) Site 892B. Our studies detected diverse sulfur-utilizing microbes, methanogens, methanotrophs, and non-thermophilic members of the kingdom Crenarchaeota. This is the first culture-independent phylogenetic analysis of a gas hydrate habitat. PMID:10436927

  9. Magnetorheological fluids with two-component dispersed phase

    NASA Astrophysics Data System (ADS)

    Korobko, E. V.; Novikova, Z. A.; Zhurauski, M. A.

    2015-04-01

    In the paper the results of investigations of rheological properties of magnetorheological fluids with two-component dispersed phase are presented. Normal and tangential components of the mechanical stress in fluids in the magnetic field are determined. It is showed that using of carbonyl iron and chromium oxide as dispersed phase components allows to achieve essential structural response on magnetic influence

  10. Phase changes of filled ice Ih methane hydrate under low temperature and high pressure.

    PubMed

    Tanaka, Takehiko; Hirai, Hisako; Matsuoka, Takahiro; Ohishi, Yasuo; Yagi, Takehiko; Ohtake, Michika; Yamamoto, Yoshitaka; Nakano, Satoshi; Irifune, Tetsuo

    2013-09-14

    Low-temperature and high-pressure experiments were performed with filled ice Ih structure of methane hydrate under 2.0-77.0 GPa and 30-300 K using diamond anvil cells and a helium-refrigeration cryostat. In situ X-ray diffractometry revealed distinct changes in the compressibility of the axial ratios of the host framework with pressure. Raman spectroscopy showed a split in the C-H vibration modes of the guest methane molecules, which was previously explained by the orientational ordering of the guest molecules. The pressure and temperature conditions at the split of the vibration modes agreed well with those of the compressibility change. The results indicate the following: (i) the orientational ordering of the guest methane molecules from an orientationally disordered state occurred at high pressures and low temperatures; and (ii) this guest ordering led to anisotropic contraction in the host framework. Such guest orientational ordering and subsequent anisotropic contraction of the host framework were similar to that reported previously for filled ice Ic hydrogen hydrate. Since phases with different guest-ordering manners were regarded as different phases, existing regions of the guest disordered-phase and the guest ordered-phase were roughly estimated by the X-ray study. In addition, above the pressure of the guest-ordered phase, another high-pressure phase developed in the low-temperature region. The deuterated-water host samples were also examined, and the influence of isotopic effects on guest ordering and phase transformation was observed. PMID:24050356

  11. Entropic description of gas hydrate ice/liquid equilibrium via enhanced sampling of coexisting phases

    SciTech Connect

    Malolepsza, Edyta; Kim, Jaegil; Keyes, Tom

    2015-04-28

    Metastable β ice holds small guest molecules in stable gas hydrates, so its solid/liquid equilibrium is of interest. However, aqueous crystal/liquid transitions are very difficult to simulate. A new MD algorithm generates trajectories in a generalized NPT ensemble and equilibrates states of coexisting phases with a selectable enthalpy. Furthermore, with replicas spanning the range between β ice and liquid water we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions.

  12. Entropic Description of Gas Hydrate Ice-Liquid Equilibrium via Enhanced Sampling of Coexisting Phases

    NASA Astrophysics Data System (ADS)

    Małolepsza, Edyta; Kim, Jaegil; Keyes, Tom

    2015-05-01

    Metastable β ice holds small guest molecules in stable gas hydrates, so its solid-liquid equilibrium is of interest. However, aqueous crystal-liquid transitions are very difficult to simulate. A new molecular dynamics algorithm generates trajectories in a generalized N P T ensemble and equilibrates states of coexisting phases with a selectable enthalpy. With replicas spanning the range between β ice and liquid water, we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions.

  13. Entropic Description of Gas Hydrate Ice-Liquid Equilibrium via Enhanced Sampling of Coexisting Phases.

    PubMed

    Małolepsza, Edyta; Kim, Jaegil; Keyes, Tom

    2015-05-01

    Metastable β ice holds small guest molecules in stable gas hydrates, so its solid-liquid equilibrium is of interest. However, aqueous crystal-liquid transitions are very difficult to simulate. A new molecular dynamics algorithm generates trajectories in a generalized NPT ensemble and equilibrates states of coexisting phases with a selectable enthalpy. With replicas spanning the range between β ice and liquid water, we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions. PMID:25978217

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  15. Fluid, electrolyte, and renal indices of hydration during 11 days of controlled caffeine consumption.

    PubMed

    Armstrong, Lawrence E; Pumerantz, Amy C; Roti, Melissa W; Judelson, Daniel A; Watson, Greig; Dias, Joao C; Sokmen, Bulent; Casa, Douglas J; Maresh, Carl M; Lieberman, Harris; Kellogg, Mark

    2005-06-01

    This investigation determined if 3 levels of controlled caffeine consumption affected fluid-electrolyte balance and renal function differently. Healthy males (mean +/- standard deviation; age, 21.6 +/- 3.3 y) consumed 3 mg caffeine . kg(-1) . d(-1). on days 1 to 6 (equilibration phase). On days 7 to 11 (treatment phase), subjects consumed either 0 mg (C0; placebo; n= 20), 3 mg (C3; n = 20), or 6 mg (C6; n = 19) caffeine . kg(-1) . d(-1) in capsules, with no other dietary caffeine intake. The following variables were unaffected (P > 0.05) by different caffeine doses on days 1, 3, 6, 9, and 11 and were within normal clinical ranges: body mass, urine osmolality, urine specific gravity, urine color, 24-h urine volume, 24-h Na+ and K+ excretion, 24-h creatinine, blood urea nitrogen, serum Na+ and K+, serum osmolality, hematocrit, and total plasma protein. Therefore, C0, C3, and C6 exhibited no evidence of hypohydration. These findings question the widely accepted notion that caffeine consumption acts chronically as a diuretic. PMID:16131696

  16. The transport of gold and molybdenum through hydration in aqueous vapor and vapor-like fluids: Application to porphyry Au and Mo deposits

    NASA Astrophysics Data System (ADS)

    Hurtig, N. C.; Williams-Jones, A. E.

    2013-12-01

    The hypothesis that vapor is a viable medium for the transport of gold and molybdenum in ore forming magmatic-hydrothermal systems is supported by fluid inclusion data, analyses of volcanic gas condensates and the occurrence of metal-rich incrustations around fumaroles. Experiments have shown that hydration of metal species in water vapor is an essential factor in making such transport possible [1,2,3]. Indeed, hydration has been shown to increase concentrations of Au and Mo in the aqueous vapor phase by several orders of magnitude over those calculated using volatility data. Nevertheless metal concentrations determined experimentally in previous studies are substantially lower than those reported for vapor inclusions in magmatic hydrothermal systems, and are limited to one or two dominant hydrated metal species. To bridge this gap, we performed a series of new experiments extending the density-range to near critical vapor density, and intermediate-density in the case of supercritical fluids. Experiments were carried out in batch-type Ti autoclaves at temperatures between 300 and 500 °C and pressures up to 366 bar in HCl-bearing water vapor. Oxygen fugacity was buffered either by the assemblage MoO2/MoO3 or WO2/WO3 or graphite. Gold and molybdenum concentrations measured in the experimental condensates ranged from 0.9 ppb and 3 ppm in low-density vapor at 300 °C to 4.6 ppm and 481 ppm at 297 bar and 400 °C, respectively. The fugacity of both metals increased exponentially with increasing water fugacity, resulting in an increase in metal solubility between 1 and 3 orders of magnitude from the lowest pressures investigated. Curves representing the experimentally determined relationship between metal fugacity and fH2O were fitted to a step-wise hydration model to extract a set of logarithmic equilibrium constants for P and T extrapolation. We have used the above data to model Au and Mo mobilization in magmatic-hydrothermal vapor plumes. This modeling shows that the

  17. Direct phase coexistence molecular dynamics study of the phase equilibria of the ternary methane-carbon dioxide-water hydrate system.

    PubMed

    Michalis, Vasileios K; Tsimpanogiannis, Ioannis N; Stubos, Athanassios K; Economou, Ioannis G

    2016-09-14

    Molecular dynamics simulation is used to predict the phase equilibrium conditions of a ternary hydrate system. In particular, the direct phase coexistence methodology is implemented for the determination of the three-phase coexistence temperature of the methane-carbon dioxide-water hydrate system at elevated pressures. The TIP4P/ice, TraPPE-UA and OPLS-UA forcefields for water, carbon dioxide and methane respectively are used, in line with our previous studies of the phase equilibria of the corresponding binary hydrate systems. The solubility in the aqueous phase of the guest molecules of the respective binary and ternary systems is examined under hydrate-forming conditions, providing insight into the predictive capability of the methodology as well as the combination of these forcefields to accurately describe the phase behavior of the ternary system. The three-phase coexistence temperature is calculated at 400, 1000 and 2000 bar for two compositions of the methane-carbon dioxide mixture. The predicted values are compared with available calculations with satisfactory agreement. An estimation is also provided for the fraction of the guest molecules in the mixed hydrate phase under the conditions examined. PMID:27507133

  18. Phase equilibria of carbon dioxide hydrate system in the presence of sucrose, glucose, and fructose

    SciTech Connect

    Chun, M.K.; Lee, H.

    1999-09-01

    The three-phase (H-L{sub w}-V) equilibria of the carbon dioxide hydrate formation system in aqueous solutions containing sucrose, glucose, and fructose were experimentally determined at pressures ranging from 1.580 to 4.355 MPa and at temperatures between 273.6 and 281.7 K. The upper quadruple points (H-L{sub w}-L{sub CO{sub 2}}-V) were also measured at concentrations of 10, 20, and 30 mass % sucrose, glucose, and fructose. The addition of carbohydrates exhibited a similar inhibition effect as that observed for electrolytes and alcohols. A thermodynamic model predicting the three- and four-phase hydrate equilibria while accounting for the inhibition effect of carbohydrates was developed on the basis of the van der Waals-Platteeuw model and the Redlich-Kwong-Soave equation of state with a modified version of the Huron-Vidal mixing rule. The calculated results were found to be in good agreement with the experimental data.

  19. Tuning of crystal phase structure in hydrated WO3 nanoparticles under wet chemical conditions and studies on their photochromic properties

    NASA Astrophysics Data System (ADS)

    Songara, Sandhya; Gupta, Vatsana; Kumar Patra, Manoj; Singh, Jitendra; Saini, Lokesh; Siddaramana Gowd, Genekehal; Raj Vadera, Sampat; Kumar, Narendra

    2012-07-01

    Hydrated tungsten oxide nanoparticles have been synthesized using a simple wet chemical method while varying the concentration of HCl. XRD studies show that the variation in HCl concentration from 1 M to 6 M in the reaction results into gradual change in crystal structure of hydrated WO3 from hexagonal (WO3·0.33H2O) to pure orthorhombic (WO3·H2O), through a series of samples with mixed phase of the two indifferent ratios. The similar variations in the degree of hydration and phase variations have also been observed from Raman, FTIR and TGA studies. The average crystallite size of the hydrated WO3 particles was estimated to be ∼26 nm from XRD line broadening and AFM studies showed the formation of spherical shaped particles for all the samples. The photochromic studies were carried out on the composite films of these materials in the polymeric matrix of polyvinyl alcohol (PVA) while exposing to UV light. The composite films show interesting variations in the photochromic behavior depending on the crystal structure of hydrated WO3 filler. The photochromic behavior has been explained on the basis of EPR spectra of hydrated WO3.

  20. Brillouin-scattering study of hyaluronic acid: Dynamic coupling with the water of hydration and phase transitions

    NASA Astrophysics Data System (ADS)

    Lee, S. A.; Flowers, M. R.; Oliver, W. F.; Rupprecht, A.; Lindsay, S. M.

    1993-01-01

    Brillouin spectra have been measured from wet-spun films of Li and Na hyaluronate (NaHA) between 0% and 93% relative humidity (RH). The speed of sound is very high (about 5 km/s) in both Li and NaHA films at low values of RH. The Brillouin spectra show substantial coupling between the longitudinal-acoustic phonons and a relaxation mode of the water of hydration. A coupled-modes model is used to interpret these data. This analysis shows that the relaxation time of the water of hydration (about 50 ps) is constant over the range of hydration. The microscopic coupling constant also appears to be independent of hydration. Between 84% and 88% RH, the uncoupled phonon frequency for both Li and NaHA is found to drop by ~40%, and ~25% for phonons propagating in the parallel and perpendicular directions, respectively, indicative of a phase transition.

  1. Natural Methane and Carbon Dioxide Hydrates in the Earth System

    NASA Astrophysics Data System (ADS)

    Research Team; Milkereit, B.

    2004-05-01

    Both CH4 and CO2 are abundant volatiles in the earth's crust. Methane hydrates occur in permafrost regions and continental slopes of oceans. It is currently estimated that the energy stored in CH4 hydrate reserves totals more than twice the global reserves of all conventional oil, gas, and coal deposits combined. This means that methane hydrate could prove to be a very important source of energy in the future. Pressure versus temperature phase diagrams for methane and carbon dioxide define characteristic stability fields for gas, fluid and hydrates states. Sequestration of carbon dioxide in the earths crust and production of methane hydrate reservoirs are critically dependent on knowledge of the in situ elastic moduli of natural hydrates. The physical properties of simple methane and carbon dioxide hydrates are similar [1]. Our compilation of experimental data confirms high compressional wave velocities and elastic moduli for CH4 and CO2 hydrates and low compressional wave velocities for the fluid and gas phases. As methane and carbon dioxide hydrates are stable over similar pressure-temperature ranges, the two types of hydrates form in similar settings in the earth's crust. For example, temperature and pressure conditions in deepwater marine environments require both CO2 and CH4 to be in hydrate phase. However, not much is known about the origin, distribution and total volume of natural carbon dioxide hydrates stored in the earth's crust. For a number of tectonic/geological settings, CO2-rich fluids from deep crustal reservoirs must be considered: rifted margins, volcanic arcs, deepwater vents [2], mud volcanoes and mud diapirs [3]. Both methane and carbon dioxide hydrates work to cement sea floors in similar ways. Slope failure, a phenomenon usually taken as a hallmark of the presence of methane hydrate, could also be attributed to the existence of carbon dioxide hydrates. Perhaps most critically, many of the estimations of the amounts of methane hydrates are

  2. A Phase-Field Approach to Modeling Hydrate Formation on Methane Gas Bubbles in a Water Column

    NASA Astrophysics Data System (ADS)

    Fu, X.; Cueto-Felgueroso, L.; Waite, W. F.; Ruppel, C. D.; Juanes, R.

    2014-12-01

    Methane hydrates are water-based crystalline solids, where gas molecules are trapped inside the lattice structure formed by water. Most commonly found in deep ocean floors where low temperature and high pressure are primal conditions for hydrate to form, gas hydrates contain most of the world's mobile carbon and yet it remains an important and open question how methane leakage from gas hydrate impacts ocean and the atmosphere. While current work focus on the breakdown of gas hydrate in marine environment and the the release of methane from seafloor, few studies explore the fate of a single or a plume of methane bubbles when entering the water column after the release. We propose to study the fate of an individual and a series of methane bubbles through mathematical modeling, specifically using a phase-field approach. Phase-field modeling is a mathematical framework that describes systems that are out of thermodynamic equilibrium. First introduced in the context of solidification process and phase transitions, it has since been adopted in the field of multiphase flow. In this work, we present a new phase-field formulation for multiphase/multicomponent flows that allows us to model the fate of methane bubbles in the water system as a nonequilibrium process.

  3. Full quantitative phase analysis of hydrated lime using the Rietveld method

    SciTech Connect

    Lassinantti Gualtieri, Magdalena

    2012-09-15

    Full quantitative phase analysis (FQPA) using X-ray powder diffraction and Rietveld refinements is a well-established method for the characterization of various hydraulic binders such as Portland cement and hydraulic limes. In this paper, the Rietveld method is applied to hydrated lime, a non-hydraulic traditional binder. The potential presence of an amorphous phase in this material is generally ignored. Both synchrotron radiation and a conventional X-ray source were used for data collection. The applicability of the developed control file for the Rietveld refinements was investigated using samples spiked with glass. The results were cross-checked by other independent methods such as thermal and chemical analyses. The sample microstructure was observed by transmission electron microscopy. It was found that the consistency between the different methods was satisfactory, supporting the validity of FQPA for this material. For the samples studied in this work, the amount of amorphous material was in the range 2-15 wt.%.

  4. Thermodynamics of aqueous solutes at high temperatures and pressures: Application of the hydration theory and implications for fluid-mediated mass transfer

    NASA Astrophysics Data System (ADS)

    Sulak, M.; Dolejs, D.

    2012-04-01

    Magmatic activity and prograde devolatilization of subducting or underplating lithologies release large quantities of aqueous fluids that act as mass and heat transfer agents in the planetary interiors. Understanding of mineral-melt-fluid interactions is essential for evaluating the effects of fluid-mediated mass transport in subduction zones, collisional orogens as well as in igneous provinces. The thermodynamic properties of aqueous species were frequently described by the Helgeson-Kirkham-Flowers equation of state [1] but its utility is limited by inavailability of the solvent dielectric properties at high pressures and temperatures, and by decoupling of species-solvent mechanical and electrostatic interactions that cannot be separated within the Born theory. Systematic description of the hydration process in a Born-Haber cycle leads to the following thermochemical contributions: (i) thermodynamic properties of an unhydrated species, (ii) the pressure-volume work required to create a cavity within the solvent to accommodate the species, described by the scaled particle theory, (iii) entropic contribution related to changes in the solute's and the solvent's kinetic degrees of freedom, and (iv) contribution from the solute-solvent molecular interactions and corresponding rearrangement of the solvent molecules to form the hydration shell. Application of the spatial correlation functions [2, 3] results in apparent Gibbs energy of aqueous species, ΔaGi = a + bT + cTlnT + dP + eTlnρ + fTρlnρ, where athrough f represent constants related to standard thermodynamic properties of aqueous species (ΔfH, S, V, cP) and to solvent volumetric properties at 298.15 K and 1 bar (ρ, α, β etc.). In phase equilibrium calculations, the number of required parameters often reduces to four (c = f = 0) while noting that H2O density as the only solvent-related property is accurately known to extreme temperatures and pressures. The equation of state parameters were calibrated for 30

  5. Phase behaviour and thermoelastic properties of ammonia hydrate and ice polymorphs from 0 - 2 GPa

    NASA Astrophysics Data System (ADS)

    Fortes, A. D.; Wood, I. G.; Vocadlo, L.

    2008-12-01

    Ammonia remains amongst the most plausible planetary "antifreeze" agents, and its physical properties in hydrate compounds under the appropriate conditions (roughly 0 - 5 GPa, 100 - 300 K) must be known in order for it to be accommodated in planetary models. The pressure melting curve, and the expected polymorphism of the stoichiometric ammonia hydrates have implications for the internal structure of large icy moons like Titan, leading to phase layering and the possible persistence of deep subsurface oceans, the latter being sites of high astrobiological potential. Aqueous ammonia is also a candidate substance involved in cryomagmatism on Titan, and again the melting behaviour, and densities of liquids and solids, in the ammonia-water system must be known to model properly the partial melting and propagation of magma. We describe the results of a series of powder neutron diffraction experiments over the range 0 - 2.0 GPa, 150 - 280 K which were carried out with the objective of determining the phase behaviour and thermoelastic properties of ammonia dihydrate. In addition to the low-pressure cubic crystalline phase, ADH I, we have identified two closely related monoclinic polymorphs of ammonia dihydrate (ADH IIa and IIb) in the range 0.45 - 0.60 GPa (at 175 K), and have determined that this phase dissociates to a mixture of ammonia monohydrate phase II and ice II when warmed to ~190 K, which in turn melts at a binary eutectic at ~196 K; AMH II has a large (Z = 16) orthorhombic unit cell. Above 0.60 GPa, an orthorhombic polymorph of ammonia dihydrate, which we have referred to previously as ADH IV, persists to pressures > 3 GPa, and appears to be the liquidus phase over this whole pressure range. We have observed this phase co- existing with both ice II and ice VI. Here we describe the most plausible synthesis of the high-pressure phase diagram which explains our observations, and provide measurements of the densities, thermal expansion, bulk moduli, and crystal

  6. Theoretical study of phase transitions in Kr and Ar clathrate hydrates from structure II to structure I under pressure

    NASA Astrophysics Data System (ADS)

    Subbotin, Oleg S.; Adamova, Tatiana P.; Belosludov, Rodion V.; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki; Kudoh, Jun-ichi; Rodger, P. M.; Belosludov, Vladimir R.

    2009-09-01

    The theory developed in our earlier papers is extended to predict dynamical and thermodynamic properties of clathrate structures by accounting for the possibility of multiple filling of cavities by guest molecules. The method is applied to the thermodynamic properties of argon and krypton hydrates, considering both structures I (sI) and II (sII), in which the small cages can be singly occupied and large cages of sII can be singly or doubly occupied. It was confirmed that the structure of the clathrate hydrate is determined by two main factors: intermolecular interaction between guest and host molecules and the configurational entropy. It is shown that for guests weakly interacting with water molecules, such as argon or krypton, the free energy of host lattices without the contribution of entropy is the main structure-determining factor for clathrate hydrates, and it is a cause of hydrate sII formation at low pressure with these guests. Explicit account of the entropy contribution in the Gibbs free energy allows one to determine the stability of hydrate phases and to estimate the line of structural transition from sII to sI in P-T plane. The structural transition between sII and sI in argon and krypton hydrates at high pressure is shown to be the consequence of increasing intermolecular interaction and the degree of occupancy of the large cavities.

  7. Theoretical study of phase transitions in Kr and Ar clathrate hydrates from structure II to structure I under pressure.

    PubMed

    Subbotin, Oleg S; Adamova, Tatiana P; Belosludov, Rodion V; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki; Kudoh, Jun-ichi; Rodger, P M; Belosludov, Vladimir R

    2009-09-21

    The theory developed in our earlier papers is extended to predict dynamical and thermodynamic properties of clathrate structures by accounting for the possibility of multiple filling of cavities by guest molecules. The method is applied to the thermodynamic properties of argon and krypton hydrates, considering both structures I (sI) and II (sII), in which the small cages can be singly occupied and large cages of sII can be singly or doubly occupied. It was confirmed that the structure of the clathrate hydrate is determined by two main factors: intermolecular interaction between guest and host molecules and the configurational entropy. It is shown that for guests weakly interacting with water molecules, such as argon or krypton, the free energy of host lattices without the contribution of entropy is the main structure-determining factor for clathrate hydrates, and it is a cause of hydrate sII formation at low pressure with these guests. Explicit account of the entropy contribution in the Gibbs free energy allows one to determine the stability of hydrate phases and to estimate the line of structural transition from sII to sI in P-T plane. The structural transition between sII and sI in argon and krypton hydrates at high pressure is shown to be the consequence of increasing intermolecular interaction and the degree of occupancy of the large cavities. PMID:19778129

  8. Observation of microwave superfluid phenomena of multiple phase magnetic fluid

    NASA Astrophysics Data System (ADS)

    Kono, Kazuhito; Kono, Buhei

    2015-05-01

    We observe superfluid phenomena by microwaves irradiation to multiple phase magnetic fluid in room temperature or room pressure. Ferromagnetism transformation of diamagnetic or paramagnetic particles in multiple phase magnetic fluid containing constant rate of ferromagnetic particles, diamagnetic or paramagnetic particles mixing organic polyphenol and irradiation of microwaves is, observed by superexchange interaction. Superfluid phenomena are observed by irradiation of microwaves to aforementioned multiple phase of magnetic fluid containing ferromagnetism transformed diamagnetic or paramagnetic particles with ferromagnetic particles. Mixing semiconductor pigments amplifying superfluid energy by photosensitivity is observed. Visible light LED selecting wavelength is irradiated to superfluid condition of aforementioned multiple phase magnetic fluid thus magnetic field and energy of superfluid is enhanced by light quantum amplification effect.

  9. Comparative Assessment of Advanced Gay Hydrate Production Methods

    SciTech Connect

    M. D. White; B. P. McGrail; S. K. Wurstner

    2009-06-30

    Displacing natural gas and petroleum with carbon dioxide is a proven technology for producing conventional geologic hydrocarbon reservoirs, and producing additional yields from abandoned or partially produced petroleum reservoirs. Extending this concept to natural gas hydrate production offers the potential to enhance gas hydrate recovery with concomitant permanent geologic sequestration. Numerical simulation was used to assess a suite of carbon dioxide injection techniques for producing gas hydrates from a variety of geologic deposit types. Secondary hydrate formation was found to inhibit contact of the injected CO{sub 2} regardless of injectate phase state, thus diminishing the exchange rate due to pore clogging and hydrate zone bypass of the injected fluids. Additional work is needed to develop methods of artificially introducing high-permeability pathways in gas hydrate zones if injection of CO{sub 2} in either gas, liquid, or micro-emulsion form is to be more effective in enhancing gas hydrate production rates.

  10. Mantle hydration and Cl-rich fluids in the subduction forearc

    NASA Astrophysics Data System (ADS)

    Reynard, Bruno

    2016-12-01

    In the forearc region, aqueous fluids are released from the subducting slab at a rate depending on its thermal state. Escaping fluids tend to rise vertically unless they meet permeability barriers such as the deformed plate interface or the Moho of the overriding plate. Channeling of fluids along the plate interface and Moho may result in fluid overpressure in the oceanic crust, precipitation of quartz from fluids, and low Poisson ratio areas associated with tremors. Above the subducting plate, the forearc mantle wedge is the place of intense reactions between dehydration fluids from the subducting slab and ultramafic rocks leading to extensive serpentinization. The plate interface is mechanically decoupled, most likely in relation to serpentinization, thereby isolating the forearc mantle wedge from convection as a cold, potentially serpentinized and buoyant, body. Geophysical studies are unique probes to the interactions between fluids and rocks in the forearc mantle, and experimental constrains on rock properties allow inferring fluid migration and fluid-rock reactions from geophysical data. Seismic velocities reveal a high degree of serpentinization of the forearc mantle in hot subduction zones, and little serpentinization in the coldest subduction zones because the warmer the subduction zone, the higher the amount of water released by dehydration of hydrothermally altered oceanic lithosphere. Interpretation of seismic data from petrophysical constrain is limited by complex effects due to anisotropy that needs to be assessed both in the analysis and interpretation of seismic data. Electrical conductivity increases with increasing fluid content and temperature of the subduction. However, the forearc mantle of Northern Cascadia, the hottest subduction zone where extensive serpentinization was first demonstrated, shows only modest electrical conductivity. Electrical conductivity may vary not only with the thermal state of the subduction zone, but also with time for

  11. Coupled THCM Modeling of Gas Hydrate Bearing Sediments

    NASA Astrophysics Data System (ADS)

    Sanchez, M. J.; Gai, X., Sr.; Shastri, A.; Santamarina, J. C.

    2014-12-01

    Gas hydrates are crystalline clathrate compounds made of water and a low molecular gas, like methane. Gas hydrates are generally present in oil-producing areas and in permafrost regions. Methane hydrate deposits can lead to large-scale submarine slope failures, blowouts, platform foundation failures, and borehole instability. Gas hydrates constitute also an attractive source of energy as they are estimated to contain very large reserves of methane. Hydrate formation, dissociation and methane production from hydrate bearing sediments are coupled Thermo-Hydro-Mechanical (THM) processes that involve, amongst other, exothermic formation and endothermic dissociation of hydrate and ice phases, mixed fluid flow and large changes in fluid pressure. A comprehensive THM formulation is briefly presented here. Momentum balance, mass balance and energy balance equations take into consideration the interaction among all phases (i.e. solid, liquid, gas, hydrates and ice) and mechanical equilibrium. Constitutive equations describe the intrinsic THM behavior of the sediment. Simulation results conducted for hydrate bearing sediments subjected to boundary conditions highlight the complex interaction among THM processes in hydrate bearing sediments.

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

    SciTech Connect

    Manohara, G.V.; Vishnu Kamath, P.; Milius, Wolfgang

    2012-12-15

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

  13. The impact of transitions between two-fluid and three-fluid phases on fluid configuration and fluid-fluid interfacial area in porous media

    NASA Astrophysics Data System (ADS)

    Carroll, Kenneth C.; McDonald, Kieran; Marble, Justin; Russo, Ann E.; Brusseau, Mark L.

    2015-09-01

    Multiphase-fluid distribution and flow is inherent in numerous areas of hydrology. Yet pore-scale characterization of transitions between two and three immiscible fluids is limited. The objective of this study was to examine the impact of such transitions on the pore-scale configuration of organic liquid in a multifluid system comprising natural porous media. Three-dimensional images of an organic liquid (trichloroethene) in two-phase (organic-liquid/water) and three-phase (air/organic-liquid/water) systems were obtained using X-ray microtomography before and after drainage and imbibition. Upon transition from a two-phase to a three-phase system, a significant portion of the organic liquid (intermediate wetting fluid) was observed to exist as lenses and films in contact with air (nonwetting fluid). In these cases, the air was either encased by or contiguous to the organic liquid. The presence of air resulted in an increase in the surface-area-to-volume ratios for the organic-liquid blobs. Upon imbibition, the air was displaced downgradient, and concomitantly, the morphology of the organic-liquid blobs no longer in contact with air reverted to that characteristic of a two-phase distribution (i.e., more spherical blobs and ganglia). This change in morphology resulted in a reduction in the surface-area-to-volume ratio. These results illustrate the impact of transitions between two-phase and three-phase conditions on fluid configuration, and they demonstrate the malleable nature of fluid configuration under dynamic, multiphase-flow conditions. The results have implications for characterizing and modeling pore-scale flow and mass transfer processes.

  14. Sedimentological control on saturation distribution in Arctic gas-hydrate-bearing sands

    NASA Astrophysics Data System (ADS)

    Behseresht, Javad; Bryant, Steven L.

    2012-08-01

    A mechanistic model is proposed to predict/explain hydrate saturation distribution in “converted free gas” hydrate reservoirs in sub-permafrost formations in the Arctic. This 1-D model assumes that a gas column accumulates and subsequently is converted to hydrate. The processes considered are the volume change during hydrate formation and consequent fluid phase transport within the column, the descent of the base of gas hydrate stability zone through the column, and sedimentological variations with depth. Crucially, the latter enable disconnection of the gas column during hydrate formation, which leads to substantial variation in hydrate saturation distribution. One form of variation observed in Arctic hydrate reservoirs is that zones of very low hydrate saturations are interspersed abruptly between zones of large hydrate saturations. The model was applied to data from Mount Elbert well, a gas hydrate stratigraphic test well drilled in the Milne Point area of the Alaska North Slope. The model is consistent with observations from the well log and interpretations of seismic anomalies in the area. The model also predicts that a considerable amount of fluid (of order one pore volume of gaseous and/or aqueous phases) must migrate within or into the gas column during hydrate formation. This paper offers the first explanatory model of its kind that addresses “converted free gas reservoirs” from a new angle: the effect of volume change during hydrate formation combined with capillary entry pressure variation versus depth.

  15. Role of Presolvation and Anharmonicity in Aqueous Phase Hydrated Proton Solvation and Transport.

    PubMed

    Biswas, Rajib; Tse, Ying-Lung Steve; Tokmakoff, Andrei; Voth, Gregory A

    2016-03-01

    Results from condensed phase ab initio molecular dynamics (AIMD) simulations suggest a proton transfer reaction is facilitated by "presolvation" in which the hydronium is transiently solvated by four water molecules, similar to the typical solvation structure of water, by accepting a weak hydrogen bond from the fourth water molecule. A new version 3.2 multistate empirical valence bond (MS-EVB 3.2) model for the hydrated excess proton incorporating this presolvation behavior is therefore developed. The classical MS-EVB simulations show similar structural properties as those of the previous model but with significantly improved diffusive behavior. The inclusion of nuclear quantum effects in the MS-EVB also provides an even better description of the proton diffusion rate. To quantify the influence of anharmonicity, a second model (aMS-EVB 3.2) is developed using the anharmonic aSPC/Fw water model, which provides similar structural properties but improved spectroscopic responses at high frequencies. PMID:26575795

  16. Thermodynamic and kinetic stability of zwitterionic histidine: Effects of gas phase hydration

    NASA Astrophysics Data System (ADS)

    Lee, Sung-Sik; Kim, Ju-Young; Han, Yuna; Shim, Hyun-Jin; Lee, Sungyul

    2015-09-01

    We present calculations for histidine-(H2O)n (n = 0-6) to examine the effects of micro-hydrating water molecules on the relative stability of the zwitterionic vs. canonical forms of histidine. We calculate the structures and Gibbs free energies of the conformers at wB97XD/6-311++G(d,p) level of theory. We find that six water molecules are required to produce the thermodynamically stable histidine zwitterion. By calculating the barriers of canonical ↔ zwitterionic transformation, we predict that both the most stable canonical and zwitterionic forms of histidine-(H2O)6 may be observed in low temperature gas phase environment.

  17. Dynamics of phase separation of binary fluids

    NASA Technical Reports Server (NTRS)

    Ma, Wen-Jong; Maritan, Amos; Banavar, Jayanth R.; Koplik, Joel

    1992-01-01

    The results of molecular-dynamics studies of surface-tension-dominated spinodal decomposition of initially well-mixed binary fluids in the absence and presence of gravity are presented. The growth exponent for the domain size and the decay exponent of the potential energy of interaction between the two species with time are found to be 0.6 +/- 0.1, inconsistent with scaling arguments based on dimensional analysis.

  18. Information geometry and phase transitions of fluids with global anomalies

    NASA Astrophysics Data System (ADS)

    Surowka, Piotr

    2015-11-01

    Fluid helicity is an important observable that captures topological properties of hydrodynamics. It naturally emerges in the context of parity-breaking fluids with knotted vortex lines. If the fluid constituents exhibit quantum anomalies the topological nature of fluid helicity can be elucidated using microscopic physics. In this case the helicity is given by a polynomial function of temperature and chiral chemical potential and completely fixed by the anomalies. We explain this relation and address the question of phase structure of such fluids using methods of information geometry. We introduce the metric on a parameter space and show that a non-zero vorticity leads to a curvature on the statistical manifold. We calculate the curvature invariant and analyze its divergences, which contain the information about phase transitions of the system. The transition points are universal and expressed in terms of ratios of anomaly coefficients.

  19. Hydration State and Aqueous Phase Connectivity Shape Microbial Dispersal Rates in Unsaturated Angular Pore Networks

    NASA Astrophysics Data System (ADS)

    Or, D.; Ebrahimi, A.

    2014-12-01

    The limited dispersal of self-propelled microorganisms and constrained nutrient transport in unsaturated soils are considered key factors in the promotion and maintenance of soil microbial diversity. Despite the importance of microbial dispersal to biogeochemical and ecological functioning of soil, little is known about how pore spaces and hydration conditions affect dispersal ranges and rates of motile bacteria. To address these questions quantitatively, we developed a novel 3-D pore network model (PNM) composed of triangular bonds connected to cubic (volumeless) bonds to mimic the salient geometrical and physical properties of natural pore spaces. Within this abstracted physical domain we employed individual based models for motile microorganisms that are capable of motion, nutrient consumption, growth and cell division. We focused on dispersal rates through the network as a function of hydration conditions through its impact on aqueous phase fragmentation that suppress nutrient diffusion (hence growth rates) and dispersal rates in good agreement with limited experimental data. Chemotactically-biased mean travel rates of microbial cells across the saturated PNM was ~3 mm/hr and decreased exponentially to 0.45 mm/hr for matric potential of (at dispersal practically ceases and cells are pinned by capillary forces). Individual-based results were upscaled to describe population scale dispersal rates, and PNM predictions considering different microbial cell sizes were in good agreement with experimental results for unsaturated soils. The role of convection for most unsaturated conditions was negligible relative to self-motility highlighting the need to constrain continuum models with respect to cell size and motility to imporve predictions of transport of motile microorganisms. The modeling platform confirms universal predictions based on percolation theory for the onset of aqueous phase fragmentation that limit dispersal and provide niches essential for species

  20. Two-phase computational fluid dynamics

    SciTech Connect

    Rothe, P.H.

    1991-07-26

    The results of the project illustrate the feasibility of multiphase computerized fluid dynamics (CFD) software. Existing CFD software is capable of simulating particle fields, certain droplet fields, and certain free surface flows, and does so routinely in engineering applications. Stratified flows can be addressed by a multiphase CFD code, once one is developed with suitable capabilities. The groundwork for such a code has been laid. Calculations performed for stratified flows demonstrate the accuracy achievable and the convergence of the methodology. Extension of the stratified flow methodology to other segregated flows such as slug or annular faces no inherent limits. The research has commercial application in the development of multiphase CFD computer programs.

  1. Optimization of crystal nucleation close to a metastable fluid-fluid phase transition

    PubMed Central

    Wedekind, Jan; Xu, Limei; Buldyrev, Sergey V.; Stanley, H. Eugene; Reguera, David; Franzese, Giancarlo

    2015-01-01

    The presence of a metastable fluid-fluid critical point is thought to dramatically influence the crystallization pathway, increasing the nucleation rate by many orders of magnitude over the predictions of classical nucleation theory. We use molecular dynamics simulations to study the kinetics of crystallization in the vicinity of this metastable critical point and throughout the metastable fluid-fluid phase diagram. To quantitatively understand how the fluid-fluid phase separation affects the crystal nucleation, we evaluate accurately the kinetics and reconstruct the thermodynamic free-energy landscape of crystal formation. Contrary to expectations, we find no special advantage of the proximity of the metastable critical point on the crystallization rates. However, we find that the ultrafast formation of a dense liquid phase causes the crystallization to accelerate both near the metastable critical point and almost everywhere below the fluid-fluid spinodal line. These results unveil three different scenarios for crystallization that could guide the optimization of the process in experiments PMID:26095898

  2. Metastable ripple phase of fully hydrated dipalmitoylphosphatidylcholine as studied by small angle x-ray scattering

    PubMed Central

    Yao, Haruhiko; Matuoka, Sinzi; Tenchov, Boris; Hatta, Ichiro

    1991-01-01

    Fully hydrated dipalmitoylphosphatidylcholine (DPPC) undergoes liquid crystalline to metastable Pβ, phase transition in cooling. A small angle x-ray scattering study has been performed for obtaining further evidence about the structure of this phase. From a high-resolution observation of x-ray diffraction profiles, a distinct multipeak pattern has become obvious. Among them the (01) reflection in the secondary ripple structure is identified clearly. There are peaks assigned straightforwardly to (10) and (20) reflections in the primary ripple structure and peaks assigned to (10) and (20) reflections in the secondary ripple structure. Therefore the multipeak pattern is due to superposition of the reflections cause by the primary and secondary ripple structures. The lattice parameters are estimated as follows: for the primary ripple structure a = 7.09 nm, b = 13.64 nm, and γ = 95°, and for the secondary ripple structure a = 8.2 nm, b = 26.6 nm, and γ = 90°. The lattice parameters thus obtained for the secondary ripple structure are not conclusive, however. The hydrocarbon chains in the primary ripple structure have been reported as being tilted against the bilayer plane and, on the other hand, the hydrocarbon chains in the secondary ripple structure are likely to be perpendicular to the bilayer plane. This fact seems to be related to a sequential mechanism of phase transitions. On heating from the Lβ, phase where the hydrocarbon chains are tilted the primary ripple structure having tilted hydrocarbon chains takes place and on cooling from the Lα phase where the hydrocarbon chains are not tilted the secondary ripple structure with untilted chains tends to be stabilized. It appears that the truly metastable ripple phase is expressed by the second ripple structure although in the course of the actual cooling transition both the secondary and primary ripple structures form and coexist. PMID:19431787

  3. Structures and phase relations of aluminum-substituted calcium silicate hydrate

    SciTech Connect

    Kwan, S.; LaRosa-Thompson, J.; Grutzeck, M.W.

    1996-04-01

    The structures of aluminum-substituted calcium silicate hydrate (C-S-H) forming in a series of aqueous suspensions formulated with colloidal silica, reactive alumina, and lime and aged for 1 year have been studied using {sup 29}Si and {sup 27}Al magic angle spinning nuclear magnetic resonance spectroscopy (with and without cross polarization (CP)), solution pH, electron microscopy, and X-ray diffraction. As in earlier work dealing with the nature of C-S-H in the system CaO-SiO{sub 2}-H{sub 2}O, two aluminum-substituted C-S-H phases, having distinctly different anionic structures on the atomic level (Q{sub 2} versus Q{sub 1}Q{sub 2}), were found to extend into the system CaO-Al{sub 2}O{sub 3}-SiO{sub 2}-H{sub 2}O. X-ray diffraction patterns of the two aluminum-containing C-S-H phases are nearly identical, suggesting that their intermediate-range order is very similar, but MASNMR spectra show that these two phases have markedly different silicate structures on the atomic-level scale. Both C-S-H structures can accommodate approximately 5 mol% of Al{sub 2}O{sub 3} in tetrahedral and possibly octahedral coordination as well.

  4. Hydration-Induced Phase Separation in Amphiphilic Polymer Matrices and its Influence on Voclosporin Release

    PubMed Central

    Khan, I. John; Murthy, N. Sanjeeva; Kohn, Joachim

    2012-01-01

    Voclosporin is a highly potent, new cyclosporine-A derivative that is currently in Phase 3 clinical trials in the USA as a potential treatment for inflammatory diseases of the eye. Voclosporin represents a number of very sparingly soluble drugs that are difficult to administer. We therefore selected it as a model drug that is dispersed within amphiphilic polymer matrices, and investigated the changing morphology of the matrices using neutron and x-ray scattering during voclosporin release and polymer resorption. The hydrophobic segments of the amphiphilic polymer chain are comprised of desaminotyrosyl-tyrosine ethyl ester (DTE) and desaminotyrosyl-tyrosine (DT), and the hydrophilic component is poly(ethylene glycol) (PEG). Water uptake in these matrices resulted in the phase separation of hydrophobic and hydrophilic domains that are a few hundred Angstroms apart. These water-driven morphological changes influenced the release profile of voclosporin and facilitated a burst-free release from the polymer. No such morphological reorganization was observed in poly(lactide-co-glycolide) (PLGA), which exhibits an extended lag period, followed by a burst-like release of voclosporin when the polymer was degraded. An understanding of the effect of polymer composition on the hydration behavior is central to understanding and controlling the phase behavior and resorption characteristics of the matrix for achieving long-term controlled release of hydrophobic drugs such as voclosporin. PMID:24955746

  5. The role of intermolecular interactions in the prediction of the phase equilibria of carbon dioxide hydrates

    NASA Astrophysics Data System (ADS)

    Costandy, Joseph; Michalis, Vasileios K.; Tsimpanogiannis, Ioannis N.; Stubos, Athanassios K.; Economou, Ioannis G.

    2015-09-01

    The direct phase coexistence methodology was used to predict the three-phase equilibrium conditions of carbon dioxide hydrates. Molecular dynamics simulations were performed in the isobaric-isothermal ensemble for the determination of the three-phase coexistence temperature (T3) of the carbon dioxide-water system, at pressures in the range of 200-5000 bar. The relative importance of the water-water and water-guest interactions in the prediction of T3 is investigated. The water-water interactions were modeled through the use of TIP4P/Ice and TIP4P/2005 force fields. The TraPPE force field was used for carbon dioxide, and the water-guest interactions were probed through the modification of the cross-interaction Lennard-Jones energy parameter between the oxygens of the unlike molecules. It was found that when using the classic Lorentz-Berthelot combining rules, both models fail to predict T3 accurately. In order to rectify this problem, the water-guest interaction parameters were optimized, based on the solubility of carbon dioxide in water. In this case, it is shown that the prediction of T3 is limited only by the accuracy of the water model in predicting the melting temperature of ice.

  6. Hydration-Induced Phase Separation in Amphiphilic Polymer Matrices and its Influence on Voclosporin Release

    SciTech Connect

    Khan, I. John; Murthy, N. Sanjeeva; Kohn, Joachim

    2015-10-30

    Voclosporin is a highly potent, new cyclosporine -- a derivative that is currently in Phase 3 clinical trials in the USA as a potential treatment for inflammatory diseases of the eye. Voclosporin represents a number of very sparingly soluble drugs that are difficult to administer. It was selected as a model drug that is dispersed within amphiphilic polymer matrices, and investigated the changing morphology of the matrices using neutron and x-ray scattering during voclosporin release and polymer resorption. The hydrophobic segments of the amphiphilic polymer chain are comprised of desaminotyrosyl-tyrosine ethyl ester (DTE) and desaminotyrosyl-tyrosine (DT), and the hydrophilic component is poly(ethylene glycol) (PEG). Water uptake in these matrices resulted in the phase separation of hydrophobic and hydrophilic domains that are a few hundred Angstroms apart. These water-driven morphological changes influenced the release profile of voclosporin and facilitated a burst-free release from the polymer. No such morphological reorganization was observed in poly(lactide-co-glycolide) (PLGA), which exhibits an extended lag period, followed by a burst-like release of voclosporin when the polymer was degraded. An understanding of the effect of polymer composition on the hydration behavior is central to understanding and controlling the phase behavior and resorption characteristics of the matrix for achieving long-term controlled release of hydrophobic drugs such as voclosporin.

  7. How Hydrate Saturation Anomalies are Diffusively Constructed and Advectively Smoothed

    NASA Astrophysics Data System (ADS)

    Rempel, A. W.; Irizarry, J. T.; VanderBeek, B. P.; Handwerger, A. L.

    2015-12-01

    The physical processes that control the bulk characteristics of hydrate reservoirs are captured reasonably well by long-established model formulations that are rooted in laboratory-verified phase equilibrium parameterizations and field-based estimates of in situ conditions. More detailed assessments of hydrate distribution, especially involving the occurrence of high-saturation hydrate anomalies have been more difficult to obtain. Spatial variations in sediment properties are of central importance for modifying the phase behavior and promoting focussed fluid flow. However, quantitative predictions of hydrate anomaly development cannot be made rigorously without also addressing the changes in phase behavior and mechanical balances that accompany changes in hydrate saturation level. We demonstrate how pore-scale geometrical controls on hydrate phase stability can be parameterized for incorporation in simulations of hydrate anomaly development along dipping coarse-grained layers embedded in a more fine-grained background that is less amenable to fluid transport. Model simulations demonstrate how hydrate anomaly growth along coarse-layer boundaries is promoted by diffusive gas transport from the adjacent fine-grained matrix, while advective transport favors more distributed growth within the coarse-grained material and so effectively limits the difference between saturation peaks and background levels. Further analysis demonstrates how sediment contacts are unloaded once hydrate saturation reaches sufficient levels to form a load-bearing skeleton that can evolve to produce segregated nodules and lenses. Decomposition of such growth forms poses a significant geohazard that is expected to be particularly sensitive to perturbations induced by gas extraction. The figure illustrates the predicted evolution of hydrate saturation Sh in a coarse-grained dipping layer showing how prominent bounding hydrate anomalies (spikes) supplied by diffusive gas transport at early times

  8. A multi-phase, micro-dispersion reactor for the continuous production of methane gas hydrate

    SciTech Connect

    Taboada Serrano, Patricia L; Ulrich, Shannon M; Szymcek, Phillip; McCallum, Scott; Phelps, Tommy Joe; Palumbo, Anthony Vito; Tsouris, Costas

    2009-01-01

    A continuous-jet hydrate reactor originally developed to generate a CO2 hydrate stream has been modified to continuously produce CH4 hydrate. The reactor has been tested in the Seafloor Process Simulator (SPS), a 72-L pressure vessel available at Oak Ridge National Laboratory. During experiments, the reactor was submerged in water inside the SPS and received water from the surrounding through a submersible pump and CH4 externally through a gas booster pump. Thermodynamic conditions in the hydrate stability regime were employed in the experiments. The reactor produced a continuous stream of CH4 hydrate, and based on pressure values and amount of gas injected, the conversion of gas to hydrate was estimated. A conversion of up to 70% was achieved using this reactor.

  9. Theoretical description of Coulomb balls: Fluid phase

    SciTech Connect

    Wrighton, J.; Dufty, J. W.; Kaehlert, H.; Bonitz, M.

    2009-12-15

    A theoretical description for the radial density profile of a finite number of identical charged particles confined in a harmonic trap is developed for application over a wide range of Coulomb coupling (or, equivalently, temperatures) and particle numbers. A simple mean-field approximation neglecting correlations yields a density profile which is monotonically decreasing with radius for all temperatures, in contrast to molecular dynamics simulations and experiments showing shell structure at lower temperatures. A more complete theoretical description including charge correlations is developed here by an extension of the hypernetted chain approximation, developed for bulk fluids, to the confined charges. The results reproduce all of the qualitative features observed in molecular dynamics simulations and experiments. These predictions are then tested quantitatively by comparison with benchmark Monte Carlo simulations. Quantitative accuracy of the theory is obtained by correcting the hypernetted chain approximation with a representation for the associated bridge functions.

  10. Molecular dynamics investigation of the structure of a fully hydrated gel-phase dipalmitoylphosphatidylcholine bilayer.

    PubMed

    Tu, K; Tobias, D J; Blasie, J K; Klein, M L

    1996-02-01

    We report the results of a constant pressure and temperature molecular dynamics simulation of a gel-phase dipalmitoylphosphatidylcholine bilayer with nw = 11.8 water molecules/lipid at 19 degrees C. The results of the simulation were compared in detail with a variety of x-ray and neutron diffraction data. The average positions of specific carbon atoms along the bilayer normal and the interlamellar spacing and electron density profile were in very good agreement with neutron and x-ray diffraction results. The area per lipid and the details of the in-plane hydrocarbon chain structure were in excellent agreement with wide-angle x-ray diffraction results. The only significant deviation is that the chains met in a pleated arrangement at the bilayer center, although they should be parallel. Novel discoveries made in the present work include the observation of a bimodal headgroup orientational distribution. Furthermore, we found that there are a significant number of gauche conformations near the ends of the hydrocarbon chains and, in addition to verifying a previous suggestion that there is partial rotational ordering in the hydrocarbon chains, that the two chains in a given molecule are inequivalent with respect to rotations. Finally, we have investigated the lipid/water interface and found that the water penetrates beneath the headgroups, but not as far as the carbonyl groups, that the phosphates are strongly hydrated almost exclusively at the nonesterified oxygen atoms, and that the hydration of the ammonium groups is more diffuse, with some water molecules concentrated in the grooves between the methyl groups. PMID:8789079

  11. Formation and phase transitions of methane hydrates under dynamic loadings: Compression rate dependent kinetics

    NASA Astrophysics Data System (ADS)

    Chen, Jing-Yin; Yoo, Choong-Shik

    2012-03-01

    We describe high-pressure kinetic studies of the formation and phase transitions of methane hydrates (MH) under dynamic loading conditions, using a dynamic-diamond anvil cell (d-DAC) coupled with time-resolved confocal micro-Raman spectroscopy and high-speed microphotography. The time-resolved spectra and dynamic pressure responses exhibit profound compression-rate dependences associated with both the formation and the solid-solid phase transitions of MH-I to II and MH-II to III. Under dynamic loading conditions, MH forms only from super-compressed water and liquid methane in a narrow pressure range between 0.9 and 1.6 GPa at the one-dimensional (1D) growth rate of 42 μm/s. MH-I to II phase transition occurs at the onset of water solidification 0.9 GPa, following a diffusion controlled mechanism. We estimated the activation volume to be -109 ± 29 Å3, primarily associated with relatively slow methane diffusion which follows the rapid interfacial reconstruction, or martensitic displacements of atomic positions and hydrogen bonds, of 51262 water cages in MH-I to 4351263 cages in MH-II. MH-II to III transition, on the other hand, occurs over a broad pressure range between 1.5 and 2.2 GPa, following a reconstructive mechanism from super-compressed MH-II clathrates to a broken ice-filled viscoelastic solid of MH-III. It is found that the profound dynamic effects observed in the MH formation and phase transitions are primarily governed by the stability of water and ice phases at the relevant pressures.

  12. Formation and phase transitions of methane hydrates under dynamic loadings: compression rate dependent kinetics.

    PubMed

    Chen, Jing-Yin; Yoo, Choong-Shik

    2012-03-21

    We describe high-pressure kinetic studies of the formation and phase transitions of methane hydrates (MH) under dynamic loading conditions, using a dynamic-diamond anvil cell (d-DAC) coupled with time-resolved confocal micro-Raman spectroscopy and high-speed microphotography. The time-resolved spectra and dynamic pressure responses exhibit profound compression-rate dependences associated with both the formation and the solid-solid phase transitions of MH-I to II and MH-II to III. Under dynamic loading conditions, MH forms only from super-compressed water and liquid methane in a narrow pressure range between 0.9 and 1.6 GPa at the one-dimensional (1D) growth rate of 42 μm/s. MH-I to II phase transition occurs at the onset of water solidification 0.9 GPa, following a diffusion controlled mechanism. We estimated the activation volume to be -109±29 Å(3), primarily associated with relatively slow methane diffusion which follows the rapid interfacial reconstruction, or martensitic displacements of atomic positions and hydrogen bonds, of 5(12)6(2) water cages in MH-I to 4(3)5(12)6(3) cages in MH-II. MH-II to III transition, on the other hand, occurs over a broad pressure range between 1.5 and 2.2 GPa, following a reconstructive mechanism from super-compressed MH-II clathrates to a broken ice-filled viscoelastic solid of MH-III. It is found that the profound dynamic effects observed in the MH formation and phase transitions are primarily governed by the stability of water and ice phases at the relevant pressures. PMID:22443783

  13. Gyroid phase of fluids with spherically symmetric competing interactions.

    PubMed

    Edelmann, Markus; Roth, Roland

    2016-06-01

    We study the phase diagram of a fluid with spherically symmetric competing pair interactions that consist of a short-ranged attraction and a longer-ranged repulsion in addition to a hard core. To this end we perform free minimizations of three-dimensional triple periodic structures within the framework of classical density functional theory. We compare our results to those from Landau theory. Our main finding is that the double gyroid phase can exist as a thermodynamically stable phase. PMID:27415247

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

    NASA Astrophysics Data System (ADS)

    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

  15. Long-Term Continuous Monitoring of Fluid Chemistry and Flux at the Bush Hill Gas Hydrate Field, Gulf of Mexico Using a New Flow Meter, The MOSQUITO

    NASA Astrophysics Data System (ADS)

    Solomon, E.; Kastner, M.; Jannasch, H.; Weinstein, Y.; Robertson, G.; Aubrey, A.

    2004-12-01

    Long-term monitoring of fluid, solute, and methane fluxes that influence marine gas hydrate formation and dissociation has important implications for the seafloor biochemical environment, ocean chemistry, and potentially the atmosphere. Four newly designed flux meters called the MOSQUITO (Multiple Orifice Sampler and Quantitative Injection Tracer Observer) and two temperature loggers were deployed adjacent to the Bush Hill hydrate mound in the northern Gulf of Mexico (GC185) in order to understand how chemistry, physics, biology, and subsurface hydrology dynamically influence the growth and dissociation of the hydrate mound. The MOSQUITO contains a network of osmotic samplers and a tracer injection device, each connected to a titanium capillary tube that penetrates the sediment. The tracer is injected as a point source, and fluid chemistry and tracer concentrations are continuously sampled simultaneously at multiple depths below the seafloor in a three dimensional array with respect to the tracer injection point. Bottom water chemistry is also sampled continuously. Vertical and horizontal flow rates as low as 1 cm/yr are determined by modeling the variability in tracer concentration at each depth over time. MOSQUITOs can be deployed at passive margins, ridge crests, ridge flanks, subduction zones, and lakes. MOSQUITOs were deployed over a period of 430 days from June 2002 to August 2003 and were sampled at weekly resolution. The temperature loggers were attached to the MOSQUITOs and recorded seafloor temperature every 40 minutes. Three MOSQUITOs were deployed within 3 m of the hydrate mound and ˜ 5 m apart, adjacent to transient methane seeps; in a mussel field, in a bacterial mat, and in a tubeworm field. The fourth MOSQUITO was placed ˜150 m southwest of the hydrate mound to monitor background fluid flow, geochemistry, and temperature. The average bottom water temperature over the 430-day deployment period was 7.94° C, with minimum temperatures occurring every

  16. Thermodynamics of Manganese Oxides at Bulk and Nanoscale: Phase Formation, Transformation, Oxidation-Reduction, and Hydration

    NASA Astrophysics Data System (ADS)

    Birkner, Nancy R.

    Natural manganese oxides are generally formed in surficial environments that are near ambient temperature and water-rich, and may be exposed to wet-dry cycles and a variety of adsorbate species that influence dramatically their level of hydration. Manganese oxide minerals are often poorly crystalline, nanophase, and hydrous. In the near-surface environment they are involved in processes that are important to life, such as water column oxygen cycling, biomineralization, and transport of minerals/nutrients through soils and water. These processes, often involving transformations among manganese oxide polymorphs, are governed by a complex interplay between thermodynamics and kinetics. Manganese oxides are also used in technology as catalysts, and for other applications. The major goal of this dissertation is to examine the energetics of bulk and nanophase manganese oxide phases as a function of particle size, composition, and surface hydration. Careful synthesis and characterization of manganese oxide phases with different surface areas provided samples for the study of enthalpies of formation by high temperature oxide melt solution calorimetry and of the energetics of water adsorption on their surfaces. These data provide a quantitative picture of phase stability and how it changes at the nanoscale. The surface energy of the hydrous surface of Mn3O4 is 0.96 +/- 0.08 J/m2, of Mn2O3 is 1.29 +/- 0.10 J/m2, and of MnO2 is 1.64 +/- 0.10 J/m2. The surface energy of the anhydrous surface of Mn3O4 is 1.62 +/- 0.08 J/m 2, of Mn2O3 is 1.77 +/- 0.10 J/m 2, and of MnO2 is 2.05 +/- 0.10 J/m2. Supporting preliminary findings (Navrotsky et al., 2010), the spinel phase (Mn3O4) has a lower surface energy (more stabilizing) than bixbyite, while the latter has a smaller surface energy than pyrolusite. These differences significantly change the positions in oxygen fugacity---temperature space of the redox couples Mn3O4-Mn2O 3 and Mn2O3-MnO2 favoring the lower surface enthalpy phase (the

  17. NATURAL GAS HYDRATES STORAGE PROJECT PHASE II. CONCEPTUAL DESIGN AND ECONOMIC STUDY

    SciTech Connect

    R.E. Rogers

    1999-09-27

    DOE Contract DE-AC26-97FT33203 studied feasibility of utilizing the natural-gas storage property of gas hydrates, so abundantly demonstrated in nature, as an economical industrial process to allow expanded use of the clean-burning fuel in power plants. The laboratory work achieved breakthroughs: (1) Gas hydrates were found to form orders of magnitude faster in an unstirred system with surfactant-water micellar solutions. (2) Hydrate particles were found to self-pack by adsorption on cold metal surfaces from the micellar solutions. (3) Interstitial micellar-water of the packed particles were found to continue forming hydrates. (4) Aluminum surfaces were found to most actively collect the hydrate particles. These laboratory developments were the bases of a conceptual design for a large-scale process where simplification enhances economy. In the design, hydrates form, store, and decompose in the same tank in which gas is pressurized to 550 psi above unstirred micellar solution, chilled by a brine circulating through a bank of aluminum tubing in the tank employing gas-fired refrigeration. Hydrates form on aluminum plates suspended in the chilled micellar solution. A low-grade heat source, such as 110 F water of a power plant, circulates through the tubing bank to release stored gas. The design allows a formation/storage/decomposition cycle in a 24-hour period of 2,254,000 scf of natural gas; the capability of multiple cycles is an advantage of the process. The development costs and the user costs of storing natural gas in a scaled hydrate process were estimated to be competitive with conventional storage means if multiple cycles of hydrate storage were used. If more than 54 cycles/year were used, hydrate development costs per Mscf would be better than development costs of depleted reservoir storage; above 125 cycles/year, hydrate user costs would be lower than user costs of depleted reservoir storage.

  18. A vibrational spectral study of hydrated tantalum phosphate(TaPO 5) phases

    NASA Astrophysics Data System (ADS)

    Stranford, G. T.; Condrate, R. A.

    1990-04-01

    Infrared and Raman spectra were measured for various hydrated tantalum phosphate (TaPO 5) materialsafter dehydration at various temperatures, and the spectral differences were interpreted on the basis of structure. The structural nature of water along with protonated phosphate and TaO 6 groups in the amorphous hydrated materials was discussed.

  19. Voluntary fluid intake, hydration status, and aerobic performance of adolescent athletes in the heat.

    PubMed

    Wilk, Boguslaw; Timmons, Brian W; Bar-Or, Oded

    2010-12-01

    We determined whether beverage flavoring and composition would stimulate voluntary drink intake, prevent dehydration, and maintain exercise performance in heat-acclimated adolescent males running in the heat. Eight adolescent (age, 13.7 ± 1.1 years) runners (peak oxygen uptake, 59.5 ± 4.0 mL·kg-1·min-1) underwent at least four 80-min exercise heat-acclimation sessions before completing 3 experimental sessions. All sessions were performed at 30 °C and 60%-65% relative humidity. Each experimental session consisted of five 15-min treadmill runs at a speed eliciting 65% peak oxygen uptake, with a 5 min rest prior to each run. Ten minutes after the final run, a time to exhaustion test was performed at a speed eliciting 90% peak oxygen uptake. Counterbalanced experimental sessions were identical, except for fluid intake, which consisted of tap water (W), flavored water (FW), and FW with 6% carbohydrate and 18 mmol·L-1 NaCl (CNa) consumed ad libitum. Fluid intake and body weight were monitored to calculate dehydration. Voluntary fluid intake was similar to fluid losses in W (1032 ± 130 vs. 1340 ± 246 g), FW (1086 ± 86 vs. 1451 ± 253 g), and CNa (1259 ± 119 vs. 1358 ± 234 g). As a result, significant dehydration was avoided in all trials (-0.45% ± 0.68% body weight in W, -0.66% ± 0.50% body weight in FW, and -0.13% ± 0.71% body weight in CNa). Core temperature increased by ~1 °C during exercise, but was not different between trials. Time to exhaustion was not different between trials and averaged 8.8 ± 1.7 min. Under exercise conditions more closely reflecting real-life situations, heat-acclimatized adolescent male runners can appropriately gauge fluid intake regardless of the type of beverage made available, resulting in consistency in exercise performance. PMID:21164555

  20. Microgravity experiments on phase change of self-rewetting fluids.

    PubMed

    Abe, Yoshiyuki; Iwasaki, Akira; Tanaka, Kotaro

    2004-11-01

    A series of microgravity experiments on self-rewetting fluids has been conducted at the 10-second drop shaft of the Japan Microgravity Center (JAMIC). In all the experiments, 1.5 wt% of 1-butanol aqueous solution were employed as a self-rewetting fluid. The objective of the first experiment was to observe the boiling behavior of two-dimensional adjacent dual vapor bubbles with the aid of a two-wavelength interferometer and tracer particles. A significant difference was observed between a self-rewetting fluid and a normal fluid (CFC-113 in this experiment) in bubble interaction and flow developed along vapor/bubble interface. The second experiment focused on the flow at the bubble/heater contact area and around the three-phase interline, visualized with tracer particles. Differing behavior among three fluids, 1-butanol aqueous solution, CFC-113, and ethanol aqueous solution, was observed. The last microgravity experiment was a demonstration of wickless heat pipes containing three different fluids as a working fluid, 1-butanol aqueous solution, water, and ethanol aqueous solution. The temperature variation of working fluid in the heat pipe was monitored, and the liquid flow returning from the condensation region to the evaporation region was visualized by tracer particles. In addition to microgravity experiments, the performance of conventional heat pipes with 1-butanol aqueous solution was evaluated on the ground, and compared with water heat pipes. Our preliminary results are presented. PMID:15644361

  1. Phase separation and emergent structures in an active nematic fluid

    PubMed Central

    Putzig, Elias; Baskaran, Aparna

    2015-01-01

    We consider a phenomenological continuum theory for an active nematic fluid and show that there exists a universal, model independent instability which renders the homogeneous nematic state unstable to order fluctuations. Using numerical and analytic tools we show that, in the vicinity of a critical point, this instability leads to a phase separated state in which the ordered regions form bands in which the direction of nematic order is perpendicular to the direction of density gradient. We argue that the underlying mechanism that leads to this phase separation is a universal feature of active fluids of different symmetries. PMID:25375491

  2. Acyl chain composition and coexisting fluid phases in lipid bilayers

    NASA Astrophysics Data System (ADS)

    Gu, Yongwen; Bradley, Miranda; Mitchell, Drake

    2011-10-01

    At room temperature phospholipid bilayers enriched in sphingolipids and cholesterol may form a solid phase as well as two coexisting fluid phases. These are the standard fluid phase, or the liquid-disordered phase, ld, and the liquid-ordered phase, lo, which is commonly associated with lipid rafts. Ternary mixtures of palmitoyl-oleoyl-phosphocholine (POPC; 16:0,18:1 PC), sphingomyelin (SPM), and cholesterol (Chol) form coexisting lo, ld and solid phases over a wide range of molar ratios. We are examining the ability of two fluorescent probes to detect these 2 phases: NBD linked to di-16:0 PE which partitions strongly into the lo phase and NBD linked to di-18:1 PE which partitions strongly into the ld phase. We are also examining the effect of the highly polyunsaturated phospholipid stearoyl-docosahexanoyl-phosphocholine (SDPC; 18:0, 22:6 PC) on the ternary phase diagram of POPC/SPM/Chol with particular focus on the functionally important lo/ld coexistence region. We report on the fluorescence lifetime and anisotropy decay dynamics of these two fluorescent probes.

  3. Phase coexistence of a Stockmayer fluid in an applied field

    NASA Astrophysics Data System (ADS)

    Stevens, Mark J.; Grest, Gary S.

    1995-06-01

    We examine two apects of Stockmayer fluids, which consist of point dipoles that additionally interact via an attractive Lennard-Jones potential. We perform Monte Carlo simulations to examine the effect of an applied field on the liquid-gas phase coexistence and show that a magnetic fluid phase does exist in the absence of an applied field. As part of the search for the magnetic fluid phase, we perform Gibbs ensemble simulations to determine phase coexistence curves at large dipole moments, μ. The critical temperature is found to depend linearly on μ2 for intermediate values of μ beyond the initial nonlinear behavior near μ=0 and less than the μ where no liquid-gas phase coexistence has been found. For phase coexistence in an applied field, the critical temperatures as a function of the applied field for two different μ are mapped onto a single curve. The critical densities change very little as a function of applied field. We also verify that in an applied field the liquid droplets within the two-phase coexistence region become elongated in the direction of the field.

  4. An Update on Maternal Hydration Strategies for Amniotic Fluid Improvement in Isolated Oligohydramnios and Normohydramnios: Evidence from a Systematic Review of Literature and Meta-Analysis

    PubMed Central

    Gizzo, Salvatore; Noventa, Marco; Vitagliano, Amerigo; Dall’Asta, Andrea; D’Antona, Donato; Aldrich, Clive J.; Quaranta, Michela; Frusca, Tiziana; Patrelli, Tito Silvio

    2015-01-01

    Objective Several trials aimed at evaluating the efficacy of maternal hydration (MH) in increasing amniotic-fluid-volume (AFV) in pregnancies with isolated oligohydramnios or normohydramnos have been conducted. Unfortunately, no evidences support this intervention in routine-clinical-practice. The aim of this systematic-literature-review and meta-analysis was to collect all data regarding proposed strategies and their efficacy in relation to each clinical condition for which MH-therapy was performed with the aim of increasing amniotic-fluid (AF) and improving perinatal outcomes. Materials and Methods A systematic literature search was conducted in electronic-database MEDLINE, EMBASE, ScienceDirect and the Cochrane-Library in the time interval between 1991 and 2014. Following the identification of eligible trials, we estimated the methodological quality of each study (using QADAS-2) and clustered patients according to the following outcome measures: route of administration (oral versus intravenous versus combined), total daily dose of fluids administered (<2000 versus >2000), duration of hydration therapy: (1 day, >1 day but <1 week, >1 week), type of fluid administered (isotonic versus hypotonic versus combination). Results In isolated-oligohydramnios (IO), maternal oral hydration is more effective than intravenous hydration and hypotonic solutions superior to isotonic solutions. The improvement in AFV appears to be time-dependent rather than daily-dose dependent. Regarding normohydramnios pregnancies, all strategies seem equivalent though the administration of hypotonic-fluid appears to have a slightly greater effect than isotonic-fluid. Regarding perinatal outcomes, data is fragmentary and heterogeneous and does not allow us to define the real clinical utility of MH. Conclusions Available data suggests that MH may be a safe, well-tolerated and useful strategy to improve AFV especially in cases of IO. In view of the numerous obstetric situations in which a reduced

  5. Phase-separation models for swimming enhancement in complex fluids

    NASA Astrophysics Data System (ADS)

    Man, Yi; Lauga, Eric

    2015-08-01

    Swimming cells often have to self-propel through fluids displaying non-Newtonian rheology. While past theoretical work seems to indicate that stresses arising from complex fluids should systematically hinder low-Reynolds number locomotion, experimental observations suggest that locomotion enhancement is possible. In this paper we propose a physical mechanism for locomotion enhancement of microscopic swimmers in a complex fluid. It is based on the fact that microstructured fluids will generically phase-separate near surfaces, leading to the presence of low-viscosity layers, which promote slip and decrease viscous friction near the surface of the swimmer. We use two models to address the consequence of this phase separation: a nonzero apparent slip length for the fluid and then an explicit modeling of the change of viscosity in a thin layer near the swimmer. Considering two canonical setups for low-Reynolds number locomotion, namely the waving locomotion of a two-dimensional sheet and that of a three-dimensional filament, we show that phase-separation systematically increases the locomotion speeds, possibly by orders of magnitude. We close by confronting our predictions with recent experimental results.

  6. Phase-separation models for swimming enhancement in complex fluids.

    PubMed

    Man, Yi; Lauga, Eric

    2015-08-01

    Swimming cells often have to self-propel through fluids displaying non-Newtonian rheology. While past theoretical work seems to indicate that stresses arising from complex fluids should systematically hinder low-Reynolds number locomotion, experimental observations suggest that locomotion enhancement is possible. In this paper we propose a physical mechanism for locomotion enhancement of microscopic swimmers in a complex fluid. It is based on the fact that microstructured fluids will generically phase-separate near surfaces, leading to the presence of low-viscosity layers, which promote slip and decrease viscous friction near the surface of the swimmer. We use two models to address the consequence of this phase separation: a nonzero apparent slip length for the fluid and then an explicit modeling of the change of viscosity in a thin layer near the swimmer. Considering two canonical setups for low-Reynolds number locomotion, namely the waving locomotion of a two-dimensional sheet and that of a three-dimensional filament, we show that phase-separation systematically increases the locomotion speeds, possibly by orders of magnitude. We close by confronting our predictions with recent experimental results. PMID:26382500

  7. All-atom molecular dynamics simulation studies of fully hydrated gel phase DPPG and DPPE bilayers

    NASA Astrophysics Data System (ADS)

    Pimthon, Jutarat; Willumeit, Regine; Lendlein, Andreas; Hofmann, Dieter

    2009-03-01

    Here in silico lipid membranes are described providing a structural background of the organization of the lipid components of membranes and aiding further biological or biophysical studies. An all-atom molecular dynamics simulations has been performed to investigate structural and dynamical properties of two fully hydrated gel-phase bilayers of 1,2-dipalmitoyl- sn-glycero-3-phosphoglycerol (DPPG) and 1,2-dipalmitoyl- sn-glycero-3-phospho-ethanolamine (DPPE) bilayers at 303 K. The respective starting configuration of lipids in the simulation bilayer unit cells were taken on the basis of scattering data. In both simulations, we found overall reasonably good agreement with the available experimental data (area per lipid, phosphorus-phosphorus distance). The distribution of the water/counterions at the membrane interface, interactions/orientations of lipid headgroups, and hydrocarbon chain organization were extensively studied in terms of pair distribution functions between main structural components of the system. Intra/intermolecular hydrogen bond formation was discussed in detail. The water orientation at the lipid membrane interface was explored thoroughly in terms of dipole moment as a function of the water molecule positions along the membrane, where we found that the counterions changed the orientation of the water at the interface. Special attention has been devoted to the distribution of the sodium counterions around the DPPG headgroup. We found preferential binding of Na + ions to the phosphate oxygen species.

  8. Ternary phase behaviour and vesicle formation of a sodium N-lauroylsarcosinate hydrate/1-decanol/water system

    NASA Astrophysics Data System (ADS)

    Akter, Nasima; Radiman, Shahidan; Mohamed, Faizal; Rahman, Irman Abdul; Reza, Mohammad Imam Hasan

    2011-08-01

    The phase behaviour of a system composed of amino acid-based surfactant (sodium N-lauroylsarcosinate hydrate), 1-decanol and deionised water was investigated for vesicle formation. Changing the molar ratio of the amphiphiles, two important aggregate structures were observed in the aqueous corner of the phase diagram. Two different sizes of microemulsions were found at two amphiphile-water boundaries. A stable single vesicle lobe was found for 1∶2 molar ratios in 92 wt% water with vesicles approximately 100 nm in size and with high zeta potential value. Structural variation arises due to the reduction of electrostatic repulsions among the ionic headgroups of the surfactants and the hydration forces due to adsorbed water onto monolayer's. The balance of these two forces determines the aggregate structures. Analysis was followed by the molecular geometrical structure. These findings may have implications for the development of drug delivery systems for cancer treatments, as well as cosmetic and food formulations.

  9. High-Resolution 3D-Seismic Investigations Indicate Focused Fluid Flow Systems in Hydrated Sediments at the Vestnesa Ridge off the W-Svalbard Margin.

    NASA Astrophysics Data System (ADS)

    Petersen, C.; Buenz, S.; Hustoft, S.; Mienert, J.

    2007-12-01

    High-resolution seismic data were acquired using the 3D seismic P-Cable system of the University of Tromsoe to investigate how the fluid flow penetrates gas hydrate systems of the Vestnesa Ridge. The ridge represents a current-controlled sediment drift on the continental margin offshore western Svalbard. The survey area is located at the northwestern part of the Vestnesa Ridge and centered at the ridge crest that resembles an anticline in a water depth of 1250-1320 m. The seafloor morphology at the crest is characterized by an abundance of pockmarks with a diameter between 50-500 m indicating recent fluid flow activity. Since the area is within the gas hydrate stability zone (GHSZ), it is an ideal site to understand where and how fluids escape through a hydrated sediment drift. 35 reflection seismic profiles with a spacing of about 40-60 m were shot resulting in a seismic cube covering an area of approximately 22 km2. In addition, regional single channel streamer (SCS) seismic lines were acquired across the ridge perpendicular to the crest to connect the 3D area with the regional structural setting. The seismic data provide images of the subsurface to about 500 ms TWT (two-way time) below the seafloor (bsf), where gas accumulations cause acoustic attenuations that hinder deeper acoustic signal penetration. The well-stratified sediments exhibit a bottom simulating reflector (BSR) at about 200 ms TWT bsf at the base of the GHSZ. The BSR is difficult to identify due to the stratification, but it is accompanied by the onset of an ubiquitous band of strong reflectivity indicating free gas accumulation zones beneath the GHSZ. Fluid flow activity is evident from a link between gas accumulations (bright spots), gas wipeouts and disturbed reflectivity in the seismic data. These features are observed not only beneath the pockmark structures, but also in the sediment without seafloor expressions of fluid venting. The fluid source might be related to deep tectonic processes at

  10. Fluid structure interaction solver coupled with volume of fluid method for two-phase flow simulations

    NASA Astrophysics Data System (ADS)

    Cerroni, D.; Fancellu, L.; Manservisi, S.; Menghini, F.

    2016-06-01

    In this work we propose to study the behavior of a solid elastic object that interacts with a multiphase flow. Fluid structure interaction and multiphase problems are of great interest in engineering and science because of many potential applications. The study of this interaction by coupling a fluid structure interaction (FSI) solver with a multiphase problem could open a large range of possibilities in the investigation of realistic problems. We use a FSI solver based on a monolithic approach, while the two-phase interface advection and reconstruction is computed in the framework of a Volume of Fluid method which is one of the more popular algorithms for two-phase flow problems. The coupling between the FSI and VOF algorithm is efficiently handled with the use of MEDMEM libraries implemented in the computational platform Salome. The numerical results of a dam break problem over a deformable solid are reported in order to show the robustness and stability of this numerical approach.

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

    USGS Publications Warehouse

    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.

  12. Rayleigh-Taylor instability of viscous fluids with phase change

    NASA Astrophysics Data System (ADS)

    Kim, Byoung Jae; Kim, Kyung Doo

    2016-04-01

    Film boiling on a horizontal surface is a typical example of the Rayleigh-Taylor instability. During the film boiling, phase changes take place at the interface, and thus heat and mass transfer must be taken into consideration in the stability analysis. Moreover, since the vapor layer is not quite thick, a viscous flow must be analyzed. Existing studies assumed equal kinematic viscosities of two fluids, and/or considered thin viscous fluids. The purpose of this study is to derive the analytical dispersion relation of the Rayleigh-Taylor instability for more general conditions. The two fluids have different properties. The thickness of the vapor layer is finite, but the liquid layer is thick enough to be nearly semi-infinite in view of perturbation. Initially, the vapor is in equilibrium with the liquid at the interface, and the direction of heat transfer is from the vapor side to the liquid side. In this case, the phase change has a stabilizing effect on the growth rate of the interface. When the vapor layer is thin, there is a coupled effect of the vapor viscosity, phase change, and vapor thickness on the critical wave number. For the other limit of a thick vapor, both the liquid and vapor viscosities influence the critical wave number. Finally, the most unstable wavelength is investigated. When the vapor layer is thin, the most unstable wavelength is not affected by phase change. When the vapor layer is thick, however, it increases with the increasing rate of phase change.

  13. Rayleigh-Taylor instability of viscous fluids with phase change.

    PubMed

    Kim, Byoung Jae; Kim, Kyung Doo

    2016-04-01

    Film boiling on a horizontal surface is a typical example of the Rayleigh-Taylor instability. During the film boiling, phase changes take place at the interface, and thus heat and mass transfer must be taken into consideration in the stability analysis. Moreover, since the vapor layer is not quite thick, a viscous flow must be analyzed. Existing studies assumed equal kinematic viscosities of two fluids, and/or considered thin viscous fluids. The purpose of this study is to derive the analytical dispersion relation of the Rayleigh-Taylor instability for more general conditions. The two fluids have different properties. The thickness of the vapor layer is finite, but the liquid layer is thick enough to be nearly semi-infinite in view of perturbation. Initially, the vapor is in equilibrium with the liquid at the interface, and the direction of heat transfer is from the vapor side to the liquid side. In this case, the phase change has a stabilizing effect on the growth rate of the interface. When the vapor layer is thin, there is a coupled effect of the vapor viscosity, phase change, and vapor thickness on the critical wave number. For the other limit of a thick vapor, both the liquid and vapor viscosities influence the critical wave number. Finally, the most unstable wavelength is investigated. When the vapor layer is thin, the most unstable wavelength is not affected by phase change. When the vapor layer is thick, however, it increases with the increasing rate of phase change. PMID:27176406

  14. Reexamining the phase diagram of the Gay-Berne fluid

    NASA Astrophysics Data System (ADS)

    de Miguel, Enrique

    This work reexamines and updates earlier investigations on the phase behaviour of the Gay- Berne liquid crystal model, concentrating on the effect of varying temperature. Constant volume and constant pressure Monte Carlo simulations are combined for systems consisting of N = 500 molecules along different isotherms over the reduced temperature range 0.60 Ř T Ř1.25. As in previous simulation studies of the model, the study identifies nematic and smectic B phases on compressing the isotropic fluid, the particular phase sequence depending on temperature. The nematic phase is found to be stable with respect to the isotropic phase for reduced temperatures T ≥0.75. In the temperature range 0.75 Ř T Ř1.25, the phase boundaries of the isotropic-nematic transition are obtained by computing the Helmholtz free energy of both phases from thermodynamic integration. From the simulation data, the relative volume change at the isotropic-nematic transition is about 2%, and this value appears to be rather insensitive to changes in temperature. On compressing the nematic phase, the Gay-Berne fluid undergoes a strong first-order transition to the smectic B phase. This transition is studied by using constant pressure simulation, and the coexistence properties are estimated from the limits of mechanical stability of the nematic phase. Larger relative volume changes are found at the transition than those suggested by previous studies, with typical values increasing up to 10.5% as the temperature is decreased. The results are consistent with the existence of strong coupling between nematic and smectic order parameters. For temperatures T Ř0.70 the nematic phase is no longer stable, and the phase sequence isotropic-smectic B is observed. Therefore, the Gay-Berne model exhibits an isotropic- nematic-smectic B triple point. Extrapolating the present simulation data, this triple point is located approximately at reduced temperature P INB ≈1.825. T INB ≈0.70 and reduced pressure

  15. Hydrate Control for Gas Storage Operations

    SciTech Connect

    Jeffrey Savidge

    2008-10-31

    The overall objective of this project was to identify low cost hydrate control options to help mitigate and solve hydrate problems that occur in moderate and high pressure natural gas storage field operations. The study includes data on a number of flow configurations, fluids and control options that are common in natural gas storage field flow lines. The final phase of this work brings together data and experience from the hydrate flow test facility and multiple field and operator sources. It includes a compilation of basic information on operating conditions as well as candidate field separation options. Lastly the work is integrated with the work with the initial work to provide a comprehensive view of gas storage field hydrate control for field operations and storage field personnel.

  16. Phase State and Dynamics of Fluids in Mesoporous Solids

    NASA Astrophysics Data System (ADS)

    Valiullin, Rustem

    2011-03-01

    Fundamental understanding of the correlations between the phase state and dynamics of fluids confined to mesoporous solids is an important prerequisite for their optimal use in practical applications. The present contribution describes some recent progress in the exploration of such interrelations using nuclear magnetic resonance. In particular, transport properties of fluids during gas-liquid, solid-liquid and liquid-liquid transitions occurring in pore spaces of mesoporous solids are discussed and are shown to bear strong correlations. From the results presented it will, in particular, become evident that molecular diffusivity is a sensitive microscopic parameter not only to the thermodynamic state of the system, but also the history of its preparation.

  17. Is there a third order phase transition for supercritical fluids?

    PubMed

    Zhu, Jinglong; Zhang, Pingwen; Wang, Han; Site, Luigi Delle

    2014-01-01

    We prove that according to Molecular Dynamics (MD) simulations of liquid mixtures of Lennard-Jones (L-J) particles, there is no third order phase transition in the supercritical regime beyond Andrew's critical point. This result is in open contrast with recent theoretical studies and experiments which instead suggest not only its existence but also its universality regarding the chemical nature of the fluid. We argue that our results are solid enough to go beyond the limitations of MD and the generic character of L-J models, thus suggesting a rather smooth liquid-vapor thermodynamic behavior of fluids in supercritical regime. PMID:24410228

  18. Positron annihilation and nuclear magnetic resonance study of the phase behavior of water confined in mesopores at different levels of hydration.

    PubMed

    Maheshwari, Priya; Dutta, Dhanadeep; Mukherjee, Saurabh; Madhu, Perunthiruthy K; Mote, Kaustubh R; Pujari, Pradeep K

    2016-05-14

    We investigated the molecular origin of the phase behavior of water confined in MCM 41 mesopores at different levels of hydration using positron annihilation spectroscopic and nuclear magnetic resonance techniques. The level of hydration influenced the phase behavior of the nanoconfined water. Two transitions above and below the bulk freezing temperature were observed depending on the level of hydration. At the highest level of hydration, nucleation seemed to predominate over the effect of confinement, leading to the complete freezing of water, whereas disrupted H-bonding dominated at the lowest level of hydration, leading to the disappearance of the transitions. A transition at c. T = 188 K (close to the reported glass transition temperature of interface-affected water) was observed at intermediate hydration level. This study suggests that the H-bonding network within nanoconfined water, which can be tampered by the degree of hydration, is the key factor responsible for the phase behavior of supercooled water. This study on the phase behavior and associated transitions of nanoconfined water has implications for nanofluidics and drug-delivery systems, in addition to understanding the fundamentals of water in confinement. PMID:27105178

  19. Molecular mechanism of the hydration of Candida antarctica lipase B in the gas phase: Water adsorption isotherms and molecular dynamics simulations.

    PubMed

    Branco, Ricardo J F; Graber, Marianne; Denis, Vinciane; Pleiss, Jürgen

    2009-12-14

    Hydration is a major determinant of activity and selectivity of enzymes in organic solvents or in gas phase. The molecular mechanism of the hydration of Candida antarctica lipase B (CALB) and its dependence on the thermodynamic activity of water (a(w)) was studied by molecular dynamics simulations and compared to experimentally determined water sorption isotherms. Hydration occurred in two phases. At low water activity, single water molecules bound to specific water binding sites at the protein surface. As the water activity increased, water networks gradually developed. The number of protein-bound water molecules increased linearly with a(w), until at a(w)=0.5 a spanning water network was formed consisting of 311 water molecules, which covered the hydrophilic surface of CALB, with the exception of the hydrophobic substrate-binding site. At higher water activity, the thickness of the hydration shell increased up to 10 A close to a(w)=1. Above a limit of 1600 protein-bound water molecules the hydration shell becomes unstable and the formation of pure water droplets occurs in these oversaturated simulation conditions. While the structure and the overall flexibility of CALB was independent of the hydration state, the flexibility of individual loops was sensitive to hydration: some loops, such as those part of the substrate-binding site, became more flexible, while other parts of the protein became more rigid upon hydration. However, the molecular mechanism of how flexibility is related to activity and selectivity is still elusive. PMID:19847841

  20. Concept of Methane Hydrate System in the eastern Nankai Trough

    NASA Astrophysics Data System (ADS)

    Nagakubo, S.; Fujii, T.; Noguchi, S.; Kawasaki, T.

    2008-12-01

    By the study of the Phase 1 (FY2001-2008) of the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium), MH21 Research Consortium showed that methane hydrates pore-filled in sandy sediments had a potential to develop in the future. It is important to clarify the accumulation mechanism and processes of methane hydrates pore-filled in sandy sediment because it would contribute to explore new methane hydrate field to develop other than the eastern Nankai Trough in the future. Therefore Japan Oil, Gas and Metals National Corporation (JOGMEC), as a member of MH21 Research Consortium, has been constructing a concept of Methane Hydrate System (methane generation and migration, MH formation and dissociation) with methane hydrates pore-filled in sandy sediment. We extracted critical elements and executed processes to summarize Methane Hydrate System in the eastern Nankai Trough by reviewing past geochemical analysis, well logs and core analyses, seismic interpretations, and laboratory studies for the eastern Nankai Trough. We also conducted case studies using 1D and 2D numerical simulators developed for the clarification of methane hydrate accumulation mechanism. It was determined that there are still many unsolved issues as listed below though we try to construct a concept of Methane Hydrate System in the eastern Nankai Trough. 1.Methane source and migration -methane-dominant generation depth -methane generation rate. -driving forces of methane migration 2.Occurrences and distribution -occurrences and distribution of methane hydrates other than methane hydrates pore-filled in sandy sediment. -methane-bearing fluid condition (properties, distribution) below methane hydrate bearing zones. 3.Relation between seafloor phenomena and methane hydrate occurences. 4.Impact of geohistory and sea level (water depth) change to methane hydrate accumulation. New investigation surveys (drilling and geological/geochemical surveys on seafloor) are required to

  1. Spatial distribution of seafloor bio-geological and geochemical processes as proxies of fluid flux regime and evolution of a carbonate/hydrates mound, northern Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    Macelloni, Leonardo; Brunner, Charlotte A.; Caruso, Simona; Lutken, Carol B.; D'Emidio, Marco; Lapham, Laura L.

    2013-04-01

    Woolsey Mound, a carbonate/hydrate complex of cold seeps, vents, and seafloor pockmarks in Mississippi Canyon Block 118, is the site of the Gulf of Mexico Hydrates Research Consortium's (GOMHRC) multi-sensor, multi-disciplinary, permanent seafloor observatory. In preparation for installing the observatory, the site has been studied through geophysical, biological, geological, and geochemical surveys. By integrating high-resolution, swath bathymetry, acoustic imagery, seafloor video, and shallow geological samples in a morpho-bio-geological model, we have identified a complex mound structure consisting of three main crater complexes: southeast, northwest, and southwest. Each crater complex is associated with a distinct fault. The crater complexes exhibit differences in morphology, bathymetric relief, exposed hydrates, fluid venting, sediment accumulation rates, sediment diagenesis, and biological community patterns. Spatial distribution of these attributes suggests that the complexes represent three different fluid flux regimes: the southeast complex seems to be an extinct or quiescent vent; the northwest complex exhibits young, vigorous activity; and the southwest complex is a mature, fully open vent. Geochemical evidence from pore-water gradients corroborates this model suggesting that upward fluid flux waxes and wanes over time and that microbial activity is sensitive to such change. Sulfate and methane concentrations show that microbial activity is patchy in distribution and is typically higher within the northwest and southwest complexes, but is diminished significantly over the southeast complex. Biological community composition corroborates the presence of distinct conditions at the three crater complexes. The fact that three different fluid flux regimes coexist within a single mound complex confirms the dynamic nature of the plumbing system that discharges gases into bottom water. Furthermore, the spatial distribution of bio-geological processes appears to

  2. High-Resolution Scanning Tunneling Microscopy of Fully Hydrated Ripple-Phase Bilayers

    PubMed Central

    Woodward IV, J. T.; Zasadzinski, J. A.

    1997-01-01

    A modified freeze-fracture replication technique for use with the scanning tunneling microscope (STM) has provided a quantitative, high-resolution description of the waveform and amplitude of rippled bilayers in the Pβ, phase of dimyristoylphosphatidylcholine (DMPC) in excess water. The ripples are uniaxial and asymmetrical, with a temperature-dependent amplitude of 2.4 nm near the chain melting temperature that decreases to zero at the chain crystallization temperature. The wavelength of 11 nm does not change with temperature. The observed ripple shape and the temperature-induced structural changes are not predicted by any current theory. Calibration and reproducibility of the STM/replica technique were tested with replicas of well-characterized bilayers of cadmium arachidate on mica that provide regular 5.5-nm steps. STM images were analyzed using a cross-correlation averaging program to eliminate the effects of noise and the finite size and shapes of the metal grains that make up the replica. The correlation averaging allowed us to develop a composite ripple profile averaged over hundreds of individual ripples measured on different samples with different STM tips. The STM/replica technique avoids many of the previous artifacts of biological STM imaging and can be used to examine a variety of periodic hydrated lipid and protein samples at a lateral resolution of about 1 nm and a vertical resolution of about 0.3 nm. This resolution is superior to conventional and tapping mode AFM of soft biological materials; the technique is substrate-free, and the conductive and chemically uniform replicas make image interpretation simple and direct. ImagesFIGURE 1FIGURE 2FIGURE 3FIGURE 5 PMID:9017222

  3. A model of attractive interactions to account for fluid-fluid phase separation of protein solutions

    NASA Astrophysics Data System (ADS)

    Malfois, Marc; Bonneté, Françoise; Belloni, Luc; Tardieu, Annette

    1996-08-01

    Concentrated γ-crystallin and lysozyme solutions have been reported to undergo a fluid-fluid phase separation when cooled below a critical temperature. This behavior is under control of the weak forces acting in solution between macromolecules. We have used small angle x-ray scattering at the synchrotron radiation facility LURE (Orsay, France) to analyze the interaction potentials. A model of attractive interactions which depends upon three parameters, protein diameter, potential depth, and range, is able to account for both the x-ray structure factors measured at high temperature and for the low temperature phase separation. Although van der Waals forces could be at the origin of the attractive interaction potentials, other more specific effects also contribute to the protein phase diagrams.

  4. Methane Recovery from Hydrate-bearing Sediments

    SciTech Connect

    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

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

    NASA Astrophysics Data System (ADS)

    Manohara, G. V.; Vishnu Kamath, P.; Milius, Wolfgang

    2012-12-01

    Acetate-intercalated layered double hydroxides (LDHs) of Ni and Al undergo reversible hydration in the solid state in response to the ambient humidity. The LDH with a high layer charge (0.33/formula unit) undergoes facile hydration in a single step, whereas the LDH with a lower layer charge (0.24/formula unit) exhibits an ordered interstratified intermediate, comprising the hydrated and dehydrated layers stacked alternatively. This phase, also known as the staged S-2 phase, coexists with the end members suggesting the existence of a solution-type equilibrium between the S-2 phase and the end members of the hydration cycle. These LDHs also undergo facile aqueous exfoliation into 2-5 nm-thick tactoids with a radial dimension of 0.2-0.5 μm.

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

    NASA Astrophysics Data System (ADS)

    Seol, Yongkoo; Kneafsey, Timothy J.

    2011-08-01

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

  7. Microscopic observation and in-situ Raman scattering studies on high-pressure phase transformations of Kr hydrate.

    PubMed

    Sasaki, Shigeo; Hori, Shinsuke; Kume, Tetsuji; Shimizu, Hiroyasu

    2006-05-25

    Direct observations through a microscope and in-situ Raman scattering measurements of synthesized single-crystalline Kr hydrate have been performed at pressures up to 5.2 GPa and 296 K. We have observed that the initial cubic structure II (sII) of Kr hydrate successively transforms to a cubic structure I (sI), a hexagonal structure, and an orthorhombic structure (sO) called "filled ice" at 0.45, 0.75, and 1.8 GPa, respectively. The sO phase exists at least up to 5.2 GPa. In addition to these transformations, we have also found the new phase behavior at 1.0 GPa, which is most likely caused by the change of cage occupancy of host water cages by guest Kr atoms without structural change. Raman scattering measurements for observed phases have shown that the lattice vibrational peak at around 130 cm(-1) disappears in the pressure region of sI, which enables us to distinguish the sI phase from sII and sH phases. PMID:16706436

  8. Fluid hydrogen at high density - The plasma phase transition

    NASA Technical Reports Server (NTRS)

    Saumon, D.; Chabrier, G.

    1989-01-01

    A new model equation of state is applied, based on realistic interparticle potentials and a self-consistent treatment of the internal levels, to fluid hydrogen at high density. This model shows a strong connection between molecular dissociation and pressure ionization. The possibility of a first-order plasma phase transition is considered, and for which both the evolution in temperature and the critical point is given.

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

    SciTech Connect

    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.

  10. Elevating salinity and temperature with hydrate formation at deepwater Gulf of Mexico vents

    NASA Astrophysics Data System (ADS)

    Smith, Andrew J.; Flemings, Peter B.; Liu, Xiaoli

    2013-04-01

    We study the Ursa vent in ~1070 meters water depth at lease blocks MC852/853 in the northern Gulf of Mexico. Elevated salinities and temperatures at the vent shift the base of the hydrate stability zone (HSZ) to the seafloor (Paull et al., 2005; Ruppel et al., 2005). We model the coexistence of high salinities, high temperatures, and an uplifted hydrate phase boundary with a one-dimensional, multicomponent, multiphase, fluid- and heat-flow model of hydrate formation. In this model, free gas supplied from depth migrates vertically through a high-permeability conduit to the regional hydrate stability zone (RHSZ). Once reaching the base of the RHSZ, gas combines with water to form hydrate, salt is excluded, and heat is released. Hydrate formation continues until water is too warm and saline for further hydrate formation. This process self generates three-phase (gas, liquid, hydrate) equilibrium through the RHSZ and allows gas to vent from the base of the RHSZ to the seafloor. Once the reaction front breaches the seafloor, a pseudo steady state is reached in which a continuous salt flux diffuses from the seafloor, and further hydrate formation occurs at a rate necessary to replace the diffuse salt loss. This continued hydrate formation has the potential to produce large, steady fluxes of salt and heat from the seafloor. Such gas-hydrate and fluid-flow systems are important because they are especially sensitive to global ocean warming due to the large concentrations of hydrate that exist at three-phase equilibrium near the seafloor. References: Paull, C., Ussler, W., Lorenson, T., Winters, W., Dougherty, J., 2005. Geochemical constraints on the distribution of gas hydrates in the Gulf of Mexico. Geo-Marine Letters 25, 273-280. Ruppel, C., Dickens, G.R., Castellini, D.G., Gilhooly, W., Lizarralde, D., 2005. Heat and salt inhibition of gas hydrate formation in the northern Gulf of Mexico. Geophys. Res. Lett. 32, L04605.

  11. A Phase-Field Method for Simulating Fluid-Structure Interactions in Multi-Phase Flow

    NASA Astrophysics Data System (ADS)

    Zheng, Xiaoning; Karniadakis, George

    2015-11-01

    We investigate two-phase flow instabilities by numerical simulations of fluid structure interactions in two-phase flow. The first case is a flexible pipe conveying two fluids, which exhibits self-sustained oscillations at high Reynolds number and tension related parameter. Well-defined two-phase flow patterns, i.e., slug flow and bubbly flow, are observed. The second case is external two-phase cross flow past a circular cylinder, which induces a Kelvin-Helmholtz instability due to density stratification. We solve the Navier-Stokes equation coupled with the Cahn-Hilliard equation and the structure equation in an arbitrary Lagrangian Eulerian (ALE) framework. For the fluid solver, a spectral/hp element method is employed for spatial discretization and backward differentiation for time discretization. For the structure solver, a Galerkin method is used in Lagrangian coordinates for spatial discretization and the Newmark- β scheme for time discretization.

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

    PubMed

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

    2015-05-21

    Water condensing as liquid drops within the fluid bulk has traditionally been the only scenario accepted in the industrial analysis of hydrate risks. We have applied a combination of absolute thermodynamics and molecular dynamics modeling to analyze the five primary routes of hydrate formation in a rusty pipeline carrying dense carbon dioxide with methane, hydrogen sulfide, argon, and nitrogen as additional impurities. We have revised the risk analysis of all possible routes in accordance with the combination of the first and the second laws of thermodynamics to determine the highest permissible content of water. It was found that at concentrations lower than five percent, hydrogen sulfide will only support the formation of carbon dioxide-dominated hydrate from adsorbed water and hydrate formers from carbon dioxide phase rather than formation in the aqueous phase. Our results indicate that hydrogen sulfide leaving carbon dioxide for the aqueous phase will be able to create an additional hydrate phase in the aqueous region adjacent to the first adsorbed water layer. The growth of hydrate from different phases will decrease the induction time by substantially reducing the kinetically limiting mass transport across the hydrate films. Hydrate formation via adsorption of water on rusty walls will play the decisive role in hydrate formation risk, with the initial concentration of hydrogen sulfide being the critical factor. We concluded that the safest way to eliminate hydrate risks is to ensure that the water content of carbon dioxide is low enough to prevent water dropout via the adsorption mechanism. PMID:25903085

  13. Detection of phase separation in fluid phosphatidylserine/phosphatidylcholine mixtures.

    PubMed

    Hinderliter, A K; Huang, J; Feigenson, G W

    1994-11-01

    The nonideal mixing of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoserine, (16:0, 18:1)PS, and 1,2-didodecenoyl-sn-glycero-3-phosphocholine, (12:1, 12:1)PC, in fluid lamellar model membranes was studied by measuring binding of aqueous Ca2+ ions and by x-ray diffraction. A region of two-phase coexistence was found by invariance of the aqueous concentration and by the appearance of two sets of lamellar spacings. The phases were identified as fluid from the diffuse x-ray diffraction in the wide-angle region. The width of the two-phase coexistence region was greater at higher ionic strength. In 800 mM KCl, the phase boundaries were at PS mole fraction 0.5 and 0.8. In 100 mM KCl, the phase boundaries were at PS mole fraction 0.52 and 0.62. Monte Carlo simulations of the lateral distributions of these PS/PC mixtures show pronounced clustering of the lipids. PMID:7858127

  14. Growth and Morphology of Phase Separating Supercritical Fluids

    NASA Technical Reports Server (NTRS)

    Hegseth, John; Beysens, Daniel; Perrot, Francoise; Nikolayev, Vadim; Garrabos, Yves

    1996-01-01

    The scientific objective is to study the relation between the morphology and the growth kinetics of domains during phase separation. We know from previous experiments performed near the critical point of pure fluids and binary liquids that there are two simple growth laws at late times. The 'fast' growth appears when the volumes of the phases are nearly equal and the droplet pattern is interconnected. In this case the size of the droplets grows linearly in time. The 'slow' growth appears when the pattern of droplets embedded in the majority phase is disconnected. In this case the size of the droplets increases in proportion to time to the power 1/3. The volume fraction of the minority phase is a good candidate to determine this change of behavior. All previous attempts to vary the volume fraction in a single experimental cell have failed because of the extreme experimental difficulties.

  15. Membrane Elasticity in Giant Vesicles with Fluid Phase Coexistence

    PubMed Central

    Baumgart, T.; Das, S.; Webb, W. W.; Jenkins, J. T.

    2005-01-01

    Biological membranes are known to contain compositional heterogeneities, often termed rafts, with distinguishable composition and function, and these heterogeneities participate in vigorous transport processes. Membrane lipid phase coexistence is expected to modulate these processes through the differing mechanical properties of the bulk domains and line tension at phase boundaries. In this contribution, we compare the predictions from a shape theory derived for vesicles with fluid phase coexistence to the geometry of giant unilamellar vesicles with coexisting liquid-disordered (Ld) and liquid-ordered (Lo) phases. We find a bending modulus for the Lo phase higher than that of the Ld phase and a saddle-splay (Gauss) modulus difference with the Gauss modulus of the Lo phase being more negative than the Ld phase. The Gauss modulus critically influences membrane processes that change topology, such as vesicle fission or fusion, and could therefore be of significant biological relevance in heterogeneous membranes. Our observations of experimental vesicle geometries being modulated by Gaussian curvature moduli differences confirm the prediction by the theory of Juelicher and Lipowsky. PMID:15894634

  16. Fractionation of Cl/Br during fluid phase separation in magmatic-hydrothermal fluids

    NASA Astrophysics Data System (ADS)

    Seo, Jung Hun; Zajacz, Zoltán

    2016-06-01

    Brine and vapor inclusions were synthesized to study Cl/Br fractionation during magmatic-hydrothermal fluid phase separation at 900 °C and pressures of 90, 120, and 150 MPa in Li/Na/K halide salt-H2O systems. Laser ablation ICP-MS microanalysis of high-density brine inclusions show an elevated Cl/Br ratio compared to the coexisting low-density vapor inclusions. The degree of Cl/Br fractionation between vapor and brine is significantly dependent on the identity of the alkali metal in the system: stronger vapor partitioning of Br occurs in the Li halide-H2O system compared to the systems of K and Na halide-H2O. The effect of the identity of alkali-metals in the system is stronger compared to the effect of vapor-brine density contrast. We infer that competition between alkali-halide and alkali-OH complexes in high-temperature fluids might cause the Cl/Br fractionation, consistent with the observed molar imbalances of alkali metals compared to halides in the analyzed brine inclusions. Our experiments show that the identity of alkali metals controls the degrees of Cl/Br fractionation between the separating aqueous fluid phases at 900 °C, and suggest that a significant variability in the Cl/Br ratios of magmatic fluids can arise in Li-rich systems.

  17. Implementing stationary-phase optimized selectivity in supercritical fluid chromatography.

    PubMed

    Delahaye, Sander; Lynen, Frédéric

    2014-12-16

    The performance of stationary-phase optimized selectivity liquid chromatography (SOS-LC) for improved separation of complex mixtures has been demonstrated before. A dedicated kit containing column segments of different lengths and packed with different stationary phases is commercially available together with algorithms capable of predicting and ranking isocratic and gradient separations over vast amounts of possible column combinations. Implementation in chromatographic separations involving compressible fluids, as is the case in supercritical fluid chromatography, had thus far not been attempted. The challenge of this approach is the dependency of solute retention with the mobile-phase density, complicating linear extrapolation of retention over longer or shorter columns segments, as is the case in conventional SOS-LC. In this study, the possibilities of performing stationary-phase optimized selectivity supercritical fluid chromatography (SOS-SFC) are demonstrated with typical low density mobile phases (94% CO2). The procedure is optimized with the commercially available column kit and with the classical isocratic SOS-LC algorithm. SOS-SFC appears possible without any density correction, although optimal correspondence between prediction and experiment is obtained when isopycnic conditions are maintained. As also the influence of the segment order appears significantly less relevant than expected, the use of the approach in SFC appears as promising as is the case in HPLC. Next to the classical use of SOS for faster baseline separation of all solutes in a mixture, the benefits of the approach for predicting as wide as possible separation windows around to-be-purified solutes in semipreparative SFC are illustrated, leading to significant production rate improvements in (semi)preparative SFC. PMID:25393519

  18. Understanding gas hydrate dissolution

    NASA Astrophysics Data System (ADS)

    Lapham, Laura; Chanton, Jeffrey; MacDonald, Ian; Martens, Christopher

    2010-05-01

    In order to understand the role gas hydrates play in climate change or their potential as an energy source, we must first understand their basic behaviors. One such behavior not well understood is their dissolution and the factors that control it. Theoretically, hydrates are stable in areas of high pressure, low temperature, moderate salt concentrations, and saturated methane. Yet in nature, we observe hydrate to outcrop seafloor sediments into overlying water that is under-saturated with respect to methane. How do these hydrates not dissolve away? To address this question, we combine both field and laboratory experiments. In the field, we have collected pore-waters directly surrounding gas hydrate outcrops and measured for in situ methane concentrations. This gives us an understanding of the concentration gradients, and thus methane flux, directly from the hydrate to the surrounding environment. From these samples, we found that methane concentrations decreased further from hydrate yet are always under-saturated with respect to methane hydrate. The resulting low methane gradients were then used to calculate low dissolution rates. This result suggests that hydrates are meta-stable in the environment. What controls their apparent meta-stability? We hypothesize that surrounding oils or microbial slimes help protect the hydrate and slow down their dissolution. To test this hypothesis, we conducted a series of laboratory experiments where hydrate was formed at in situ pressure and temperature and the source gas removed; first with no oils, then with oils. Dissolved methane concentrations were then measured in surrounding fluids over time and dissolution rates calculated. To date, both methane and mixed gas hydrate (methane, ethane, and propane) have similar dissolution rates of 0.12 mM/hr. Future experiments will add oils to determine how different hydrate dissolves with such contaminants. This study will further our understanding of factors that control hydrate

  19. On the thermodynamic stability of clathrate hydrates V: phase behaviors accommodating large guest molecules with new reference states.

    PubMed

    Tanaka, Hideki; Matsumoto, Masakazu

    2011-12-01

    We present a method that brings prediction of phase behaviors of various clathrate hydrates with firm statistical mechanical ground adopting a different reference state from the usual one. Accommodation of a large guest molecule makes the frequencies of the lattice vibrational motions higher, which is one of the breakdowns of the assumptions in the original van der Waals and Platteeuw theory. The frequency modulations are incorporated in the free energy of cage occupation in the present method. Moreover, the reference state, which is originally the corresponding empty clathrate structure, is alternated to a state where cages of at least one sort are fully occupied. This meets the stability condition of clathrate hydrates that most of the cages should be accommodated. Owing to this new reference state, the thermodynamic stability is evaluated with reasonable accuracy from the free energy of cage occupation especially by a large guest molecule without considering its dependence on the cage occupancy. This conversion is also beneficial to establish a relation between the chemical potential of water and the cage occupancy from grandcanonical Monte Carlo simulation. We show a new method indeed works well in predicting the dissociation pressures of clathrate hydrates containing isobutane, propane, ethane, Xe, and CF(4). PMID:21902174

  20. TEM and NanoSIMS Study of Hydrated/Anhydrous Phase Mixed IDPs: Cometary or Asteroidal Origin?

    NASA Technical Reports Server (NTRS)

    Nakamura, K.; Messenger, S.; Keller, L. P.

    2005-01-01

    Chondritic interplanetary dust particles (IDPs) are subdivided into (1) particles that form highly porous aggregates (chondritic porous "CP" IDPs), and (2) smooth particles ("CS" IDPs). Infrared (IR) spectroscopy has been a valuable tool for non-destructively determining the bulk mineralogy of IDPs. Most IDPs fall within three distinct IR groups: (1) olivine-rich particles, (2) pyroxene-rich particles, and (3) phyllosilicate-rich particles. From the IR studies, IDPs dominated by anhydrous minerals tend to be fine grained (CP), while phyllosilicate-rich IDPs are mostly CS. CP IDPs have been linked to cometary sources based on their compositions, spectral properties, and atmospheric entry velocities. Since no spectral signatures of hydrated minerals have been detected in comets, CS IDPs are thought to derive from primitive asteroids. Transmission electron microscopy (TEM) studies have revealed that the mineralogical distinctions between CP and CS IDPs are not always clear. Previous investigators have reported trace amounts of hydrous minerals in dominantly anhydrous particles. A better understanding of these particles will help to elucidate whether there is a genetic relationship between anhydrous and hydrated IDPs, provide insight into the earliest stages of aqueous alteration of primitive materials, and may help to determine whether comets have experienced any aqueous processing. Here we report a combined TEM and isotopic imaging study of an unusual anhydrous IDP with hydrated phases. Additional information is included in the original extended abstract.

  1. An immersed boundary method for two-phase fluids and gels and the swimming of Caenorhabditis elegans through viscoelastic fluids

    NASA Astrophysics Data System (ADS)

    Lee, Pilhwa; Wolgemuth, Charles W.

    2016-01-01

    The swimming of microorganisms typically involves the undulation or rotation of thin, filamentary objects in a fluid or other medium. Swimming in Newtonian fluids has been examined extensively, and only recently have investigations into microorganism swimming through non-Newtonian fluids and gels been explored. The equations that govern these more complex media are often nonlinear and require computational algorithms to study moderate to large amplitude motions of the swimmer. Here, we develop an immersed boundary method for handling fluid-structure interactions in a general two-phase medium, where one phase is a Newtonian fluid and the other phase is viscoelastic (e.g., a polymer melt or network). We use this algorithm to investigate the swimming of an undulating, filamentary swimmer in 2D (i.e., a sheet). A novel aspect of our method is that it allows one to specify how forces produced by the swimmer are distributed between the two phases of the fluid. The algorithm is validated by comparing theoretical predictions for small amplitude swimming in gels and viscoelastic fluids. We show how the swimming velocity depends on material parameters of the fluid and the interaction between the fluid and swimmer. In addition, we simulate the swimming of Caenorhabditis elegans in viscoelastic fluids and find good agreement between the swimming speeds and fluid flows in our simulations and previous experimental measurements. These results suggest that our methodology provides an accurate means for exploring the physics of swimming through non-Newtonian fluids and gels.

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

    USGS Publications Warehouse

    Lee, Myung W.; Waite, William F.

    2008-01-01

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

  3. Heat transfer and multiphase flow with hydrate formation in subsea pipelines

    NASA Astrophysics Data System (ADS)

    Odukoya, A.; Naterer, G. F.

    2015-07-01

    A new predictive model is developed to analyze hydrate formation with coupled heat and mass transfer in a pipe. The model tracks the particle velocity at each time step, while estimating the growth of the hydrate using the change in Biot number and dimensionless time. The numerical results are validated experimental results for R134a hydrates. The effects of change in heat transfer ratio, phase change number, superheating, and pipe diameter on hydrate formation are reported in this paper. The results indicate that higher heat transfer ratio between the internal and external fluids reduces the possibility of hydrates creating a blockage in the pipeline. The pipes with smaller diameters are also found to reduce the possibility of hydrate formation at a constant pipeline pressure. The results show that at temperatures below -10 °C, changing thermophysical properties have limited impact on the rate of hydrate formation in the pipe.

  4. Draft: Modeling Two-Phase Flow in Porous Media Including Fluid-Fluid Interfacial Area

    SciTech Connect

    Crandall, Dustin; Niessner, Jennifer; Hassanizadeh, S Majid

    2008-01-01

    We present a new numerical model for macro-scale twophase flow in porous media which is based on a physically consistent theory of multi-phase flow.The standard approach for modeling the flow of two fluid phases in a porous medium consists of a continuity equation for each phase, an extended form of Darcy’s law as well as constitutive relationships for relative permeability and capillary pressure. This approach is known to have a number of important shortcomings and, in particular, it does not account for the presence and role of fluid - fluid interfaces. An alternative is to use an extended model which is founded on thermodynamic principles and is physically consistent. In addition to the standard equations, the model uses a balance equation for specific interfacial area. The constitutive relationship for capillary pressure involves not only saturation, but also specific interfacial area. We show how parameters can be obtained for the alternative model using experimental data from a new kind of flow cell and present results of a numerical modeling study

  5. Reverse micelle and microemulsion phases in supercritical fluids

    SciTech Connect

    Fulton, J.L.; Smith, R.D.

    1988-05-19

    The surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT) was used to form reverse micelle and microemulsion phases in supercritical ethane and propane for systems consisting of 80-100% alkane by weight. Phase diagrams obtained from view cell studies of microemulsion phases formed in supercritical fluids are reported and shown to be strongly dependent on pressure. The properties of these solutions were also characterized by conductivity, density, and surfactant solubility measurements. The solubility of AOT in ethane and propane over a range of pressures shows behavior typical of solids in supercritical fluids. The maximum water-to-surfactant ratio (W/sub 0/) increased dramatically in both ethane and propane systems as pressure was increased. At 300 bar and 103/sup 0/C, the supercritical propane-surfactant system is capable of solubilizing much more water (W/sub 0/ = 12) than the supercritical ethane-surfactant system (W/sub 0/ = 4) at 300 bar and 37/sup 0/C. Some of the important thermodynamic contributions that are likely responsible for this pressure-dependent phase behavior are discussed, and potential applications of this new class of solvents are considered.

  6. A phase diagram for fluid-driven sediment trasport

    NASA Astrophysics Data System (ADS)

    Clark, Abe

    When a fluid flows laterally over a granular bed, grains may be transported with the flow. This process shapes much of the natural world. The boundary between states with and without grain motion has been studied for decades. However, this boundary is not well understood, since the process whereby grains are transported involves the coupling of several complex phenomena: turbulent fluid flow near a rough boundary, Darcy flow through the pore structure of the granular bed, the yield strength of granular beds comprised of frictional grains with irregular shape, and inertial effects of grains that become entrained in the flow. In order to clarify the essential physics that governs the onset of granular motion, we study this process computationally by including only the minimal features and then adding complexities one by one. We start with a simple numerical model that includes only gravity, grain-grain interactions that are repulsive and frictionless, and a purely horizontal viscous fluid flow. By varying the fluid flow rate and the effective viscosity, we find behavior that is qualitatively consistent with a large collection of experimental data known as the Shields curve. Thus, our results suggest that the main features of this curve result from a competition between grain inertia and viscous damping. We find this phase diagram to be qualitatively insensitive to secondary effects, such as friction, irregular grain shape, and restitution losses. Funded by U.S. Army Research Office under Grant No. W911NF-14-1-0005.

  7. Gas hydrate dissociation in sediments: Pressure-temperature evolution

    NASA Astrophysics Data System (ADS)

    Kwon, Tae-Hyuk; Cho, Gye-Chun; Santamarina, J. Carlos

    2008-03-01

    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. A comprehensive formulation is derived for the prediction of fluid pressure evolution in hydrate-bearing sediments subjected to thermal stimulation without mass transfer. The formulation considers pressure- and temperature-dependent volume changes in all phases, effective stress-controlled sediment compressibility, capillarity, and the relative solubilities of fluids. Salient implications are explored through parametric studies. The model properly reproduces experimental data, including the PT evolution along the phase boundary during dissociation and the effect of capillarity. 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. When the sediment stiffness is high, the generated pore pressure reflects thermal and pressure changes in water, hydrate, and mineral densities. Comparative analyses for CO2 and CH4 highlight the role of gas solubility in excess pore fluid pressure generation. Dissociation in small pores experiences melting point depression due to changes in water activity, and lower pore fluid pressure generation due to the higher gas pressure in small gas bubbles. Capillarity effects may be disregarded in silts and sands, when hydrates are present in nodules and lenses and when the sediment experiences hydraulic fracture.

  8. Microgravity fluid management in two-phase thermal systems

    NASA Technical Reports Server (NTRS)

    Parish, Richard C.

    1987-01-01

    Initial studies have indicated that in comparison to an all liquid single phase system, a two-phase liquid/vapor thermal control system requires significantly lower pumping power, demonstrates more isothermal control characteristics, and allows greater operational flexibility in heat load placement. As a function of JSC's Work Package responsibility for thermal management of space station equipment external to the pressurized modules, prototype development programs were initiated on the Two-Phase Thermal Bus System (TBS) and the Space Erectable Radiator System (SERS). JSC currently has several programs underway to enhance the understanding of two-phase fluid flow characteristics. The objective of one of these programs (sponsored by the Microgravity Science and Applications Division at NASA-Headquarters) is to design, fabricate, and fly a two-phase flow regime mapping experiment in the Shuttle vehicle mid-deck. Another program, sponsored by OAST, involves the testing of a two-phase thermal transport loop aboard the KC-135 reduced gravity aircraft to identify system implications of pressure drop variation as a function of the flow quality and flow regime present in a representative thermal system.

  9. On the theory of phase transitions in magnetic fluids

    SciTech Connect

    Zubarev, A. Yu. Iskakova, L. Yu.

    2007-11-15

    Particles of magnetic fluids (ferrofluids), as is known from experiments, can condense to bulk dense phases at low temperatures (that are close to room temperature) in response to an external magnetic field. It is also known that a uniform external magnetic field increases the threshold temperature of the observed condensation, thus stimulating the condensation process. Within the framework of early theories, this phenomenon is interpreted as a classical gas-liquid phase transition in a system of individual particles involved in a dipole-dipole interaction. However, subsequent investigations have revealed that, before the onset of a bulk phase transition, particles can combine to form a chain cluster or, possibly, a topologically more complex heterogeneous cluster. In an infinitely strong magnetic field, the formation of chains apparently suppresses the onset of a gas-liquid phase transition and the condensation of magnetic particles most likely proceeds according to the scenario of a gas-solid phase transition with a wide gap between spinodal branches. This paper reports on the results of investigations into the specific features of the condensation of particles in the absence of an external magnetic field. An analysis demonstrates that, despite the formation of chains, the condensation of particles in this case can proceed according to the scenario of a gas-liquid phase transition with a critical point in the continuous binodal. Consequently, a uniform magnetic field not only can stimulate the condensation phase transition in a system of magnetic particles but also can be responsible for a qualitative change in the scenario of the phase transition. This inference raises the problem regarding a threshold magnetic field in which there occurs a change in the scenario of the phase transition.

  10. Dynamic Studies of Lung Fluid Clearance with Phase Contrast Imaging

    NASA Astrophysics Data System (ADS)

    Kitchen, Marcus J.; Lewis, Rob A.; Hooper, Stuart B.; Wallace, Megan J.; Siu, Karen K. W.; Williams, Ivan; Irvine, Sarah C.; Morgan, Michael J.; Paganin, David M.; Pavlov, Konstantin; Yagi, Naoto; Uesugi, Kentaro

    2007-01-01

    Clearance of liquid from the airways at birth is a poorly understood process, partly due to the difficulties of observing and measuring the distribution of air within the lung. Imaging dynamic processes within the lung in vivo with high contrast and spatial resolution is therefore a major challenge. However, phase contrast X-ray imaging is able to exploit inhaled air as a contrast agent, rendering the lungs of small animals visible due to the large changes in the refractive index at air/tissue interfaces. In concert with the high spatial resolution afforded by X-ray imaging systems (<100 μm), propagation-based phase contrast imaging is ideal for studying lung development. To this end we have utilized intense, monochromatic synchrotron radiation, together with a fast readout CCD camera, to study fluid clearance from the lungs of rabbit pups at birth. Local rates of fluid clearance have been measured from the dynamic sequences using a single image phase retrieval algorithm.