WorldWideScience

Sample records for clathrates

  1. Methane clathrates in the solar system.

    Science.gov (United States)

    Mousis, Olivier; Chassefière, Eric; Holm, Nils G; Bouquet, Alexis; Waite, Jack Hunter; Geppert, Wolf Dietrich; Picaud, Sylvain; Aikawa, Yuri; Ali-Dib, Mohamad; Charlou, Jean-Luc; Rousselot, Philippe

    2015-04-01

    We review the reservoirs of methane clathrates that may exist in the different bodies of the Solar System. Methane was formed in the interstellar medium prior to having been embedded in the protosolar nebula gas phase. This molecule was subsequently trapped in clathrates that formed from crystalline water ice during the cooling of the disk and incorporated in this form into the building blocks of comets, icy bodies, and giant planets. Methane clathrates may play an important role in the evolution of planetary atmospheres. On Earth, the production of methane in clathrates is essentially biological, and these compounds are mostly found in permafrost regions or in the sediments of continental shelves. On Mars, methane would more likely derive from hydrothermal reactions with olivine-rich material. If they do exist, martian methane clathrates would be stable only at depth in the cryosphere and sporadically release some methane into the atmosphere via mechanisms that remain to be determined. In the case of Titan, most of its methane probably originates from the protosolar nebula, where it would have been trapped in the clathrates agglomerated by the satellite's building blocks. Methane clathrates are still believed to play an important role in the present state of Titan. Their presence is invoked in the satellite's subsurface as a means of replenishing its atmosphere with methane via outgassing episodes. The internal oceans of Enceladus and Europa also provide appropriate thermodynamic conditions that allow formation of methane clathrates. In turn, these clathrates might influence the composition of these liquid reservoirs. Finally, comets and Kuiper Belt Objects might have formed from the agglomeration of clathrates and pure ices in the nebula. The methane observed in comets would then result from the destabilization of clathrate layers in the nuclei concurrent with their approach to perihelion. Thermodynamic equilibrium calculations show that methane-rich clathrate

  2. Methane clathrates in the solar system.

    Science.gov (United States)

    Mousis, Olivier; Chassefière, Eric; Holm, Nils G; Bouquet, Alexis; Waite, Jack Hunter; Geppert, Wolf Dietrich; Picaud, Sylvain; Aikawa, Yuri; Ali-Dib, Mohamad; Charlou, Jean-Luc; Rousselot, Philippe

    2015-04-01

    We review the reservoirs of methane clathrates that may exist in the different bodies of the Solar System. Methane was formed in the interstellar medium prior to having been embedded in the protosolar nebula gas phase. This molecule was subsequently trapped in clathrates that formed from crystalline water ice during the cooling of the disk and incorporated in this form into the building blocks of comets, icy bodies, and giant planets. Methane clathrates may play an important role in the evolution of planetary atmospheres. On Earth, the production of methane in clathrates is essentially biological, and these compounds are mostly found in permafrost regions or in the sediments of continental shelves. On Mars, methane would more likely derive from hydrothermal reactions with olivine-rich material. If they do exist, martian methane clathrates would be stable only at depth in the cryosphere and sporadically release some methane into the atmosphere via mechanisms that remain to be determined. In the case of Titan, most of its methane probably originates from the protosolar nebula, where it would have been trapped in the clathrates agglomerated by the satellite's building blocks. Methane clathrates are still believed to play an important role in the present state of Titan. Their presence is invoked in the satellite's subsurface as a means of replenishing its atmosphere with methane via outgassing episodes. The internal oceans of Enceladus and Europa also provide appropriate thermodynamic conditions that allow formation of methane clathrates. In turn, these clathrates might influence the composition of these liquid reservoirs. Finally, comets and Kuiper Belt Objects might have formed from the agglomeration of clathrates and pure ices in the nebula. The methane observed in comets would then result from the destabilization of clathrate layers in the nuclei concurrent with their approach to perihelion. Thermodynamic equilibrium calculations show that methane-rich clathrate

  3. Methane clathrates in the Solar System

    CERN Document Server

    Mousis, Olivier; Holm, Nils G; Bouquet, Alexis; Waite, Jack Hunter; Geppert, Wolf Dietrich; Picaud, Sylvain; Aikawa, Yuri; Ali-Dib, Mohamad; Charlou, Jean-Luc; Rousselot, Philippe

    2015-01-01

    We review the reservoirs of methane clathrates that may exist in the different bodies of the Solar System. Methane was formed in the interstellar medium prior to having been embedded in the protosolar nebula gas phase. This molecule was subsequently trapped in clathrates that formed from crystalline water ice during the cooling of the disk and incorporated in this form in the building blocks of comets, icy bodies, and giant planets. Methane clathrates may play an important role in the evolution of planetary atmospheres. On Earth, the production of methane in clathrates is essentially biological, and these compounds are mostly found in permafrost regions or in the sediments of continental shelves. On Mars, methane would more likely derive from hydrothermal reactions with olivine-rich material. If they do exist, martian methane clathrates would be stable only at depth in the cryosphere and sporadically release some methane into the atmosphere via mechanisms that remain to be determined.

  4. Earth Abundant Element Type I Clathrate Phases

    Directory of Open Access Journals (Sweden)

    Susan M. Kauzlarich

    2016-08-01

    Full Text Available Earth abundant element clathrate phases are of interest for a number of applications ranging from photovoltaics to thermoelectrics. Silicon-containing type I clathrate is a framework structure with the stoichiometry A8-xSi46 (A = guest atom such as alkali metal that can be tuned by alloying and doping with other elements. The type I clathrate framework can be described as being composed of two types of polyhedral cages made up of tetrahedrally coordinated Si: pentagonal dodecahedra with 20 atoms and tetrakaidecahedra with 24 atoms in the ratio of 2:6. The cation sites, A, are found in the center of each polyhedral cage. This review focuses on the newest discoveries in the group 13-silicon type I clathrate family: A8E8Si38 (A = alkali metal; E = Al, Ga and their properties. Possible approaches to new phases based on earth abundant elements and their potential applications will be discussed.

  5. Thermodynamic modeling for clathrate hydrates of ozone

    International Nuclear Information System (INIS)

    Highlights: • We present a phase-equilibrium model for ozone-containing clathrate hydrates. • We determine intermolecular potential parameters for O3. • There is good agreement between the developed model and the experimental data. • The results show the capability of O3 as a guest substance for clathrate hydrates. • We perform parametric studies for O3 storage capacity with various thermodynamic conditions. -- Abstract: We report a theoretical study to predict the phase-equilibrium properties of ozone-containing clathrate hydrates based on the statistical thermodynamics model developed by van der Waals and Platteeuw. The Patel–Teja–Valderrama equation of state is employed for an accurate estimation of the properties of gas phase ozone. We determined the three parameters of the Kihara intermolecular potential for ozone as a = 6.815 · 10−2 nm, σ = 2.9909 · 10−1 nm, and ε · kB−1 = 184.00 K. An infinite set of ε–σ parameters for ozone were determined, reproducing the experimental phase equilibrium pressure–temperature data of the (O3 + O2 + CO2) clathrate hydrate. A unique parameter pair was chosen based on the experimental ozone storage capacity data for the (O3 + O2 + CCl4) hydrate that we reported previously. The prediction with the developed model showed good agreement with the experimental phase equilibrium data within ±2% of the average deviation of the pressure. The Kihara parameters of ozone showed slightly better suitability for the structure-I hydrate than CO2, which was used as a help guest. Our model suggests the possibility of increasing the ozone storage capacity of clathrate hydrates (∼7% on a mass basis) from the previously reported experimental capacity (∼1%)

  6. Clathrate hydrate tuning for technological purposes

    Science.gov (United States)

    di Profio, Pietro; Germani, Raimondo; Savelli, Gianfranco

    2010-05-01

    Gas hydrates are being increasingly considered as convenient media for gas storage and transportation as the knowledge of their properties increases, in particular as relates to methane and hydrogen. Clathrate hydrates may also represent a feasible sequestration technology for carbon dioxide, due to a well defined P/T range of stability, and several research programs are addressing this possibility. Though the understanding of the molecular structure and supramolecular interactions which are responsible of most properties of hydrates have been elucitated in recent years, the underlying theoretical physico-chemical framework is still poor, especially as relates to the role of "conditioners" (inhibitors and promoters) from the molecular/supramolecular point of view. In the present communication we show some results from our research approach which is mainly focused on the supramolecular properties of clathrate hydrate systems - and their conditioners - as a way to get access to a controlled modulation of the formation, dissociation and stabilization of gas hydrates. In particular, this communication will deal with: (a) a novel, compact apparatus for studying the main parameters of formation and dissociation of gas hydrates in a one-pot experiment, which can be easily and rapidly carried out on board of a drilling ship;[1] (b) the effects of amphiphile molecules (surfactants) as inhibitors or promoters of gas hydrate formation;[2] (c) a novel nanotechnology for a reliable and quick production of hydrogen hydrates, and its application to fuel cells;[3,4] and (d) the development of a clathrate hydrate tecnology for the sequestration and geological storage of man-made CO2, possibly with concomitant recovery of natural gas from NG hydrate fields. Furthermore, the feasibility of catalyzing the reduction of carbon dioxide to energy-rich species by hydrates is being investigated. [1] Di Profio, P., Germani, R., Savelli, G., International Patent Application PCT/IT2006

  7. Volatile inventories in clathrate hydrates formed in the primordial nebula

    CERN Document Server

    Mousis, O; Picaud, S; Cordier, D

    2010-01-01

    Examination of ambient thermodynamic conditions suggest that clathrate hydrates could exist in the martian permafrost, on the surface and in the interior of Titan, as well as in other icy satellites. Clathrate hydrates probably formed in a significant fraction of planetesimals in the solar system. Thus, these crystalline solids may have been accreted in comets, in the forming giant planets and in their surrounding satellite systems. In this work, we use a statistical thermodynamic model to investigate the composition of clathrate hydrates that may have formed in the primordial nebula. In our approach, we consider the formation sequence of the different ices occurring during the cooling of the nebula, a reasonable idealization of the process by which volatiles are trapped in planetesimals. We then determine the fractional occupancies of guests in each clathrate hydrate formed at given temperature. The major ingredient of our model is the description of the guest-clathrate hydrate interaction by a spherically a...

  8. Investigating the Metastability of Clathrate Hydrates for Energy Storage

    Energy Technology Data Exchange (ETDEWEB)

    Koh, Carolyn Ann [Colorado School of Mines

    2014-11-18

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

  9. Stability and metastability of bromine clathrate polymorphs.

    Science.gov (United States)

    Nguyen, Andrew H; Molinero, Valeria

    2013-05-23

    Clathrate hydrates are crystals in which water forms a network of fully hydrogen-bonded polyhedral cages that contain small guests. Clathrate hydrates occur mostly in two cubic crystal polymorphs, sI and sII. Bromine is one of two guests that yield a hydrate with the tetragonal structure (TS), the topological dual of the Frank-Kasper σ phase. There has been a long-standing disagreement on whether bromine hydrate also forms metastable sI and sII crystals. To date there are no data on the thermodynamic range of stability (e.g., the melting temperatures) of the metastable polymorphs. Here we use molecular dynamics simulations with the coarse-grained model of water mW to (i) investigate the thermodynamic stability of the empty and guest-filled the sI, sII, TS, and HS-I hydrate polymorphs, (ii) develop a coarse-grained model of bromine compatible with mW water, and (iii) evaluate the stability of the bromine hydrate polymorphs. The mW model predicts the same relative energy of the empty clathrate polymorphs and the same phase diagram as a function of water-guest interaction than the fully atomistic TIP4P water model. There is a narrow region in water-guest parameter space for which TS is marginally more stable than sI or sII. We parametrize a coarse-grained model of bromine compatible with mW water and use it to determine the order of stability of the bromine hydrate polymorphs. The melting temperatures of the bromine hydrate polymorphs predicted by the coarse-grained model are 281 ± 1 K for TS, 279 ± 1 K for sII, and 276 ± 1 K for sI. The closeness of the melting temperatures supports the plausibility of formation of metastable sII and sI bromine hydrates.

  10. Practical reactor production of {sup 41}Ar from argon clathrate

    Energy Technology Data Exchange (ETDEWEB)

    Mercer, J.R. E-mail: jmercer@pharmacy.ualberta.ca; Duke, M.J.M.; McQuarrie, S.A

    2000-06-01

    The radionuclide {sup 41}Ar has many ideal properties as a gas flow tracer. However, the modest cross-section of {sup 40}Ar for thermal neutron activation makes preparation of suitable activities of {sup 41}Ar technically difficult particularly for low flux reactors. Argon can however be trapped in a molecular complex called a clathrate that can then be irradiated. We prepared argon clathrate and explored its irradiation and stability characteristics. Argon clathrate can be used to provide gigabecquerel quantities of {sup 41}Ar even with low power reactors.

  11. Equilibrium composition between liquid and clathrate reservoirs on Titan

    CERN Document Server

    Mousis, Olivier; Lunine, Jonathan I; Sotin, Christophe

    2015-01-01

    Hundreds of lakes and a few seas of liquid hydrocarbons have been observed by the Cassini spacecraft to cover the polar regions of Titan. A significant fraction of these lakes or seas could possibly be interconnected with subsurface liquid reservoirs of alkanes. In this paper, we investigate the interplay that would happen between a reservoir of liquid hydrocarbons located in Titan's subsurface and a hypothetical clathrate reservoir that progressively forms if the liquid mixture diffuses throughout a preexisting porous icy layer. To do so, we use a statistical-thermodynamic model in order to compute the composition of the clathrate reservoir that forms as a result of the progressive entrapping of the liquid mixture. This study shows that clathrate formation strongly fractionates the molecules between the liquid and the solid phases. Depending on whether the structure I or structure II clathrate forms, the present model predicts that the liquid reservoirs would be mainly composed of either propane or ethane, r...

  12. Crystal structure of clathrates of Hofmann dma-type

    International Nuclear Information System (INIS)

    Seven new clathrates Cd(DMA)2Ni(CN)4·xG (x=1, G=aniline, 2,3-xylidine, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,5-xylidine, and x=2, G=2,4,6-trimethylaniline) of Hofmann type are synthesized by amine substitution for dimethylamine (DMA). On the base of x-ray diffraction data it is shown that geometry of guest molecule in cage-like hollow determines the structure of the host and crystal structure of clathrates. Two-dimension metallocomplex of the host of studied clathrates is characterized by elastic folded structure appearing as a result of angular deformation of bond between Cd atoms and host cyanide bridge. Guest molecule orientation is fixed by hydrogen bond. Structural elasticity of the host complex directs to differences in crystal structure of clathrates formed and to considerable variety of incorporated guests

  13. Propane Clathrate Hydrate Formation Accelerated by Methanol.

    Science.gov (United States)

    Amtawong, Jaruwan; Guo, Jin; Hale, Jared S; Sengupta, Suvrajit; Fleischer, Everly B; Martin, Rachel W; Janda, Kenneth C

    2016-07-01

    The role of methanol as both an inhibitor and a catalyst for the formation of clathrate hydrates (CHs) has been a topic of intense study. We report a new quantitative study of the kinetics of propane CH formation at 253 K from the reaction of propane gas with ice particles that have been doped with varying amounts of methanol. We find that methanol significantly accelerates the formation reaction with quite small doping quantities. Even for only 1 methanol molecule per 10 000 water molecules, the maximum uptake rate of propane into CHs is enhanced and the initiation pressure is reduced. These results enable more efficient production of CHs for gas storage. This remarkable acceleration of the CH formation reaction by small quantities of methanol may place constraints on the mechanism of the inhibition effect observed under other conditions, usually employing much larger quantities of methanol. PMID:27275862

  14. Regimes of Decomposition of Clathrate in Natural Strata Purged by Methane

    Science.gov (United States)

    Khasanov, M.; Shagapov, V.

    2016-06-01

    The process of decomposition of a methane clathrate in a finite-length stratum initially saturated with methane clathrate and methane, which is purged by warm methane, is studied. The influence of the initial parameters of the stratum and purging conditions on the evolution of methane clathrate temperature and saturation is examined. The existence of solutions is demonstrated, which predict methane clathrate decomposition both on the frontal surface and in the volume zone.

  15. Kinetics of Methane Clathrate Formation in the Presolar Nebula

    Science.gov (United States)

    Vu, Tuan; Choukroun, Mathieu

    2016-10-01

    Clathrate hydrates are a distinct form of water ice wherein the crystal lattice of the host water molecules forms symmetric, polyhedral cages that trap volatile guest species under appropriate pressures and temperatures. These materials are an abundant source of hydrocarbons on Earth, and have been expected to be present on a number of icy celestial bodies, including Mars, Europa, Titan, and Enceladus. Clathrates are also thought to be one of the most likely traps for volatiles during the condensation of the protostellar nebulae. Prior to the Voyager mission, the prevailing expectation was that the elemental composition of the giant planets would reflect the composition of the solar nebula and therefore be similar to solar abundances. However, spacecraft observations by Voyager, Galileo, and Cassini-Huygens, as well as ground-based observations, have revealed unexpected elemental enrichment, relative to solar abundances, of C, N, S, As, P, and noble gases in the giant planets and in comets. One of the contending explanations is the retention of these volatiles as clathrate hydrates, which may have enabled their capture early in the history of the Solar System.While the formation and stability of clathrates have been addressed theoretically and, to some extent, experimentally at relatively high pressures (10-7–10-3 bar), there is a scarcity of experimental undertaking on the kinetics of clathrate formation and their stability at the low pressures relevant to the early outer solar nebula (~10-11 bar). This study seeks to elucidate the clathrate formation kinetics under nebula-relevant conditions via a series of optical Raman experiments on ice/gas mixtures over a range of pressures and temperatures. Our work on the methane gas/ice system shows that clathrate formation occurs on a rather fast timescale (typically within minutes at 223-253 K and 30-50 bar CH4). In addition, the rate of enclathration increases with pressures and temperatures, and the activation energy

  16. Nanostructured clathrate phonon glasses: beyond the rattling concept.

    Science.gov (United States)

    He, Yuping; Galli, Giulia

    2014-05-14

    Using first-principles calculations, we investigated the thermoelectric properties of a newly synthesized Si-based ternary clathrate K8Al8Si38, composed of ∼1 nm hollow cages with a metal atom inside. This compound contains solely Earth abundant elements. We found that, similar to other nanostructured type I clathrates, this system is a semiconductor and has a low thermal conductivity (∼1 W/mK). It was long believed that the mere presence of rattling centers was responsible for the low lattice thermal conductivity of type I clathrates. We found instead that the cage structural disorder induced by atomic substitution plays a crucial role in determining the conductivity of these materials, in addition to the dynamics of the guest atoms. Our calculations showed that the latter is substantially affected by the charge transfer between the metal and the cages. Our results provide design rules for the search of new types of promising nanocage structured thermoelectric materials.

  17. Oxygen-18 enrichment in the water of a clathrate hydrate

    Energy Technology Data Exchange (ETDEWEB)

    Davidson, D.W.; Leaist, D.G. (National Research Council of Canada, Ottawa, Ontario. Div. of Chemistry); Hesse, R. (McGill Univ., Montreal, Quebec (Canada). Dept of Geological Sciences)

    1983-12-01

    The equilibrium constants for the fractionation of H/sub 2//sup 18/O and H/sub 2//sup 16/O between liquid and solid phases were determined by slow freezing of ice and by slow formation of the clathrate hydrate of tetrahydrofuran from liquid solution. Both systems gave ..cap alpha.. = 1.0026/sub 8/. It is likely that oxygen-18 enrichment of the water in clathrate hydrates generally is essentially the same as for ice and that the relatively high oxygen-18 content observed in pore waters from some deep-sea sediments arises from the recent presence of methane hydrate.

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

    Science.gov (United States)

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

    2009-07-14

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Simmons, Blake Alexander; Bradshaw, Robert W.; Dedrick, Daniel E.; Cygan, Randall Timothy (Sandia National Laboratories, Albuquerque, NM); Greathouse, Jeffery A. (Sandia National Laboratories, Albuquerque, NM); Majzoub, Eric H. (University of Missouri, Columbia, MO)

    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

  20. Identification of Clathrate Hydrates, Hexagonal Ice, Cubic Ice, and Liquid Water in Simulations: the CHILL+ Algorithm.

    Science.gov (United States)

    Nguyen, Andrew H; Molinero, Valeria

    2015-07-23

    Clathrate hydrates and ice I are the most abundant crystals of water. The study of their nucleation, growth, and decomposition using molecular simulations requires an accurate and efficient algorithm that distinguishes water molecules that belong to each of these crystals and the liquid phase. Existing algorithms identify ice or clathrates, but not both. This poses a challenge for cases in which ice and hydrate coexist, such as in the synthesis of clathrates from ice and the formation of ice from clathrates during self-preservation of methane hydrates. Here we present an efficient algorithm for the identification of clathrate hydrates, hexagonal ice, cubic ice, and liquid water in molecular simulations. CHILL+ uses the number of staggered and eclipsed water-water bonds to identify water molecules in cubic ice, hexagonal ice, and clathrate hydrate. CHILL+ is an extension of CHILL (Moore et al. Phys. Chem. Chem. Phys. 2010, 12, 4124-4134), which identifies hexagonal and cubic ice but not clathrates. In addition to the identification of hydrates, CHILL+ significantly improves the detection of hexagonal ice up to its melting point. We validate the use of CHILL+ for the identification of stacking faults in ice and the nucleation and growth of clathrate hydrates. To our knowledge, this is the first algorithm that allows for the simultaneous identification of ice and clathrate hydrates, and it does so in a way that is competitive with respect to existing methods used to identify any of these crystals. PMID:25389702

  1. The chemistry of low dosage clathrate hydrate inhibitors.

    OpenAIRE

    Perrin, A.; Musa, O. M.; STEED, J. W.

    2013-01-01

    This review aims to introduce the chemistry of low dosage inhibitors of clathrate hydrate formation within the context of their role in the oil and gas industry. The review covers both kinetic hydrate inhibitors and anti-agglomerants from the point of view of structure–function relationships, focussing on recent refinements in mechanistic understanding and chemical design, and the consequently evolving and increasingly fine-tuned properties of these fascinating compounds.

  2. Nanostructured clathrate phonon glasses: beyond the rattling concept.

    Science.gov (United States)

    He, Yuping; Galli, Giulia

    2014-05-14

    Using first-principles calculations, we investigated the thermoelectric properties of a newly synthesized Si-based ternary clathrate K8Al8Si38, composed of ∼1 nm hollow cages with a metal atom inside. This compound contains solely Earth abundant elements. We found that, similar to other nanostructured type I clathrates, this system is a semiconductor and has a low thermal conductivity (∼1 W/mK). It was long believed that the mere presence of rattling centers was responsible for the low lattice thermal conductivity of type I clathrates. We found instead that the cage structural disorder induced by atomic substitution plays a crucial role in determining the conductivity of these materials, in addition to the dynamics of the guest atoms. Our calculations showed that the latter is substantially affected by the charge transfer between the metal and the cages. Our results provide design rules for the search of new types of promising nanocage structured thermoelectric materials. PMID:24762084

  3. Physical modeling of the formation of clathrate hydrates of methane

    Science.gov (United States)

    Drobyshev, A.; Aldiyarov, A.; Kurnosov, V.; Katpaeva, K.; Korshikov, E.; Sokolov, D.; Shinbayeva, A.; Timchenko, A.

    2015-06-01

    Nowadays natural gas hydrates attract special attention as a possible source of fossil fuel. According to various estimates, the reserves of hydrocarbons in hydrates exceed considerably explored reserves of natural gas. Due to the clathrate structure the unit volume of the gas hydrate can contain up to 160-180 volumes of pure gas. In recent years interest to a problem of gas hydrates has considerably increased. Such changes are connected with the progress in searches of the alternative sources of hydrocarbonic raw materials in countries that do not possess the resources of energy carriers. Thus gas hydrates are nonconventional sources of the hydrocarbonic raw materials which can be developed in the near future. At the same time, mechanisms of methane clathrate hydrates formations have not reached an advanced level, their thermophysical and mechanical properties have not been investigated profoundly. Thereby our experimental modeling of the processes of formation of methane clathrate hydrates in water cryomatrix prepared by co-condensation from the gas phase onto a cooled substrate was carried out over the range of condensation temperatures 12-60 K and pressures 10-4-10-6 Torr. In our experiments the concentration of methane in water varied in the range of 5%-90%. The thickness deposited films was 30-60 μm. The vibrational spectra of two-component thin films of CH4 + H2O condensates were measured and analyzed.

  4. Vibrational spectroscopic and quantum theoretical study of host-guest interactions in clathrates: I. Hofmann type clathrates

    Directory of Open Access Journals (Sweden)

    VLADIMIR M. PETRUSEVSKI

    2000-06-01

    Full Text Available Hofmann type clatharates are host-guest compounds with the general formula M(NH32M'(CN4·2G, in which M(NH32M'(CN4 is the host lattice and G is benzene, the guest molecule. In previous studies, host-guest interactions have been investigated by analyzing the RT and LNT vibrational (infrared, far infrared and Raman spectra of these clathrates. All the observed changes in the vibrational spectra of these clathrates are referred to a host-guest interaction originating from weak hydrogen bonding between the ammonia hydrogen atoms from the host lattice and the p electron cloud of the guest (benzene molecules. In order to obtain an insight into the relative importance of the local crystalline field vs. the anharmonicity effects on the spectroscopic properties of the guest species upon enclathration, as well as to explain the observed band shifts and splittings, several quantum theoretical approaches are proposed.

  5. Paraffin molecule mobility in channel clathrates of urea on spectroscopic NMR relaxation data

    CERN Document Server

    Kriger, Y G; Chekhova, G N

    2001-01-01

    The temperature dependences of the protons spin-lattice relaxation time (T sub I) in the channel clathrates of urea with paraffins are measured. The data on the T sub I are interpreted within the frames of the model of the paraffins molecules and their fragments orientation in the clathrate channels. The dynamics peculiarities are connected with the disproportion effects of these compounds

  6. Phase Behaviour and Structural Aspects of Ternary Clathrate Hydrate Systems. The Role of Additives

    NARCIS (Netherlands)

    Mooijer-Van den Heuvel, M.M.

    2004-01-01

    In this study an experimental and modelling approach is applied to obtain fundamental insight into the phase behaviour of ternary systems, in which clathrate hydrates are formed. Proper interpretation of the phase behaviour requires knowledge on the clathrate hydrate structure in these systems, whic

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

    Science.gov (United States)

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

    1985-01-01

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

  8. Micro-Tomographic Investigation of Ice and Clathrate Formation and Decomposition under Thermodynamic Monitoring

    Directory of Open Access Journals (Sweden)

    Stefan Arzbacher

    2016-08-01

    Full Text Available Clathrate hydrates are inclusion compounds in which guest molecules are trapped in a host lattice formed by water molecules. They are considered an interesting option for future energy supply and storage technologies. In the current paper, time lapse 3D micro computed tomographic (µCT imaging with ice and tetrahydrofuran (THF clathrate hydrate particles is carried out in conjunction with an accurate temperature control and pressure monitoring. µCT imaging reveals similar behavior of the ice and the THF clathrate hydrate at low temperatures while at higher temperatures (3 K below the melting point, significant differences can be observed. Strong indications for micropores are found in the ice as well as the THF clathrate hydrate. They are stable in the ice while unstable in the clathrate hydrate at temperatures slightly below the melting point. Significant transformations in surface and bulk structure can be observed within the full temperature range investigated in both the ice and the THF clathrate hydrate. Additionally, our results point towards an uptake of molecular nitrogen in the THF clathrate hydrate at ambient pressures and temperatures from 230 K to 271 K.

  9. Geochemistry of clathrate-derived methane in Arctic Ocean waters

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-03-15

    Alterations to the composition of seawater are estimated for microbial oxidation of methane from large polar clathrate destabilizations, which may arise in the coming century. Gas fluxes are taken from porous flow models of warming Arctic sediment. Plume spread parameters are then used to bracket the volume of dilution. Consumption stoichiometries for the marine methanotrophs are based on growth efficiency and elemental/enzyme composition data. The nutritional demand implied by extra CH{sub 4} removal is compared with supply in various high latitude water masses. For emissions sized to fit the shelf break, reaction potential begins at one hundred micromolar and falls to order ten a thousand kilometers downstream. Oxygen loss and carbon dioxide production are sufficient respectively to hypoxify and acidify poorly ventilated basins. Nitrogen and the monooxygenase transition metals may be depleted in some locations as well. Deprivation is implied relative to existing ecosystems, along with dispersal of the excess dissolved gas. Physical uncertainties are inherent in the clathrate abundance, patch size, outflow buoyancy and mixing rate. Microbial ecology is even less defined but may involve nutrient recycling and anaerobic oxidizers.

  10. Synthesis and electrochemical characterization of Silicon clathrates as anode materials for Lithium ion batteries

    Science.gov (United States)

    Raghavan, Rahul

    Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown

  11. Removal of Titan's Atmospheric Noble Gases by their Sequestration in Surface Clathrates

    CERN Document Server

    Mousis, Olivier; Picaud, Sylvain; Cordier, Daniel; Waite, J Hunter; Jr.,; Mandt, Kathleen E

    2011-01-01

    A striking feature of the atmosphere of Titan is that no heavy noble gases other than argon were detected by the Gas Chromatograph Mass Spectrometer (GCMS) aboard the Huygens probe during its descent to Titan's surface in January 2005. Here we provide an explanation of the mysterious absence or rarity of these noble gases in Titan's atmosphere: the thermodynamic conditions prevailing at the surface-atmosphere interface of the satellite allow the formation of multiple guest clathrates that preferentially store some species, including all heavy noble gases, over others. The clean water ice needed for formation of these clathrates could be delivered by successive episodes of cryovolcanic lavas that have been hypothesized to regularly cover the surface of Titan. The formation of clathrates in the porous lavas and their propensity for trapping Ar, Kr and Xe would progressively remove these species from the atmosphere of Titan over its history. In some circumstances, a global clathrate crust with an average thickne...

  12. Preservation of carbon dioxide clathrate hydrate in the presence of trehalose under freezer conditions

    Science.gov (United States)

    Nagashima, Hironori D.; Takeya, Satoshi; Uchida, Tsutomu; Ohmura, Ryo

    2016-01-01

    To investigate the preservation of CO2 clathrate hydrate in the presence of sugar for the novel frozen dessert, mass fractions of CO2 clathrate hydrate in CO2 clathrate hydrate samples coexisting with trehalose were intermittently measured. The samples were prepared from trehalose aqueous solution with trehalose mass fractions of 0.05 and 0.10 at 3.0 MPa and 276.2 K. The samples having particle sizes of 1.0 mm and 5.6-8.0 mm were stored at 243.2 K and 253.2 K for three weeks under atmospheric pressure. The mass fractions of CO2 clathrate hydrate in the samples were 0.87-0.97 before the preservation, and CO2 clathrate hydrate still remained 0.56-0.76 in the mass fractions for 5.6-8.0 mm samples and 0.37-0.55 for 1.0 mm samples after the preservation. The preservation in the trehalose system was better than in the sucrose system and comparable to that in the pure CO2 clathrate hydrate system. This comparison indicates that trehalose is a more suitable sugar for the novel frozen carbonated dessert using CO2 clathrate hydrate than sucrose in terms of CO2 concentration in the dessert. It is inferred that existence of aqueous solution in the samples is a significant factor of the preservation of CO2 clathrate hydrate in the presence of sugar.

  13. Van't Hoff law for temperature dependent Langmuir constants in clathrate hydrate nanocavities

    OpenAIRE

    Lakhlifi, Azzedine; Dahoo, Pierre-Richard

    2015-01-01

    This work gives a van't Hoff law expression of Langmuir constants of different species for determining their occupancy in the nanocavities of clathrate hydrates. The van't Hoff law's parameters are derived from a fit with Langmuir constants calculated using a pairwise site-site interaction potential to model the anisotropic potential environment in the cavities, as a function of temperature. The parameters can be used for calculating clathrates compositions. Results are given for nineteen gas...

  14. A new class of low compressibility materials: Clathrates of silicon and related materials

    OpenAIRE

    San Miguel, Alfonso; Mélinon, Patrice; Blase, Xavier; Tournus, Florent; Connétable, Damien; Reny, Édouard; Yamanaka, Shoji; Itié, Jean-Paul; Cros, Christian; Pouchard, Michel

    2002-01-01

    We discuss the high pressure properties of different silicon clathrate structures that we have investigated by means of X-ray diffraction and ab initio calculations. Compressibility transition pressures or phase transformations are interpreted as a function of the nature of the guest atom intercalation, The compressibility of the clathrate structure is in all cases close to that of silicon diamond whereas transition pressures or the high pressure phases are extremely depending on the nature o...

  15. Revisiting the thermodynamic modelling of type I gas-hydroquinone clathrates.

    Science.gov (United States)

    Conde, M M; Torré, J P; Miqueu, C

    2016-04-21

    Under specific pressure and temperature conditions, certain gaseous species can be engaged in a host lattice of hydroquinone molecules, forming a supramolecular entity called a gas hydroquinone clathrate. This study is devoted to the thermodynamic modelling of type I hydroquinone clathrates. The gases considered in this work are argon, krypton, xenon, methane, nitrogen, oxygen and hydrogen sulphide. The basic van der Waals and Platteeuw model, which is, for example, not able to predict well the phase equilibrium properties of such clathrates at high temperature, is modified and extended by considering first the solubility of the guest in solid HQ and then the mutual interactions between the gaseous molecules inside the clathrate structure (i.e. guest-guest interactions). Other improvements of the basic theory, such as the choice of the reference state, are proposed, and a unique set of thermodynamic parameters valid for all the studied guests are finally calculated. Very good agreement is obtained between the model predictions and the experimental data available in the literature. Our results clearly demonstrate that the highest level of theory is necessary to describe well both the triphasic equilibrium line (where the HQ clathrate, the native hydroquinone HQα and the gas coexist), the occupancy of the guest in the clathrate, and the intercalation enthalpy.

  16. Tropospheric impact of methane emissions from clathrates in the Arctic Region

    Directory of Open Access Journals (Sweden)

    S. Bhattacharyya

    2012-10-01

    Full Text Available A highly potent greenhouse gas, methane, is locked in the solid phase as ice-like deposits containing a mixture of water and gas (mostly methane called clathrates in both ocean sediments and underneath permafrost regions. Clathrates are stable under high pressures and low temperatures. In a warming climate, increases in ocean temperatures could lead to dissociation of the clathrates and release methane into the ocean and subsequently the atmosphere. This is of particular importance in the shallow parts of the Arctic Ocean, since clathrates are expected to start outgassing abruptly at depths of around 300 m. In this paper, we present a comparison of simulations from the Community Earth System Model (CESM1 for present-day conditions with and without additional methane emissions from a plausible clathrate release scenario based on a state-of-the-art ocean sediment model. The CESM model includes a fully interactive physical ocean and we added a fast atmospheric chemistry mechanism that represents methane as a fully interactive tracer (with emissions rather than concentration boundary conditions along with the main chemical reactions for methane, ozone, and nitrous oxide. The results show that such Arctic clathrate emissions increase methane concentrations non-uniformly, and that increases in surface ozone concentrations are greatest in polluted regions. We also find that the interannual variability in surface methane and ozone increases.

  17. Dynamic free energy surfaces for sodium diffusion in type II silicon clathrates.

    Science.gov (United States)

    Slingsby, J G; Rorrer, N A; Krishna, L; Toberer, E S; Koh, C A; Maupin, C M

    2016-02-21

    Earth abundant semiconducting type II Si clathrates have attracted attention as photovoltaic materials due to their wide band gaps. To realize the semiconducting properties of these materials, guest species that arise during the synthesis process must be completely evacuated from the host cage structure post synthesis. A common guest species utilized in the synthesis of Si clathrates is Na (metal), which templates the clathrate cage formation. Previous experimental investigations have identified that it is possible to evacuate Na from type II clathrates to an occupancy of less than 1 Na per unit cell. This work investigates the energetics, kinetics, and resulting mechanism of Na diffusion through type II Si clathrates by means of biased molecular dynamics and kinetic Monte Carlo simulations. Well-tempered metadynamics has been used to determine the potential of mean force for Na moving between clathrate cages, from which the thermodynamic preferences and transition barrier heights have been obtained. Kinetic Monte Carlo simulations based on the metadynamics results have identified the mechanism of Na diffusion in type II Si clathrates. The overall mechanism consists of a coupled diffusive process linked via electrostatic guest-guest interactions. The large occupied hexakaidechedral cages initially empty their Na guests to adjacent empty large cages, thereby changing the local electrostatic environment around the occupied small pentagonal dodecahedral cages and increasing the probability of Na guests to leave the small cages. This coupled process continues through the cross-over point that is identified as the point where large and small cages are equally occupied by Na guests. Further Na removal results in the majority of guests residing in the large cages as opposed to the small cages, in agreement with experiments, and ultimately a Na free structure. PMID:26658349

  18. First-Principles Study of Electronic Structure of Type I Hybrid Carbon-Silicon Clathrates

    Science.gov (United States)

    Chan, Kwai S.; Peng, Xihong

    2016-08-01

    A new class of type I hybrid carbon-silicon clathrates has been designed using computational methods by substituting some of the Si atoms in the silicon clathrate framework with carbon atoms. In this work, the electronic structure of hybrid carbon-silicon clathrates with and without alkaline or alkaline-earth metal guest atoms has been computed within the density functional theory framework. The theoretical calculations indicate that a small number of carbon substitutions in the Si46 framework slightly reduces the density of states (DOS) near the band edge and narrows the bandgap of carbon-silicon clathrates. Weak hybridization of the conduction band occurs when alkaline metal (Li, Na, K) atoms are inserted into the structure, while strong hybridization of the conduction band occurs when alkaline-earth metal (Mg, Ca, Ba) atoms are inserted into the hybrid structure. Empty C y Si46- y clathrates within the composition range of 2 ≤ y ≤ 15 can be tuned to exhibit indirect bandgaps of 1.5 eV or less, and may be considered as potential electronic materials.

  19. Formation, properties, and function of vacancies in Si/Ge Clathrates: The importance of broken symmetries

    Science.gov (United States)

    Bhattacharya, Amrita; Carbogno, Christian; Scheffler, Matthias

    Inclusion compounds, such as clathrates, are cage-like crystal structures that can encapsulate guest atoms. Since this allows to tune their electronic and vibrational properties, they are regarded as interesting materials for thermoelectric applications. Progress in this field is, however, hindered by the fact that filling of group-IV clathrates often results in complex and unexpected structural changes, e.g., the spontaneous formation of vacancies in certain hosts: In Ge46 clathrates filled with K or Ba, the most favourable phases K8Ge44/ Ba8Ge43 feature two/three vacancies. Conversely, the framework of the isoelectronic Si46 clathrate remains intact (K8Si46/Ba8Si46) upon filling with the exact same guests. Our first-principles calculations of the formation energies and of the thermodynamic phase stabilities confirm this experimental scenario and shed light on the underlying mechanisms. Due to the spatially more delocalized 4sp3 orbitals in Ge compared to the more localized 3sp3 orbitals in Si, fundamentally different symmetry breaking distortions become possible to stabilize the vacancies. Eventually, we discuss the implications of these findings for the thermoelectric properties of clathrates.

  20. Hydration of Krypton and Consideration of Clathrate Models of Hydrophobic Effects from the Perspective of Quasi-Chemical Theory

    CERN Document Server

    Ashbaugh, H S; Pratt, L R; Rempe, S B; Ashbaugh, Henry S.; Pratt, Lawrence R.; Rempe, Susan B.

    2002-01-01

    AIMD results on a liquid krypton-water system are compared to recent XAFS results for the radial hydration structure for a Kr atom in liquid water solution. The comparisons with the liquid solution results are satisfactory and significantly different from the radial distributions extracted from the data on the solid clathrate hydrate phase. The calculations also produce the coordination number distribution that can be examined for metastable coordination structures suggesting possibilities for clathrate-like organization; none are seen in these results. Clathrate pictures of hydrophobic hydration are discussed, as is the quasi-chemical theory that should provide a basis for clathrate pictures. Outer shell contributions are discussed and accurately estimated; they are positive and larger than the positive experimental hydration free energy of Kr(aq), implying that inner shell contributions must be negative. Clathrate-like inner shell coordination structures extracted from the simulation of the liquid, and then...

  1. Monte Carlo calculations of the free energy of binary sII hydrogen clathrate hydrates for identifying efficient promoter molecules.

    Science.gov (United States)

    Atamas, Alexander A; Cuppen, Herma M; Koudriachova, Marina V; de Leeuw, Simon W

    2013-01-31

    The thermodynamics of binary sII hydrogen clathrates with secondary guest molecules is studied with Monte Carlo simulations. The small cages of the sII unit cell are occupied by one H(2) guest molecule. Different promoter molecules entrapped in the large cages are considered. Simulations are conducted at a pressure of 1000 atm in a temperature range of 233-293 K. To determine the stabilizing effect of different promoter molecules on the clathrate, the Gibbs free energy of fully and partially occupied sII hydrogen clathrates are calculated. Our aim is to predict what would be an efficient promoter molecule using properties such as size, dipole moment, and hydrogen bonding capability. The gas clathrate configurational and free energies are compared. The entropy makes a considerable contribution to the free energy and should be taken into account in determining stability conditions of binary sII hydrogen clathrates.

  2. Effects of nocloprost clathrate on absorption of acetylsalicylic acid.

    Science.gov (United States)

    Siegmund, W; Zschiesche, M; Franke, G; Amon, I

    1994-01-01

    The cytoprotective prostaglandin E2 analog nocloprost clathrate (NOCLO) is tested as a prophylactic for gastrointestinal lesions of NSAID. The effects of 400 micrograms NOCLO versus respective placebos with and without equivalent amounts of beta-cyclodextrin on the pharmacokinetic behavior of acetylsalicylic acid (ASA), given 30 min after NOCLO, were studied in two single-blind, parallel-group trials. The trials were performed in 15 male healthy volunteers (age 21-25 years, body weight 62-94 kg, body height 172-187 cm) with known N-acetylation and debrisoquine type hydroxylation phenotype. ASA, salicylic acid (SA), and salicyluric acid (SU) in plasma and SA and SU in urine were measured by HPLC. NOCLO delayed the absorption of ASA (increased tmax, lower Cmax) significantly in comparison with both placebos. AUC and clearance values were not changed by NOCLO premedication. There were neither differences between the two placebo groups nor between the two groups pretreated with NOCLO with regard to any pharmacokinetic parameter. The changes in drug absorption are caused by the sum of those cytoprotective effects of prostaglandin which are also determinants of drug absorption. PMID:8199752

  3. Interpreting Temperature Strain Data from Meso-Scale Clathrate Experiments

    Energy Technology Data Exchange (ETDEWEB)

    Leeman, John R [ORNL; Rawn, Claudia J [ORNL; Ulrich, Shannon M [ORNL; Elwood Madden, Megan [University of Oklahoma, Norman; Phelps, Tommy Joe [ORNL

    2012-01-01

    Gas hydrates are important in global climate change, carbon sequestra- tion, and seafloor stability. Currently, formation and dissociation pathways are poorly defined. We present a new approach for processing large amounts of data from meso-scale experiments, such as the LUNA distributed sensing system (DSS) in the seafloor process simulator (SPS) at Oak Ridge National Laboratory. The DSS provides a proxy for temperature measurement with a high spatial resolution allowing the heat of reaction during gas hydrate formation/dissociation to aid in locating clathrates in the vessel. The DSS fibers are placed in the sediment following an Archimedean spiral design and then the position of each sensor is solved by iterating over the arc length formula with Newtons method. The data is then gridded with 1 a natural neighbor interpolation algorithm to allow contouring of the data. The solution of the sensor locations is verified with hot and cold stimulus in known locations. An experiment was preformed with a vertically split column of sand and silt. The DSS system clearly showed hydrate forming in the sand first, then slowly creeping into the silt. Similar systems and data processing techniques could be used for monitoring of hydrates in natural environments or in any situation where a hybrid temperature/strain index is useful. Further ad- vances in fiber technology allow the fiber to be applied in any configuration and the position of each sensor to be precisely determined making practical applications easier.

  4. Modeling IR spectra of CO2 isotopologues and CH4 trapped In type I clathrate

    Directory of Open Access Journals (Sweden)

    Lakhlifi A.

    2014-02-01

    Full Text Available To test the hypothesis of atmospheric carbon dioxide or methane storage in metastable clathrate, a theoretical formalism is developed to model and simulate the spectra of the CO2 or CH4 molecule trapped in clathrates. 12-6 Lennard-Jones atomatom potentials are used to account for short and long range interactions between the atoms of the trapped molecules and atoms of H2O molecules of the cage. Effective electric charges are used for electrostatic interactions with H2O molecules. The calculations were performed on clathrates of type I, with a small and a large cage to determine equilibrium configurations for both CO2 and CH4 and vibrational shifts were determined for CO2 in an undistorted trapping nano-cage.

  5. Clathration of Volatiles in the Solar Nebula and Implications for the Origin of Titan's atmosphere

    CERN Document Server

    Mousis, Olivier; Thomas, Caroline; Pasek, Matthew; Marboeuf, Ulysse; Alibert, Yann; Ballenegger, Vincent; Cordier, Daniel; Ellinger, Yves; Pauzat, Francoise; Picaud, Sylvain

    2008-01-01

    We describe a scenario of Titan's formation matching the constraints imposed by its current atmospheric composition. Assuming that the abundances of all elements, including oxygen, are solar in the outer nebula, we show that the icy planetesimals were agglomerated in the feeding zone of Saturn from a mixture of clathrates with multiple guest species, so-called stochiometric hydrates such as ammonia hydrate, and pure condensates. We also use a statistical thermodynamic approach to constrain the composition of multiple guest clathrates formed in the solar nebula. We then infer that krypton and xenon, that are expected to condense in the 20-30 K temperature range in the solar nebula, are trapped in clathrates at higher temperatures than 50 K. Once formed, these ices either were accreted by Saturn or remained embedded in its surrounding subnebula until they found their way into the regular satellites growing around Saturn. In order to explain the carbon monoxide and primordial argon deficiencies of Titan's atmosp...

  6. Thermodynamic Properties of Hydrogen + Tetra-n-Butyl Ammonium Bromide Semi-Clathrate Hydrate

    Directory of Open Access Journals (Sweden)

    Shunsuke Hashimoto

    2010-01-01

    Full Text Available Thermodynamic stability and hydrogen occupancy on the hydrogen + tetra-n-butyl ammonium bromide semi-clathrate hydrate were investigated by means of Raman spectroscopic and phase equilibrium measurements under the three-phase equilibrium condition. The structure of mixed gas hydrates changes from tetragonal to another structure around 95 MPa and 292 K depending on surrounding hydrogen fugacity. The occupied amount of hydrogen in the semi-clathrate hydrate increases significantly associated with the structural transition. Tetra-n-butyl ammonium bromide semi-clathrate hydrates can absorb hydrogen molecules by a pressure-swing without destroying the hydrogen bonds of hydrate cages at 15 MPa or over.

  7. Thermodynamic studies on semi-clathrate hydrates of TBAB + gases containing carbon dioxide

    International Nuclear Information System (INIS)

    CO2 capture has become an important area of research mainly due to its drastic greenhouse effects. Gas hydrate formation as a separation technique shows tremendous potential, both from a physical feasibility as well as an envisaged lower energy utilization criterion. Briefly, gas (clathrate) hydrates are non-stoichiometric, ice-like crystalline compounds formed through a combination of water and suitably sized guest molecule(s) under low-temperatures and elevated pressures. As the pressure required for gas hydrate formation is generally high, therefore, aqueous solution of tetra-n-butyl ammonium bromide (TBAB) is added to the system as a gas hydrate promoter. TBAB generally reduces the required hydrate formation pressure and/or increases the formation temperature as well as modifies the selectivity of hydrate cages to capture CO2 molecules. TBAB also takes part in the hydrogen-bonded cages. Such hydrates are called 'semi-clathrate' hydrates. Evidently, reliable and accurate phase equilibrium data, acceptable thermodynamic models, and other thermodynamic studies should be provided to design efficient separation processes using the aforementioned technology. For this purpose, phase equilibria of clathrate/semi-clathrate hydrates of various gas mixtures containing CO2 (CO2 + CH4/N2/H2) in the presence of pure water and aqueous solutions of TBAB have been measured in this thesis. In the theoretical section of the thesis, a thermodynamic model on the basis of the van der Waals and Platteeuw (vdW-P) solid solution theory along with the modified equations for determination of the Langmuir constants of the hydrate formers has been successfully developed to represent/predict equilibrium conditions of semi-clathrate hydrates of CO2, CH4, and N2. Later, several thermodynamic consistency tests on the basis of Gibbs-Duhem equation as well as a statistical approach have been applied on the phase equilibrium data of the systems of mixed/simple clathrate hydrates to conclude about

  8. Guest-Host Interaction Study in Clathrate Hydrates Using Lattice Dynamics Simulation

    Institute of Scientific and Technical Information of China (English)

    Maofeng Jing; Shunle Dong

    2005-01-01

    Lattice dynamics simulation of several gas hydrates (helium, argon, and methane) with different occupancy rates has been performed using TIP3P potential model. Results show that the coupling between the guest and host is not simple as depicted by the conventional viewpoints. For clathrate hydrate enclosing small guest, the small cages are dominantly responsible for the thermodynamic stability of clathrate hydrates. And the spectrum of methane hydrate is studied compared with argon hydrate,then as a result, shrink effect from positive hydrogen shell is proposed.

  9. A NOVEL SUPRAMOLECULAR CLATHRATE OF RODLIKE p-BUTOXYBENZYLIDENE-p'-DODECOXYANILINE TRAPPED WITHIN POLYORGANOSILOXANE PORE

    Institute of Scientific and Technical Information of China (English)

    1998-01-01

    A novel supramolecular polysiloxane clathrate, POS/C, has been prepared by in-situ encapsulating rodlike p-butoxybenzylidene-p'-dodecoxyaniline (BBDA), one kind of Schiff base liquid crystal molecule, within the pore of polyorganosiloxane (POS) which is prepared by hydrosilylation coupling reaction of polyvinylsilsesquioxane (Vi-T) with tetramethyldisiloxane (H-MM). Investigation by polarized light microscopy (PLM), differential scanning calorimetry (DSC), infrared spectroscopy (IR), atomic force microscopy(AFM) and molecular simulation gives a preliminary support to the existence of the title supramolecular clathrate.

  10. A new method for screening potential sII and sH hydrogen clathrate hydrate promoters with model potentials.

    Science.gov (United States)

    Frankcombe, Terry J; Kroes, Geert-Jan

    2011-08-01

    A new predictive computational method for classifying clathrate hydrate promoter molecules is presented, based on the interaction energies between potential promoters and the water networks of sII and sH clathrates. The motivation for this work is identifying promoters for storing hydrogen compactly in clathrate hydrates. As a first step towards achieving this goal, we have developed a general method aimed at distinguishing between molecules that form sII clathrate hydrates and molecules that can-together with a weakly interacting help gas-form sH clathrate hydrates. The new computational method calculates differences in estimated formation energies of the sII and the sH clathrate hydrate. Model interaction potentials have been used, including the electrostatic interactions with newly calculated partial charges for all the considered potential promoter molecules. The methodology can discriminate between the clathrate structure types (sII or sH) formed by each potential promoter with good selectivity, i.e., better than achieved with a simple van der Waals diameter criterion.

  11. Physicochemical and structural studies of clathrate hydrates of tetrabutylammonium polyacrylates.

    Science.gov (United States)

    Terekhova, Irina S; Manakov, Andrey Yu; Komarov, Vladislav Yu; Villevald, Galina V; Burdin, Alexander A; Karpova, Tamara D; Aladko, Eugeny Ya

    2013-03-01

    In this work, physicochemical and structural studies have been carried out for semiclathrate hydrates of linear (un-cross-linked) and cross-linked tetrabutylammonium polyacrylates with different degrees of cross-linking of the polymeric guest molecules (n = 0.5, 1, 2, 3%) and different degrees of substitution of proton ions of carboxylic groups in poly(acrylic acid) for TBA cations (x = 1, 0.8, 0.6). The changes in the hydrates' stability and composition depending on the outlined parameters were examined in the course of phase diagram studies of the binary systems water-tetrabutylammonium polyacrylates using differential thermal analysis method and calorimetric measurements of fusion enthalpies of the hydrates. Phase diagram studies of the binary system water-linear tetrabutylammonium polyacrylate revealed the formation of four hydrates. Based on the data of chemical analysis of hydrate crystals the compositions of all hydrates have been determined. Single-crystal X-ray diffraction studies revealed a tetragonal structure, space group 4/m, and unit cell parameters are close for different hydrates and lie in the ranges a = 23.4289-23.4713 Å and c = 12.3280-12.3651 Å (150 K). The structure can be related to tetragonal structure I typical for the clathrate hydrates of tetraalkylammonium salts with monomeric anions. Powder X-ray diffraction analyses confirmed the identity of the above crystal structure to that of the hydrates with cross-linked tetrabutylammonium polyacrylates. The behavior of TBA polyacrylate hydrates under the pressure of methane was studied and quantitative assessment of the gas content in the hydrates was made using volumetric analysis method. PMID:23383955

  12. The strength and rheology of methane clathrate hydrate

    Science.gov (United States)

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

    2003-01-01

    Methane clathrate hydrate (structure I) is found to be very strong, based on laboratory triaxial deformation experiments we have carried out on samples of synthetic, high-purity, polycrystalline material. Samples were deformed in compressional creep tests (i.e., constant applied stress, ??), at conditions of confining pressure P = 50 and 100 MPa, strain rate 4.5 ?? 10-8 ??? ?? ??? 4.3 ?? 10-4 s-1, temperature 260 ??? T ??? 287 K, and internal methane pressure 10 ??? PCH4 ??? 15 MPa. At steady state, typically reached in a few percent strain, methane hydrate exhibited strength that was far higher than expected on the basis of published work. In terms of the standard high-temperature creep law, ?? = A??ne-(E*+PV*)/RT the rheology is described by the constants A = 108.55 MPa-n s-1, n = 2.2, E* = 90,000 J mol-1, and V* = 19 cm3 mol-1. For comparison at temperatures just below the ice point, methane hydrate at a given strain rate is over 20 times stronger than ice, and the contrast increases at lower temperatures. The possible occurrence of syntectonic dissociation of methane hydrate to methane plus free water in these experiments suggests that the high strength measured here may be only a lower bound. On Earth, high strength in hydrate-bearing formations implies higher energy release upon decomposition and subsequent failure. In the outer solar system, if Titan has a 100-km-thick near-surface layer of high-strength, low-thermal conductivity methane hydrate as has been suggested, its interior is likely to be considerably warmer than previously expected.

  13. Cryolava flow destabilization of crustal methane clathrate hydrate on Titan

    Science.gov (United States)

    Davies, Ashley Gerard; Sotin, Christophe; Choukroun, Mathieu; Matson, Dennis L.; Johnson, Torrence V.

    2016-08-01

    To date, there has been no conclusive observation of ongoing endogenous volcanic activity on Saturn's moon Titan. However, with time, Titan's atmospheric methane is lost and must be replenished. We have modeled one possible mechanism for the replenishment of Titan's methane loss. Cryolavas can supply enough heat to release large amounts of methane from methane clathrate hydrates (MCH). The volume of methane released is controlled by the flow thickness and its areal extent. The depth of the destabilisation layer is typically ≈30% of the thickness of the lava flow (≈3 m for a 10-m thick flow). For this flow example, a maximum of 372 kg of methane is released per m2 of flow area. Such an event would release methane for nearly a year. One or two events per year covering ∼20 km2 would be sufficient to resupply atmospheric methane. A much larger effusive event covering an area of ≈9000 km2 with flows 200 m thick would release enough methane to sustain current methane concentrations for 10,000 years. The minimum size of "cryo-flows" sufficient to maintain the current atmospheric methane is small enough that their detection with current instruments (e.g., Cassini) could be challenging. We do not suggest that Titan's original atmosphere was generated by this mechanism. It is unlikely that small-scale surface MCH destabilisation is solely responsible for long-term (> a few Myr) sustenance of Titan's atmospheric methane, but rather we present it as a possible contributor to Titan's past and current atmospheric methane.

  14. Formation and function of vacancies in Si/Ge Clathrates: The importance of broken symmetries

    Science.gov (United States)

    Bhattacharya, Amrita; Carbogno, Christian; Scheffler, Matthias; Dr. Matthias Scheffler Team, Prof.

    2015-03-01

    One promising material class for improved thermoelectrics are the clathrates, i.e., semiconducting host lattices encapsulating guest atom. Even in simple clathrates, such as, Si46 and Ge46, the introduction of guests can result in important but not yet understood effects: In Si hosts, the addition of K (or Ba) results in defect-free K8Si46 (Ba8Si46) phases. In spite of their structural and electronic similitude, Ge hosts behave fundamentally different upon filling, where, the spontaneously formed framework vacancies completely (or partially) balance the electron donated by K (or Ba) guests leading to K8Ge44(orBa8Ge43) clathrates. In this work, we use density-functional theory, carefully validating the exchange correlation functional, to compute the formation energies of vacancies and vacancy complexes in Si- and Ge-hosts as function of the filling of guests. By taking into account of the structural disorder, geometric relaxations, and vibrational entropies, we verify the experimentally found vacancy concentration and the thermodynamic stabilities of these compounds. We can trace back the contrasting behaviour of Si/Ge clathrates upon filling to a curious, charged vacancy induced break in symmetry that occurs in Si but not in Ge hosts.

  15. Formation and properties of ice XVI obtained by emptying a type sII clathrate hydrate.

    Science.gov (United States)

    Falenty, Andrzej; Hansen, Thomas C; Kuhs, Werner F

    2014-12-11

    Gas hydrates are ice-like solids, in which guest molecules or atoms are trapped inside cages formed within a crystalline host framework (clathrate) of hydrogen-bonded water molecules. They are naturally present in large quantities on the deep ocean floor and as permafrost, can form in and block gas pipelines, and are thought to occur widely on Earth and beyond. A natural point of reference for this large and ubiquitous family of inclusion compounds is the empty hydrate lattice, which is usually regarded as experimentally inaccessible because the guest species stabilize the host framework. However, it has been suggested that sufficiently small guests may be removed to leave behind metastable empty clathrates, and guest-free Si- and Ge-clathrates have indeed been obtained. Here we show that this strategy can also be applied to water-based clathrates: five days of continuous vacuum pumping on small particles of neon hydrate (of structure sII) removes all guests, allowing us to determine the crystal structure, thermal expansivity and limit of metastability of the empty hydrate. It is the seventeenth experimentally established crystalline ice phase, ice XVI according to the current ice nomenclature, has a density of 0.81 grams per cubic centimetre (making it the least dense of all known crystalline water phases) and is expected to be the stable low-temperature phase of water at negative pressures (that is, under tension). We find that the empty hydrate structure exhibits negative thermal expansion below about 55 kelvin, and that it is mechanically more stable and has at low temperatures larger lattice constants than the filled hydrate. These observations attest to the importance of kinetic effects and host-guest interactions in clathrate hydrates, with further characterization of the empty hydrate expected to improve our understanding of the structure, properties and behaviour of these unique materials.

  16. A molecular dynamics study of guest-host hydrogen bonding in alcohol clathrate hydrates.

    Science.gov (United States)

    Hiratsuka, Masaki; Ohmura, Ryo; Sum, Amadeu K; Alavi, Saman; Yasuoka, Kenji

    2015-05-21

    Clathrate hydrates are typically stabilized by suitably sized hydrophobic guest molecules. However, it has been experimentally reported that isomers of amyl-alcohol C5H11OH can be enclosed into the 5(12)6(4) cages in structure II (sII) clathrate hydrates, even though the effective radii of the molecules are larger than the van der Waals radii of the cages. To reveal the mechanism of the anomalous enclathration of hydrophilic molecules, we performed ab initio and classical molecular dynamics simulations (MD) and analyzed the structure and dynamics of a guest-host hydrogen bond for sII 3-methyl-1-butanol and structure H (sH) 2-methyl-2-butanol clathrate hydrates. The simulations clearly showed the formation of guest-host hydrogen bonds and the incorporation of the O-H group of 3-methyl-1-butanol guest molecules into the framework of the sII 5(12)6(4) cages, with the remaining hydrophobic part of the amyl-alcohol molecule well accommodated into the cages. The calculated vibrational spectra of alcohol O-H bonds showed large frequency shifts due to the strong guest-host hydrogen bonding. The 2-methyl-2-butanol guests form strong hydrogen bonds with the cage water molecules in the sH clathrate, but are not incorporated into the water framework. By comparing the structures of the alcohols in the hydrate phases, the effect of the location of O-H groups in the butyl chain of the guest molecules on the crystalline structure of the clathrate hydrates is indicated.

  17. The HD molecule in small and medium cages of clathrate hydrates: Quantum dynamics studied by neutron scattering measurements and computation

    Energy Technology Data Exchange (ETDEWEB)

    Colognesi, Daniele; Celli, Milva; Ulivi, Lorenzo, E-mail: lorenzo.ulivi@isc.cnr.it [Consiglio Nazionale delle Ricerche, Istituto dei Sistemi Complessi, via Madonna del Piano 10, I-50019 Sesto Fiorentino (Italy); Powers, Anna; Xu, Minzhong [Department of Chemistry, New York University, New York, New York 10003 (United States); Bačić, Zlatko, E-mail: zlatko.bacic@nyu.edu [Department of Chemistry, New York University, New York, New York 10003 (United States); NYU-ECNU Center for Computational Chemistry at NYU Shanghai, Shanghai 200062 (China)

    2014-10-07

    We report inelastic neutron scattering (INS) measurements on molecular hydrogen deuteride (HD) trapped in binary cubic (sII) and hexagonal (sH) clathrate hydrates, performed at low temperature using two different neutron spectrometers in order to probe both energy and momentum transfer. The INS spectra of binary clathrate samples exhibit a rich structure containing sharp bands arising from both the rotational transitions and the rattling modes of the guest molecule. For the clathrates with sII structure, there is a very good agreement with the rigorous fully quantum simulations which account for the subtle effects of the anisotropy, angular and radial, of the host cage on the HD microscopic dynamics. The sH clathrate sample presents a much greater challenge, due to the uncertainties regarding the crystal structure, which is known only for similar crystals with different promoter, but nor for HD (or H{sub 2}) plus methyl tert-butyl ether (MTBE-d12)

  18. Thermodynamic study of clathrates hydrates from hydrocarbon gas mixtures Consequences for capture CO2 and flow assurance

    OpenAIRE

    Bouillot, Baptiste; Le, Quang-Du; Le Quang, Duyen; Herri, Jean-Michel

    2014-01-01

    This work is a contribution to the global understanding of the coupling between kinetics and thermodynamics to explain the composition of the clathrate hydrates during their crystallization from an aqueous liquid and a hydrocarbon gas phase. In this work, we face new experimental facts that open questioning after comparing the classical modeling of clathrate hydrates following the approach of [1] with our experimental data following a new procedure allowing determining the hydrate composition...

  19. Growth mechanism of a gas clathrate hydrate from a dilute aqueous gas solution: a molecular dynamics simulation of a three-phase system.

    Science.gov (United States)

    Nada, Hiroki

    2006-08-24

    A molecular dynamics simulation of a three-phase system including a gas clathrate, liquid water, and a gas was carried out at 298 K and high pressure in order to investigate the growth mechanism of the clathrate from a dilute aqueous gas solution. The simulation indicated that the clathrate grew on interfaces between the clathrate and the liquid water, after transfer of the gas molecules from the gas phase to the interfaces. The results suggest a two-step process for growth: first, gas molecules are arranged at cage sites, and second, H(2)O molecules are ordered near the gas molecules. The results also suggest that only the H(2)O molecules, which are surrounded or sandwiched by the gas molecules, form the stable polygons that constitute the cages of the clathrate. In addition, the growth of the clathrate from a concentrated aqueous gas solution was also simulated, and the results suggested a growth mechanism in which many H(2)O and gas molecules correctively form the structure of the clathrate. The clathrate grown from the concentrated solution contained some empty cages, whereas the formation of empty cages was not observed during the growth from the dilute solution. The results obtained by both simulations are compared with the results of an experimental study, and the growth mechanism of the clathrate in a real system is discussed.

  20. A statistical method for evaluation of the experimental phase equilibrium data of simple clathrate hydrates

    DEFF Research Database (Denmark)

    Eslamimanesh, Ali; Gharagheizi, Farhad; Mohammadi, Amir H.;

    2012-01-01

    that the applied correlation for calculation/estimation of the phase behavior of simple clathrate hydrate systems is statistically valid and correct, 5 hydrate dissociation data are found to be probable doubtful ones and 10 data points are out of applicability domain of the applied correlation......., and the residuals of a selected correlation results lead to define the probable outliers. This method not only contributes to outliers diagnostics but also identifies the range of applicability of the applied model and quality of the existing experimental data. The available correlation in the literature......We, herein, present a statistical method for diagnostics of the outliers in phase equilibrium data (dissociation data) of simple clathrate hydrates. The applied algorithm is performed on the basis of the Leverage mathematical approach, in which the statistical Hat matrix, Williams Plot...

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

    International Nuclear Information System (INIS)

    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

  2. Calorimetric and X-ray studies of clathrate hydrates of tetraisoamylammonium polyacrylates.

    Science.gov (United States)

    Terekhova, Irina S; Manakov, Andrey Yu; Soldatov, Dmitriy V; Suwinska, Kinga; Skiba, Sergey S; Stenin, Yuri G; Villevald, Galina V; Karpova, Tamara D; Yunoshev, Alexander S

    2009-04-30

    The structure of clathrate hydrates with tetraisoamylammonium polyacrylate salt incorporated as guest has been studied in this work. Also, quantitative studies on the stability changes of the clathrate hydrates with different degrees of cross-linking of the guest polymer (varied from 0 to 3%) have been conducted. A single crystal X-ray diffraction study of a crystal of the hydrate with linear (uncross-linked) tetraisoamylammonium polyacrylate as guest reveals a hexagonal structure (space group P6m2, a = 12.15 A, c =12.58 A at 100 K) with 39 host framework water molecules per one guest monomeric unit. Powder X-ray diffraction analyses confirm the identity of the above crystal structure of the hydrate with linear guest polymer and the crystal structure of the hydrates with cross-linked guest (hexagonal, a = 12.25 A, c =12.72 A at 276 K). In order to quantitatively determine the stability differences of the hydrates with the included guests having various degrees of cross-linking of the anionic chain, a series of differential scanning calorimetry measurements of the fusion enthalpy of the hydrate samples has been carried out. On the basis of the results obtained, a structural model describing the decrease in the stability of the clathrate hydrates with tetraisoamylammonium polyacrylate guest as a function of the degree of cross-linking of the guest polymer has been suggested. PMID:19344169

  3. A simple van’t Hoff law for calculating Langmuir constants in clathrate hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Lakhlifi, Azzedine, E-mail: azzedine.lakhlifi@obs-besancon.fr [Institut UTINAM-UMR 6213 CNRS, Université de Franche-Comté, Observatoire de Besançon, 41 bis avenue de l’Observatoire, BP 1615, 25010 Besançon Cedex (France); Dahoo, Pierre Richard [Université de Versailles-Saint-Quentin-en-Yvelines, Sorbonne Universités, Laboratoire Atmosphères Milieux Observations Spatiales, CNRS, UMR 8190, Observatoire de Versailles Saint-Quentin-en-Yvelines, 11 Bd d’Alembert, F-78820 Guyancourt (France); Picaud, Sylvain [Institut UTINAM-UMR 6213 CNRS, Université de Franche-Comté, Observatoire de Besançon, 41 bis avenue de l’Observatoire, BP 1615, 25010 Besançon Cedex (France); Mousis, Olivier [Institut UTINAM-UMR 6213 CNRS, Université de Franche-Comté, Observatoire de Besançon, 41 bis avenue de l’Observatoire, BP 1615, 25010 Besançon Cedex (France); Aix Marseille Université, CNRS, LAM (Laboratoire d’Astrophysique de Marseille) UMR 7326, 13388 Marseille (France)

    2015-02-20

    Highlights: • Tabulated Langmuir constants of simple gas hydrates for several molecules. • A van’t Hoff law in the 50–300 K temperature range is given for each case. • Practical form of van’t Hoff parameters for planetologists. • Fractional occupancies of guest species can be easily calculated. • An anisotropic guest-water atom–atom potential is used for numerical calculations. - Abstract: This work gives a van’t Hoff law expression of Langmuir constants of different species for determining their occupancy in clathrate hydrates. First, a pairwise site–site interaction potential energy model is used to calculate the Langmuir constants in an otherwise anisotropic potential environment, as a function of temperature. The results are then fitted to a van’t Hoff law expression to give a set of parameters that can be used for calculating clathrates compositions. The van’t Hoff law’s parameters are given for eighteen gas species trapped in the small and large cavities of structure types I and II. The accuracy of this approach is based on a detailed comparison with available experimental and/or previously calculated data for ethane, cyclo-propane, methane and carbon dioxide clathrate hydrates. A comparison with the analytical cell method is also carried out to better understand the importance of asymmetry and possible limitations of the van’t Hoff temperature dependence.

  4. Volcanic Destabilisation of Methane Clathrate Hydrate on Titan: the Mechanism for Resupplying Atmospheric CH4?

    Science.gov (United States)

    Davies, Ashley; Sotin, C.; Choukroun, M.; Matson, D. L.; Johnson, T. V.

    2013-10-01

    Titan may have an upper crust rich in methane clathrates which would have formed early in Titan’s history [1-3]. The abundance of atmospheric methane, which has a limited lifetime, and the presence of 40Ar require replenishment over time. Volcanic processes may release these gases from Titan’s interior, although, so far, no conclusive evidence of an ongoing volcanic event has been observed: no “smoking gun” has been seen. Still, some process has recently supplied a considerable amount of methane to Titan’s atmosphere. We have investigated the emplacement of “cryolavas” of varying composition to quantify thermal exchange and lava solidification processes to model thermal wave penetration into a methane-rich substrate (see [4]), and to determine event detectability. Clathrate destabilisation releases methane and other trapped gases, such as argon. A 10-m-thick cryolava covering 100 km2 raises 3 x 108 m3 of substrate methane clathrates to destabilization temperature in ~108 s. With a density of 920 kg/m3, and ≈13% of the mass being methane, 4 x 1010 kg of methane is released. This is an impressive amount, but it would take 5 million similar events to yield the current mass of atmospheric methane. However, meeting Titan’s current global methane replenishment rate is feasible through the thermal interaction between cryolavas and methane clathrate deposits, but only (1) after the flow has solidified; (2) if cracks form, connecting surface to substrate; and (3) the cracks form while the temperature of the clathrates is greater than the destabilisation temperature. The relatively small scale of this activity may be hard to detect. This work was performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. Choukroun, M. and Sotin, C. (2012) GRL, 39, L04201. [2] Tobie, G. et al. (2006) Nature, 440, 61-64. [3] Lunine, J. et al. (2009) Origin and Evolution of Titan, in Titan From Cassini-Huygens, ed. R. Brown et al

  5. On molecular recognition in clathrates of l,l'-binaphthyl-2,2'-dicarboxylic acid with cyclohexanone and diethyl ether

    International Nuclear Information System (INIS)

    1.1'-Binaphthyl-2.2 '-dicarboxylic acid (BNDA) host forms a conventional clathrate with cyclohexanone, in -hich the guest molecules do not use potential H-bonding possibilities. In the inclusion complex between diethyl ether and BNDA monohydrate, the guest molecules are H-bonded to water molecules avoiding a direct host-guest interaction. This mode being unusual for the formation of BNDA clathrates and indicating a failure of a molecular recognition through host-guest H-bonding is discussed. Single crystals of all clathrates were obtained by slow evaporation of the solvent from corresponding solutions at the room temperature. Intensity data were collected at the room temperature on a Syntex P2 and on an Enraf-Nonius CAD-4 diffractometer using Cu-Kα radiation

  6. A new phase diagram of water under negative pressure: The rise of the lowest-density clathrate s-III.

    Science.gov (United States)

    Huang, Yingying; Zhu, Chongqin; Wang, Lu; Cao, Xiaoxiao; Su, Yan; Jiang, Xue; Meng, Sheng; Zhao, Jijun; Zeng, Xiao Cheng

    2016-02-01

    Ice and ice clathrate are not only omnipresent across polar regions of Earth or under terrestrial oceans but also ubiquitous in the solar system such as on comets, asteroids, or icy moons of the giant planets. Depending on the surrounding environment (temperature and pressure), ice alone exhibits an exceptionally rich and complicated phase diagram with 17 known crystalline polymorphs. Water molecules also form clathrate compounds with inclusion of guest molecules, such as cubic structure I (s-I), cubic structure II (s-II), hexagonal structure H (s-H), tetragonal structure T (s-T), and tetragonal structure K (s-K). Recently, guest-free clathrate structure II (s-II), also known as ice XVI located in the negative-pressure region of the phase diagram of water, is synthesized in the laboratory and motivates scientists to reexamine other ice clathrates with low density. Using extensive Monte Carlo packing algorithm and dispersion-corrected density functional theory optimization, we predict a crystalline clathrate of cubic structure III (s-III) composed of two large icosihexahedral cavities (8(6)6(8)4(12)) and six small decahedral cavities (8(2)4(8)) per unit cell, which is dynamically stable by itself and can be fully stabilized by encapsulating an appropriate guest molecule in the large cavity. A new phase diagram of water ice with TIP4P/2005 (four-point transferable intermolecular potential/2005) model potential is constructed by considering a variety of candidate phases. The guest-free s-III clathrate with ultralow density overtakes s-II and s-H phases and emerges as the most stable ice polymorph in the pressure region below -5834 bar at 0 K and below -3411 bar at 300 K. PMID:26933681

  7. A new phase diagram of water under negative pressure: The rise of the lowest-density clathrate s-III.

    Science.gov (United States)

    Huang, Yingying; Zhu, Chongqin; Wang, Lu; Cao, Xiaoxiao; Su, Yan; Jiang, Xue; Meng, Sheng; Zhao, Jijun; Zeng, Xiao Cheng

    2016-02-01

    Ice and ice clathrate are not only omnipresent across polar regions of Earth or under terrestrial oceans but also ubiquitous in the solar system such as on comets, asteroids, or icy moons of the giant planets. Depending on the surrounding environment (temperature and pressure), ice alone exhibits an exceptionally rich and complicated phase diagram with 17 known crystalline polymorphs. Water molecules also form clathrate compounds with inclusion of guest molecules, such as cubic structure I (s-I), cubic structure II (s-II), hexagonal structure H (s-H), tetragonal structure T (s-T), and tetragonal structure K (s-K). Recently, guest-free clathrate structure II (s-II), also known as ice XVI located in the negative-pressure region of the phase diagram of water, is synthesized in the laboratory and motivates scientists to reexamine other ice clathrates with low density. Using extensive Monte Carlo packing algorithm and dispersion-corrected density functional theory optimization, we predict a crystalline clathrate of cubic structure III (s-III) composed of two large icosihexahedral cavities (8(6)6(8)4(12)) and six small decahedral cavities (8(2)4(8)) per unit cell, which is dynamically stable by itself and can be fully stabilized by encapsulating an appropriate guest molecule in the large cavity. A new phase diagram of water ice with TIP4P/2005 (four-point transferable intermolecular potential/2005) model potential is constructed by considering a variety of candidate phases. The guest-free s-III clathrate with ultralow density overtakes s-II and s-H phases and emerges as the most stable ice polymorph in the pressure region below -5834 bar at 0 K and below -3411 bar at 300 K.

  8. Pressure induced amorphization and collapse of magnetic order in type-I clathrate Eu8Ga16Ge30

    OpenAIRE

    Mardegan, J. R. L.; Fabbris, G.; Veiga, L. S. I.; Adriano, C.; M.A. Avila; Haskel, D.; Giles, C.

    2013-01-01

    We investigate the low temperature structural and electronic properties of the type-I clathrate Eu8Ga16Ge30 under pressure using x-ray powder diffraction (XRD), x-ray absorption near-edge structure (XANES) and x-ray magnetic circular dichroism (XMCD) techniques. The XRD measurements reveal a transition to an amorphous phase above 18 GPa. Unlike previous reports on other clathrate compounds, no volume-collapse is observed prior to the crystalline-amorphous phase transition which takes place wh...

  9. Study on clathrate formation of schaeffer's complexes with 4-methylpyridine (4-MePy) by IR-spectroscopy method

    International Nuclear Information System (INIS)

    IR-spectra of Schaeffer's complex compounds [M(4-MePy)n(NCS)2] (M-Co(2), Ni(2), Zn(2), Cd(2); n=2 or 4) and their clathrates with 4-MePy have been obtained. These data indicate of the presence both ''free'' and bonded 4-MePy in the structure of clathrates. To put in another way, the enclosing of 4-MePy in the cavities of the host framework takes place without appreciable chemical interaction between the guest and the host, and reforming of crystalline modification doesn't bring to changing of the spectrum in examined area

  10. High-Temperature Thermoelectric Properties of Polycrystalline Silicon Clathrate Ba8TM x Si46- x (TM = Ni, Pt)

    Science.gov (United States)

    Kikuchi, Daisuke; Fujimura, Koji; Tadokoro, Jun; Matsumoto, Miko; Yamazaki, Satoshi; Sasaki, Hirokazu; Eguchi, Tatsuhiko; Susai, Kyota

    2016-03-01

    The n-/ p-type stability of a silicon clathrate in which silicon was substituted with nickel or platinum was evaluated by density functional theory calculations. Then, Ba8Pt5Si41 and Ba8Pt1.5Ni3.5Si41 were synthesized, and their thermoelectric properties were investigated. The polycrystalline compounds, which have a type-I clathrate structure, were prepared through arc melting and spark-plasma-sintering. The crystal structures and elemental compositions of the synthesized samples were characterized via powder x-ray diffraction and electron microprobe analyses, respectively. The temperature dependence of both the electrical resistivity and the Seebeck coefficient was measured.

  11. Methanol incorporation in clathrate hydrates and the implications for oil and gas pipeline flow assurance and icy planetary bodies

    OpenAIRE

    Shin, Kyuchul; Udachin, Konstantin A.; Moudrakovski, Igor L.; Leek, Donald M.; Alavi, Saman; Ratcliffe, Christopher I.; Ripmeester, John A.

    2013-01-01

    One of the best-known uses of methanol is as antifreeze. Methanol is used in large quantities in industrial applications to prevent methane clathrate hydrate blockages from forming in oil and gas pipelines. Methanol is also assigned a major role as antifreeze in giving icy planetary bodies (e.g., Titan) a liquid subsurface ocean and/or an atmosphere containing significant quantities of methane. In this work, we reveal a previously unverified role for methanol as a guest in clathrate hydrate c...

  12. Water proton configurations in structures I, II, and H clathrate hydrate unit cells.

    Science.gov (United States)

    Takeuchi, Fumihito; Hiratsuka, Masaki; Ohmura, Ryo; Alavi, Saman; Sum, Amadeu K; Yasuoka, Kenji

    2013-03-28

    Position and orientation of water protons need to be specified when the molecular simulation studies are performed for clathrate hydrates. Positions of oxygen atoms in water are experimentally determined by X-ray diffraction analysis of clathrate hydrate structures, but positions of water hydrogen atoms in the lattice are disordered. This study reports a determination of the water proton coordinates in unit cell of structure I (sI), II (sII), and H (sH) clathrate hydrates that satisfy the ice rules, have the lowest potential energy configuration for the protons, and give a net zero dipole moment. Possible proton coordinates in the unit cell were chosen by analyzing the symmetry of protons on the hexagonal or pentagonal faces in the hydrate cages and generating all possible proton distributions which satisfy the ice rules. We found that in the sI and sII unit cells, proton distributions with small net dipole moments have fairly narrow potential energy spreads of about 1 kJ∕mol. The total Coulomb potential on a test unit charge placed in the cage center for the minimum energy∕minimum dipole unit cell configurations was calculated. In the sI small cages, the Coulomb potential energy spread in each class of cage is less than 0.1 kJ∕mol, while the potential energy spread increases to values up to 6 kJ∕mol in sH and 15 kJ∕mol in the sII cages. The guest environments inside the cages can therefore be substantially different in the sII case. Cartesian coordinates for oxygen and hydrogen atoms in the sI, sII, and sH unit cells are reported for reference.

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

    Energy Technology Data Exchange (ETDEWEB)

    Dureckova, Hana, E-mail: houci059@uottawa.ca; Woo, Tom K., E-mail: tom.woo@uottawa.ca [Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 5N6 (Canada); Alavi, Saman, E-mail: saman.alavi@nrc-cnrc.gc.ca [Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 5N6 (Canada); National Research Council of Canada, 100 Sussex Dr., Ottawa, Ontario K1N 6N5 (Canada); Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, British Columbia V6T 1Z3 (Canada)

    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 Br{sub 2} and Cl{sub 2} 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 Br{sub 2} and Cl{sub 2} 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 Br{sub 2} and Cl{sub 2} 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 Br{sub 2} and Cl{sub 2} 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 Br{sub 2} and Cl{sub 2} guests in the hydrate cages may explain why bromine forms the unique TS-I phase.

  14. Lattice dynamics study of low energy guest-host coupling in clathrate hydrate

    Institute of Scientific and Technical Information of China (English)

    Yang Yue-Hai; Dong Shun-Le; Wang Lin

    2008-01-01

    Our lattice dynamics simulation of Xe-hydrate with four-site TIP4P oxygen-shell model can accurately reproduce each peak position in the inelastic incoherent neutron scattering spectrum at the acoustic band (below 15 meV) and yield correct relative intensity.Based on the results,the uncertain profile at ~6 meV is assigned to anharmonic guest modes coupled strongly to small cages.Blue shift is proposed in phonon dispersion sheet in the case of anticrossing and found to be an evident signal for guest-host coupling that explains the anomalous thermal conductivity of clathrate hydrate.

  15. In situ apparatus for the study of clathrate hydrates relevant to solar system bodies using synchrotron X-ray diffraction and Raman spectroscopy

    Science.gov (United States)

    Day, Sarah J.; Thompson, Stephen P.; Evans, Aneurin; Parker, Julia E.

    2015-02-01

    Context. Clathrate hydrates are believed to play a significant role in various solar system environments, e.g. comets, and the surfaces and interiors of icy satellites. However, the structural factors governing their formation and dissociation are poorly understood. Aims: We demonstrate the application of a high pressure gas cell, combined with variable temperature non-contact cooling and fast, time-resolved data collection, to the in situ study of clathrate hydrates under conditions relevant to solar system environments. Methods: Clathrates formed and processed within the sample cell are monitored in situ using time-resolved synchrotron X-ray powder diffraction and laser Raman spectroscopy. Results: X-ray diffraction allows the formation of clathrate hydrates to be observed as CO2 gas is applied to ice formed within the cell. Complete conversion is obtained by annealing at temperatures just below the ice melting point. A subsequent rise in the quantity of clathrate is observed as the cell is thermally cycled. Four regions between 100-5000 cm-1 are present in the in situ Raman spectra that carry features characteristic of both ice and clathrate formation. Conclusions: This novel experimental arrangement is well suited to studying clathrate hydrates over a wide range of temperature (80 -500 K) and pressure (1-100 bar) conditions relevant to solar system bodies and can be used with a variety of different gases and starting aqueous compositions (e.g. saline solutions). We propose the increase in clathrate formation observed during thermal cycling may be due to the formation of a quasi liquid-like phase that forms at temperatures below the ice melting point, but which allows either easier formation of new clathrate cages, or the retention and delocalisation of previously formed clathrate structures, possibly as amorphous clathrate. The structural similarities between hexagonal ice, the quasi liquid-like phase, and crystalline CO2 hydrate mean that differences in the

  16. The presence of clathrates in comet 67P/Churyumov-Gerasimenko.

    Science.gov (United States)

    Luspay-Kuti, Adrienn; Mousis, Olivier; Hässig, Myrtha; Fuselier, Stephen A; Lunine, Jonathan I; Marty, Bernard; Mandt, Kathleen E; Wurz, Peter; Rubin, Martin

    2016-04-01

    Cometary nuclei are considered to most closely reflect the composition of the building blocks of our solar system. As such, comets carry important information about the prevalent conditions in the solar nebula before and after planet formation. Recent measurements of the time variation of major and minor volatile species in the coma of the Jupiter family comet 67P/Churyumov-Gerasimenko (67P) by the ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument onboard Rosetta provide insight into the possible origin of this comet. The observed outgassing pattern indicates that the nucleus of 67P contains crystalline ice, clathrates, and other ices. The observed outgassing is not consistent with gas release from an amorphous ice phase with trapped volatile gases. If the building blocks of 67P were formed from crystalline ices and clathrates, then 67P would have agglomerated from ices that were condensed and altered in the protosolar nebula closer to the Sun instead of more pristine ices originating from the interstellar medium or the outskirts of the disc, where amorphous ice may dominate. PMID:27152351

  17. The presence of clathrates in comet 67P/Churyumov-Gerasimenko

    Science.gov (United States)

    Luspay-Kuti, Adrienn; Mousis, Olivier; Hässig, Myrtha; Fuselier, Stephen A.; Lunine, Jonathan I.; Marty, Bernard; Mandt, Kathleen E.; Wurz, Peter; Rubin, Martin

    2016-01-01

    Cometary nuclei are considered to most closely reflect the composition of the building blocks of our solar system. As such, comets carry important information about the prevalent conditions in the solar nebula before and after planet formation. Recent measurements of the time variation of major and minor volatile species in the coma of the Jupiter family comet 67P/Churyumov-Gerasimenko (67P) by the ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument onboard Rosetta provide insight into the possible origin of this comet. The observed outgassing pattern indicates that the nucleus of 67P contains crystalline ice, clathrates, and other ices. The observed outgassing is not consistent with gas release from an amorphous ice phase with trapped volatile gases. If the building blocks of 67P were formed from crystalline ices and clathrates, then 67P would have agglomerated from ices that were condensed and altered in the protosolar nebula closer to the Sun instead of more pristine ices originating from the interstellar medium or the outskirts of the disc, where amorphous ice may dominate. PMID:27152351

  18. The presence of clathrates in comet 67P/Churyumov-Gerasimenko

    Science.gov (United States)

    Luspay-Kuti, A.; Mousis, O.; Hässig, M.; Fuselier, S. A.; Lunine, J. I.; Marty, B.; Mandt, K. E.; Wurz, P.; Rubin, M.

    2016-04-01

    Cometary nuclei are considered to most closely reflect the composition of the building blocks of our solar system. As such, comets carry important information about the prevalent conditions in the solar nebula before and after planet formation. Recent measurements of the time variation of major and minor volatile species in the coma of the Jupiter family comet 67P/Churyumov-Gerasimenko (67P) by the ROSINA (Rosetta Orbiter Spectrometer for Ion and Neutral Analysis) instrument onboard Rosetta provide insight into the possible origin of this comet. The observed outgassing pattern indicates that the nucleus of 67P contains crystalline ice, clathrates, and other ices. The observed outgassing is not consistent with gas release from an amorphous ice phase with trapped volatile gases. If the building blocks of 67P were formed from crystalline ices and clathrates, then 67P would have agglomerated from ices that were condensed and altered in the protosolar nebula closer to the Sun instead of more pristine ices originating from the interstellar medium or the outskirts of the disc, where amorphous ice may dominate.

  19. Clathrate structure-type recognition: Application to hydrate nucleation and crystallisation.

    Science.gov (United States)

    Lauricella, Marco; Meloni, Simone; Liang, Shuai; English, Niall J; Kusalik, Peter G; Ciccotti, Giovanni

    2015-06-28

    For clathrate-hydrate polymorphic structure-type (sI versus sII), geometric recognition criteria have been developed and validated. These are applied to the study of the rich interplay and development of both sI and sII motifs in a variety of hydrate-nucleation events for methane and H2S hydrate studied by direct and enhanced-sampling molecular dynamics (MD) simulations. In the case of nucleation of methane hydrate from enhanced-sampling simulation, we notice that already at the transition state, ∼80% of the enclathrated CH4 molecules are contained in a well-structured (sII) clathrate-like crystallite. For direct MD simulation of nucleation of H2S hydrate, some sI/sII polymorphic diversity was encountered, and it was found that a realistic dissipation of the nucleation energy (in view of non-equilibrium relaxation to either microcanonical (NVE) or isothermal-isobaric (NPT) distributions) is important to determine the relative propensity to form sI versus sII motifs.

  20. Clathrate structure-type recognition: Application to hydrate nucleation and crystallisation.

    Science.gov (United States)

    Lauricella, Marco; Meloni, Simone; Liang, Shuai; English, Niall J; Kusalik, Peter G; Ciccotti, Giovanni

    2015-06-28

    For clathrate-hydrate polymorphic structure-type (sI versus sII), geometric recognition criteria have been developed and validated. These are applied to the study of the rich interplay and development of both sI and sII motifs in a variety of hydrate-nucleation events for methane and H2S hydrate studied by direct and enhanced-sampling molecular dynamics (MD) simulations. In the case of nucleation of methane hydrate from enhanced-sampling simulation, we notice that already at the transition state, ∼80% of the enclathrated CH4 molecules are contained in a well-structured (sII) clathrate-like crystallite. For direct MD simulation of nucleation of H2S hydrate, some sI/sII polymorphic diversity was encountered, and it was found that a realistic dissipation of the nucleation energy (in view of non-equilibrium relaxation to either microcanonical (NVE) or isothermal-isobaric (NPT) distributions) is important to determine the relative propensity to form sI versus sII motifs. PMID:26133437

  1. Molten gallium flux synthesis of known thermoelectric and novel magnetic inorganic clathrate compounds: Improving thermoelectric performance

    Science.gov (United States)

    Bryan, John Daniel

    Molten gallium metal has been used as a solvent to grow large single crystals of known inorganic thermoelectric clathrates Sr8Ga 16Ge30, Ba8Ga16Ge30, and Ba8Ga16Si30. X-ray diffraction, thermal analysis, electron microprobe, Glow Discharge Mass Spectrometry, temperature dependent electrical conductivity and Seebeck coefficient measurements characterized the single crystals. The Thermoelectric performance was shown to be heavily dependent on the synthetic conditions including container choice, thermal history and impurity concentration. Inorganic Clathrates have attracted intense interest in last several years as potential new materials for thermoelectric devices. If a small to moderate increase in thermoelectric performance over the currently used materials is realized, substantial environmental and technological gains could be achieved. Since thermoelectric refrigeration modules require no moving parts or heat exchange gas (freon) they offer significant advantages over conventional refrigeration technology that tends to fail due to the finite lifetime of the pumping equipment. High temperature devices are also extremely useful for power generation in harsh unforgiving environments where excess heat is available. The thermoelectric performance, primarily at room temperature, of these compounds was found to be heavily dependent on the synthetic procedures used to obtain them. A flux growth procedure was developed to overcome the problems of the traditional melt-quench-anneal solid-state chemical approach. This procedure yielded large single crystals of the Sr8Ga16Ge 30, Ba8Ga16Ge30 and Ba8Ga 16Si30 compounds which ready facilitated their chemical and electronic study. Finally, an outlook on the application of these compounds as thermoelectric devices is given. Application of the flux method to other systems was also successful in the discovery of two new inorganic clathrate compounds: type IV Eu4Ga 8Ge16 and type V Yb8Ga16Ge14. The Eu4Ga8Ge16 compound was found to

  2. Stable Occupancy of Hydrogen Molecules in H2 Clathrate Hydrates and H2 + THF Clathrate Hydrates Determined by Ab Initio Calculations

    Directory of Open Access Journals (Sweden)

    Prasad Yedlapalli

    2010-01-01

    Full Text Available Structure II clathrate hydrates of pure hydrogen and binary hydrates of THF+H2 are studied using ab initio calculations to determine the stable occupancies of small cavities. Ab initio calculations are carried out for a double cavity consisting of one dodecahedron (small cavity and one hexakaidecahedron (large cavity. These two cavities are attached to each other as in sII hydrates to form a double cavity. One or two H2 molecules are placed in the small cavity and one THF (or 4H2 molecules molecule is placed in the large cavity. We have determined the binding energies of the double cavities at the MP2 level using various basis sets (3-21G, 3-21G(2p, 3-21++G(2p, 6-31G, 6-31G(2p, and 6-31++G(2p. Different basis sets yield different stable occupancies of the small cavity. The results from the highest basis set (6-31++G(2p with zero point energy corrections indicate that the single occupancy is slightly more favorable than the double occupancy in both the cases of pure H2 hydrates and THF + H2 double hydrates.

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    Gas clathrate hydrate dissociation pressures are reported for mixtures of carbon dioxide, water and thermodynamic promoters forming structure II hydrates.Hydrate (H)-aqueous liquid (Lw)-vapour (V) equilibrium pressures for the ternary system composed of water, tetrahydrofuran (THF), and carbon...... dioxide (CO2), with 5.0mole percent THF in the initial aqueous phase, are presented in the temperature range from 283.3K to 285.2K. At 283.3K, the three-phase equilibrium pressure is determined to be 0.61MPa (absolute pressure).Four-phase hydrate (H)-aqueous liquid (Lw)-organic liquid (La)-vapour (V....... It is shown that upon adding THF to the pure aqueous phase to form a 4mass percent solution, the equilibrium pressure of the formed hydrates may be lowered compared to the ternary system of water, cyclopentane and carbon dioxide. © 2013 Elsevier Ltd....

  4. Analytical Cell Potentials for Clathrate-Hydrates from Inversion of Langmuir Constant Versus Temperature Curves

    CERN Document Server

    Bazant, M Z; Bazant, Martin Z.; Trout, Bernhardt L.

    2000-01-01

    Experimental Langmuir constants for clathrate-hydrates, which are inferred from phase equilibrium data using an equation of state and the statistical thermodynamical model of van der Waals and Platteeuw (vdWP), contain a wealth of information about intermolecular forces. In the simplest (Lennard-Jones and Devonshire) approximation of a spherical cell, the Langmuir constant is related to a configurational integral involving a spherically averaged cell potential. All previous attempts to interpret experimental data based on this formalism have involved numerical fitting with ad hoc functional forms, such as the popular Kihara potential. In addition to lacking analytical insight, however, such empirical fits often produce parameters contradicting those obtained by other means. As a more appealing alternative, the spherical-cell vdWP formula for the Langmuir constant versus temperature can be viewed as a nonlinear integral equation for the cell potential. In this article, a variety of exact analytical solutions a...

  5. Clathrate formation of gossypol: The structure of the complex of gossypol with tropolone

    International Nuclear Information System (INIS)

    The clathrate of gossypol with tropolone is prepared for the first time and studied by X-ray diffraction. The structure is determined and refined using 7307 reflections (Siemens SMART/CCD diffractometer). The crystals are monoclinic, C30H30O8 · 2C7H6O2 , a = 35.5892(1) A, b 12.8893(2) A, c = 18.5910(2) A, β = 118.54(3) deg., Z = 8, space group C2/c, and R = 0.058. Each gossypol molecule is linked to two tropolone molecules through hydrogen bonds. The host (gossypol) and guest (tropolone) molecules form separate bilayers that are parallel to the bc plane and alternate along the a-axis

  6. Synthesis of hydrogen-carbon clathrate material and hydrogen evolution therefrom at moderate temperatures and pressures

    Science.gov (United States)

    Lueking, Angela; Narayanan, Deepa

    2011-03-08

    A process for making a hydrogenated carbon material is provided which includes forming a mixture of a carbon source, particularly a carbonaceous material, and a hydrogen source. The mixture is reacted under reaction conditions such that hydrogen is generated and/or released from the hydrogen source, an amorphous diamond-like carbon is formed, and at least a portion of the generated and/or released hydrogen associates with the amorphous diamond-like carbon, thereby forming a hydrogenated carbon material. A hydrogenated carbon material including a hydrogen carbon clathrate is characterized by evolution of molecular hydrogen at room temperature at atmospheric pressure in particular embodiments of methods and compositions according to the present invention.

  7. Études thermodynamiques sur les Semi-Clathrate Hydrates de TBAB + gaz contenant du Dioxyde de Carbone

    OpenAIRE

    Eslamimanesh, Ali

    2012-01-01

    CO2 capture has become an important area of research mainly due to its drastic green-house effects. Gas hydrate formation as a separation technique shows tremendous potential, both from a physical feasibility as well as an envisaged lower energy utilization criterion. Briefly, gas (clathrate) hydrates are non-stoichiometric, ice-like crystalline compounds formed through a combination of water and suitably sized guest molecule(s) under low-temperatures and elevated pressures. As the pressure r...

  8. Cross-nucleation between clathrate hydrate polymorphs: assessing the role of stability, growth rate, and structure matching.

    Science.gov (United States)

    Nguyen, Andrew H; Molinero, Valeria

    2014-02-28

    Cross-nucleation is a phenomenon where a new crystal nucleates and grows upon the surface of a different polymorph. Previous studies indicate that faster growth rate of the new crystal is a necessary but not sufficient condition for cross-nucleation. The thermodynamic stability of the different polymorphs can also affect cross-nucleation by modulating the rates of crystal growth. The interplay between thermodynamic stability of the polymorphs involved, the growth rate of the crystals, and the need for creation of an interfacial transition layer that seamlessly connects the two structures has not yet been fully elucidated. Predicting cross-nucleation is particularly challenging for clathrate hydrates, for which there are sometimes several polymorphs with similar stability and for which growth rates are not known. In this work, we use molecular dynamics simulations to investigate which factor (stability, growth rate, or formation of interfacial transition layer) controls cross-nucleation between the four known Frank-Kasper clathrate hydrate polymorphs: sI, sII, TS, and HS-I. We investigate the growth and cross-nucleation of these four hydrates filled with a set of guest molecules that produce different order of stabilities for the four crystal structures. We determine that the growth rate of sII clathrate is the fastest, followed by TS, HS-I, and sI. We find that cross-nucleation into or from sII clathrates is preceded by the formation of an interfacial transition layer at the seed crystal/liquid interface because sII does not share a crystal plane with sI, HS-I, or TS. Cross-nucleation between the latter three can occur seamlessly and is determined only by their growth rates. Our results indicate that nucleation of an interfacial transition layer between non-matching polymorphs can control cross-nucleation or lack thereof under conditions of small driving force. Under conditions of sufficient supercooling clathrate hydrate polymorphs cross-nucleate into the fastest

  9. Phase equilibrium measurements for semi-clathrate hydrates of the (CO2 + N2 + tetra-n-butylammonium bromide) aqueous solution system

    International Nuclear Information System (INIS)

    Highlights: ► Semi-clathrate hydrate phase equilibrium for CO2+N2+TBAB aqueous solutions. ► Measurements for temperatures from 277.1 K to 293.2 K and pressures up to 16.21 MPa. ► TBAB has a promotion effect on semi-clathrate hydrate formation. - Abstract: The application of semi-clathrate hydrate formation technology for gas separation purposes has gained much attention in recent years. Consequently, there is a demand for experimental data for relevant semi-clathrate hydrate phase equilibria. In this work, semi-clathrate hydrate dissociation conditions for the system comprising mixtures of {CO2 (0.151/0.399 mole fraction) + N2 (0.849/0.601 mole fraction) + 0.05, 0.15, and 0.30 mass fraction tetra-n-butylammonium bromide (TBAB)} aqueous solutions have been measured and are reported. An experimental apparatus which was designed and built in-house was used for the measurements using the isochoric pressure-search method. The range of conditions for the measurements was from 277.1 K to 293.2 K for temperature and pressures up to 16.21 MPa. The phase equilibrium data measured demonstrate the high hydrate promotion effects of TBAB aqueous solutions.

  10. In situ apparatus for the study of clathrate hydrates relevant to solar system bodies using synchrotron X-ray diffraction and Raman spectroscopy

    CERN Document Server

    Day, Sarah J; Evans, Aneurin; Parker, Julia E

    2015-01-01

    Clathrate hydrates are believed to play a significant role in various solar system environments, e.g. comets, and the surfaces and interiors of icy satellites, however the structural factors governing their formation and dissociation are poorly understood. We demonstrate the use of a high pressure gas cell, combined with variable temperature cooling and time-resolved data collection, to the in situ study of clathrate hydrates under conditions relevant to solar system environments. Clathrates formed and processed within the cell are monitored in situ using synchrotron X-ray powder diffraction and Raman spectroscopy. X-ray diffraction allows the formation of clathrate hydrates to be observed as CO2 gas is applied to ice formed within the cell. Complete conversion is obtained by annealing at temperatures just below the ice melting point. A subsequent rise in the quantity of clathrate is observed as the cell is thermally cycled. Four regions between 100-5000cm-1 are present in the Raman spectra that carry feature...

  11. Clathrate Sequestration: State-of-the-Art Review and New Technical Approaches

    Directory of Open Access Journals (Sweden)

    Annick Nago

    2011-01-01

    Full Text Available This paper focuses on reviewing the currently available solutions for natural gas production from methane hydrate deposits using CO2 sequestration. Methane hydrates are ice-like materials, which form at low temperature and high pressure and are located in permafrost areas and oceanic environments. They represent a huge hydrocarbon resource, which could supply the entire world for centuries. Fossil-fuel-based energy is still a major source of carbon dioxide emissions which contribute greatly to the issue of global warming and climate change. Geological sequestration of carbon dioxide appears as the safest and most stable way to reduce such emissions for it involves the trapping of CO2 into hydrocarbon reservoirs and aquifers. Indeed, CO2 can also be sequestered as hydrates while helping dissociate the in situ methane hydrates. The studies presented here investigate the molecular exchange between CO2 and CH4 that occurs when methane hydrates are exposed to CO2, thus generating the release of natural gas and the trapping of carbon dioxide as gas clathrate. These projects include laboratory studies on the synthesis, thermodynamics, phase equilibrium, kinetics, cage occupancy, and the methane recovery potential of the mixed CO2–CH4 hydrate. An experimental and numerical evaluation of the effect of porous media on the gas exchange is described. Finally, a few field studies on the potential of this new gas hydrate recovery technique are presented.

  12. Weak interactions between water and clathrate-forming gases at low pressures

    Energy Technology Data Exchange (ETDEWEB)

    Thurmer, Konrad; Yuan, Chunqing; Kimmel, Gregory A.; Kay, Bruce D.; Smith, R. Scott

    2015-11-01

    Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10-1 mbar methane or 10-5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~107 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10-5 mbar methane does not alter their morphology, suggesting that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water-gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~43 K and isobutane desorbs near ~100 K. Similar desorption temperatures were observed for desorption from amorphous solid water.

  13. Connecting the Rheological Behavior of Clathrate Hydrate Slurries to Flow Performance

    Science.gov (United States)

    Geri, Michela; Venkatesan, Rama; McKinley, Gareth; MIT Team; Chevron ETC Team

    2014-11-01

    Clathrate hydrates represent a major flow assurance issue for deep water drilling operations. To develop a proper constitutive model, an extensive set of rheological measurements has been performed on a model hydrate forming emulsion. Upon hydrate formation a sharp increase in the fluid viscosity is observed (by a factor of 100 to 1000). Steady shear measurements show that the hydrate slurry has a shear thinning behavior as well as a yield stress on the order of 1-10 Pa which increases with aging of the fluid. Thixotropy becomes evident as a hysteretic behavior in the flow curve, even when no rheological aging has occurred. Creep tests also reveal that the fluid microstructure accumulates back stress. Oscillatory measurements show that in the linear viscoelastic region hydrate slurries develop viscoelastic gel-like behavior with the elastic modulus exceeding the viscous modulus. These characteristics guide the development of an elastoviscoplastic constitutive model that can capture the salient dynamic features in simple unidirectional flows (e.g. steady or transient Poiseuille) such as apparent wall slip, plug flow or excessive pressure drop in start-up flow.

  14. Hydrate-phobic surfaces: fundamental studies in clathrate hydrate adhesion reduction.

    Science.gov (United States)

    Smith, J David; Meuler, Adam J; Bralower, Harrison L; Venkatesan, Rama; Subramanian, Sivakumar; Cohen, Robert E; McKinley, Gareth H; Varanasi, Kripa K

    2012-05-01

    Clathrate hydrate formation and subsequent plugging of deep-sea oil and gas pipelines represent a significant bottleneck for deep-sea oil and gas operations. Current methods for hydrate mitigation are expensive and energy intensive, comprising chemical, thermal, or flow management techniques. In this paper, we present an alternate approach of using functionalized coatings to reduce hydrate adhesion to surfaces, ideally to a low enough level that hydrodynamic shear stresses can detach deposits and prevent plug formation. Systematic and quantitative studies of hydrate adhesion on smooth substrates with varying solid surface energies reveal a linear trend between hydrate adhesion strength and the practical work of adhesion (γ(total)[1 + cos θ(rec)]) of a suitable probe liquid, that is, one with similar surface energy properties to those of the hydrate. A reduction in hydrate adhesion strength by more than a factor of four when compared to bare steel is achieved on surfaces characterized by low Lewis acid, Lewis base, and van der Waals contributions to surface free energy such that the practical work of adhesion is minimized. These fundamental studies provide a framework for the development of hydrate-phobic surfaces, and could lead to passive enhancement of flow assurance and prevention of blockages in deep-sea oil and gas operations. PMID:22441203

  15. Constraints on sea to air emissions from methane clathrates in the vicinity of Svalbard

    Science.gov (United States)

    Pisso, Ignacio; Vadakkepuliyambatta, Sunil; Platt, Stephen Matthew; Eckhardt, Sabine; Allen, Grant; Pitt, Joseph; Silyakova, Anna; Hermansen, Ove; Schmidbauer, Norbert; Mienert, Jurgen; Myhre, Cathrine Lund; Stohl, Andreas

    2016-04-01

    Methane stored in the seabed in the form of clathrates has the potential to be released into the atmosphere due to ongoing ocean warming. The Methane Emissions from Arctic Ocean to Atmosphere (MOCA, http://moca.nilu.no/) proje sct conducted measurement campaigns in the vicinity of Svalbard during the summers of 2014 and 2015 in collaboration with the Centre for Arctic Gas Hydrate, Environment and Climate (CAGE, https://cage.uit.no/) and the MAMM (https://arcticmethane.wordpress.com) project . The extensive set of measurements includes air (BAe 146) and ship (RV Helmer Hansen) borne methane concentrations, complemented with the nearby monitoring site at Zeppelin mountain. In order to assess the atmospheric impact of emissions from seabed methane hydrates, we characterised the local and long range atmospheric transport during the aircraft campaign and different scenarios for the emission sources. We present a range of upper bounds for the CH4 emissions during the campaign period as well as the methodologies used to obtain them. The methodologies include a box model, Lagrangian transport and elementary inverse modelling. We emphasise the analysis of the aircraft data. We discuss in detail the different methodologies used for determining the upper flux bounds as well as its uncertainties and limitations. The additional information provided by the ship and station observations will be briefly mentioned.

  16. Sn-based type-Ⅷ single-crystal clathrates with a large figure of merit

    Institute of Scientific and Technical Information of China (English)

    Deng Shu-Kang; Li De-Cong; Shen Lan-Xian; Hao Rui-Ting; T. Takabatake

    2012-01-01

    Single-crystal samples of type-Ⅷ BasGa16-xCuxSn30 (x =0,0.03,0.06,0.15) clathrates were prepared using the Sn-flux method.At room temperature the carrier density,n,is 3.5-5 × 1019 cm-3 for all the samples,the carrier mobility,μH,increases to more than twice that of BasGa16Sn30 for all the Cu doping samples,and consequently the electrical conductivity is enhanced distinctly from 1.90 × 104 S/m to 4.40 × 104 S/m,with the Cu composition increasing from x =0 to x =0.15.The Seebeck coefficient,α,decreases slightly with the increases in Cu composition.The k values are about 0.72 W/mK at 300 K and are almost invariant with temperature up to 500 K for the samples with x =0 and x =0.03.The lattice thermal conductivity,kL,decreases from 0.59 W/mK for x =0 to 0.50 W/mK for x =0.03 at 300 K.The figure of merit for x =0.03 reaches 1.35 at 540 K.

  17. Synthesis of polyphenylacetylene by radiation-induced polymerization in deoxycholic acid clathrate

    International Nuclear Information System (INIS)

    Phenylacetylene was polymerized as inclusion compound (clathrate) inside deoxycholic acid (DOCA) crystals. The polymerization was initiated by γ radiation and a total dose of 320 kGy was employed. The resulting polyphenylacetylene (PPA) was isolated by dissolution of deoxycholic acid in boiling ethanol. PPA high polymer was accompanied by a series of phenylacetylene oligomers, which were detected by liquid chromatographic analysis (HPLC). PPA was characterized by electronic absorption spectroscopy and by FT-IR spectroscopy in comparison to a reference PPA prepared by a stereospecific catalyst. The microstructure of PPA from inclusion polymerization was highly trans type, similar to that observed on PPA prepared by bulk radiolysis. No optical activity was detected by polarimetry on PPA prepared by inclusion polymerization. The host-guest complex PPA/DOCA was studied by differential thermal analysis (DTA) and by thermogravimetry (TGA). DTA provided evidences of the host-guest complex formation from the shift of the melting point of DOCA while the TGA confirmed the identity - in terms of thermal behaviour - of the PPA from inclusion polymerization with that from stereospecific polymerization

  18. Encapsulation of saline solution by tetrahydrofuran clathrate hydrates and inclusion migration by recrystallization.

    Science.gov (United States)

    Nagashima, Kazushige; Orihashi, Suguru; Yamamoto, Yoshitaka; Takahashi, Masayoshi

    2005-05-26

    Encapsulation of saline solution as an impurity in tetrahydrofuran clathrate hydrates grown in a stoichiometric solution with 3 wt % NaCl and the release of a saline solution during melting along with inclusion migration by hydrate recrystallization during annealing are studied using a directional growth apparatus in combination with a Mach-Zender interferometer. Interferometric observation revealed that the salt concentration increased locally in the solution near the growth interface. The time evolution of salt concentration in the solution was in accordance with the numerical results obtained from the diffusion equation for salt, assuming perfect rejection of salt by the hydrate. However, after the interfacial pattern developed into a serrated pattern (periodical array of trough and crest), the salt concentration in the solution ceased to increase, deviating from the theoretical value. This indicates that the saline solution was encapsulated by the growth hydrate. On the other hand, upon melting of the slowly grown hydrate, the salt concentration near the interface was observed to be locally high at the location of the trough during growth, whereas it was dilute at the location of the growth crest. Furthermore, when the hydrate was annealed under an applied temperature gradient, the inclusions (encapsulated saline solution) in the hydrate migrated toward the bulk solution and were finally expelled by hydrate recrystallization. The migration speed of the inclusions increased with a larger temperature gradient. By melting the sample over a sufficiently long anneal time, the melt was determined to be completely desalinated.

  19. Clathrates [MPy4(NCO)2]·2Py (M=M(2)=Mn, Fe, Co, Ni, Cu, Zn, Cd; Py=pyridine)

    International Nuclear Information System (INIS)

    Investigation of addition products of six pyridine molecule to cyanates of metals M(OCN)2·6Py (M=Mn, Fe, Co, Ni, Cu, Zn, Cd; Py=pyridine) is conducted. Compounds investigated form isostructural series and are isomorphous to other clathrates [MPy4X2]·2Py. Coordination polyhedron is slightly distorted due to difference in bond lengths. Conformation of the molecule is propeller-type. Guest molecules are arranged in in hollows of crystal structure in accordance with Van-der-Waals type of packing. Thermal decomposition of cadmium clathrate in dependence on conditions is derived in one stage up to host complex or with host dissociation

  20. Thermoelectric material including a multiple transition metal-doped type I clathrate crystal structure

    Science.gov (United States)

    Yang, Jihui; Shi, Xun; Bai, Shengqiang; Zhang, Wenqing; Chen, Lidong; Yang, Jiong

    2012-01-17

    A thermoelectric material includes a multiple transition metal-doped type I clathrate crystal structure having the formula A.sub.8TM.sub.y.sub.1.sup.1TM.sub.y.sub.2.sup.2 . . . TM.sub.y.sub.n.sup.nM.sub.zX.sub.46-y.sub.1.sub.-y.sub.2.sub.- . . . -y.sub.n.sub.-z. In the formula, A is selected from the group consisting of barium, strontium, and europium; X is selected from the group consisting of silicon, germanium, and tin; M is selected from the group consisting of aluminum, gallium, and indium; TM.sup.1, TM.sup.2, and TM.sup.n are independently selected from the group consisting of 3d, 4d, and 5d transition metals; and y.sub.1, y.sub.2, y.sub.n and Z are actual compositions of TM.sup.1, TM.sup.2, TM.sup.n, and M, respectively. The actual compositions are based upon nominal compositions derived from the following equation: z=8q.sub.A-|.DELTA.q.sub.1|y.sub.1-|.DELTA.q.sub.2|y.sub.2- . . . -|.DELTA.q.sub.n|y.sub.n, wherein q.sub.A is a charge state of A, and wherein .DELTA.q.sub.1, .DELTA.q.sub.2, .DELTA.q.sub.n are, respectively, the nominal charge state of the first, second, and n-th TM.

  1. Competing quantum effects in the free energy profiles and diffusion rates of hydrogen and deuterium molecules through clathrate hydrates

    CERN Document Server

    Cendagorta, Joseph R; Hele, Timothy J H; Marsalek, Ondrej; Bačić, Zlatko; Tuckerman, Mark E

    2016-01-01

    Clathrate hydrates hold considerable promise as safe and economical materials for hydrogen storage. Here we present a quantum mechanical study of H$_2$ and D$_2$ diffusion through a hexagonal face shared by two large cages of clathrate hydrates over a wide range of temperatures. Path integral molecular dynamics simulations are used to compute the free-energy profiles for the diffusion of H$_2$ and D$_2$ as a function of temperature. Ring polymer molecular dynamics rate theory, incorporating both exact quantum statistics and approximate quantum dynamical effects, is utilized in the calculations of the H$_2$ and D$_2$ diffusion rates in a broad temperature interval. We find that the shape of the quantum free-energy profiles and their height relative to the classical free energy barriers at a given temperature, as well as the rate of diffusion, are profoundly affected by competing quantum effects: above 25 K, zero-point energy (ZPE) perpendicular to the reaction path for diffusion between cavities decreases the ...

  2. Hydrogen storage and carbon dioxide sequestration in TBAF semi-clathrate hydrates: Kinetics and evolution of hydrate-phase composition by in situ raman spectroscopy - Abstract -

    NARCIS (Netherlands)

    Torres Trueba, A.; Radoviæ, I.R.; Zevenbergen, J.F.; Kroon, M.C.; Peters, C.J.

    2012-01-01

    Carbon dioxide (CO2) represents almost one third of the emissions from the combustion of fossil fuels additionally, CO2 has been identified as the mayor contributor of global warming. Hydrogen (H2), on the other hand, due to its properties is considered a promising energy carrier. Clathrate hydrates

  3. Methods of thermoelectric enhancement in silicon-germanium alloy type I clathrates and in nanostructured lead chalcogenides

    Science.gov (United States)

    Martin, Joshua

    The rapid increase in thermoelectric (TE) materials R&D is a consequence of the growing need to increase energy efficiency and independence through waste heat recovery. TE materials enable the direct solid-state conversion of heat into electricity, with little maintenance, noise, or cost. In addition, these compact devices can be incorporated into existing technologies to increase the overall operating efficiency. High efficiency TE materials would enable the practical solid-state conversion of thermal to electrical energy. Optimizing the interdependent physical parameters to achieve acceptable efficiencies requires materials exhibiting a unique combination of properties. This research reports two methods of thermoelectric enhancement: lattice strain effects in silicon-germanium alloy type I clathrates and the nanostructured enhancement of lead chalcogenides. The synthesis and chemical, structural, and transport properties characterization of Ba8Ga16SixGe30-x type I clathrates with similar Ga-to-group IV element ratios but with increasing Si substitution (4 < x < 14) is reported. Substitution of Si within the Ga-Ge lattice framework of the type I clathrate Ba8Ga16Ge30 results in thermoelectric performance enhancement. The unique dependences of carrier concentration, electrical resistivity, Seebeck coefficient, and carrier effective mass on Si substitution level, may imply a modified band structure with Si substitution. These materials were then further optimized by adjusting the Ga-to-group IV element ratios. Recent progress in a number of higher efficiency TE materials can be attributed to nanoscale enhancement. Many of these materials demonstrate increased Seebeck coefficient and decreased thermal conductivity due to the phenomenological properties of nanometer length scales. To satisfy the demands of bulk industrial applications requires additional synthesis techniques to incorporate nanostructure directly within a bulk matrix. This research investigates, for

  4. Gas hydrates and clathrates. Flow assurance, environmental and economic perspectives and the Nigerian liquefied natural gas project

    International Nuclear Information System (INIS)

    Gas hydrates are nonstoichiometric crystalline compounds that belong to the inclusion group known as clathrates. They occur when water molecules attach themselves together through hydrogen bonding and form cavities which can be occupied by a single gas or volatile liquid molecule. Gas hydrates, asphaltenes and waxes are three major threats to flow assurance that must be well assessed by design team uptime. Gas hydrates are also looked upon as a future energy source and as a potential climate hazard. The purpose of this review is to show the chemistry and mechanism of gas hydrate formation, the problems they pose, especially to flow assurance, their system implications, their environmental and economic perspectives with respect to their prospects as storage and transport alternative to the liquefied natural gas technology. (author)

  5. Observations of CO{sub 2} clathrate hydrate formation and dissolution under deep-ocean disposal conditions

    Energy Technology Data Exchange (ETDEWEB)

    Warzinski, R.P.; Cugini, A.V. [Department of Energy, Pittsburgh, PA (United States); Holder, G.D. [Univ. of Pittsburgh, Pittsburgh, PA (United States)

    1995-11-01

    Disposal of anthropogenic emissions of CO{sub 2} may be required to mitigate rises in atmospheric levels of this greenhouse gas if other measures are ineffective and the worst global warming scenarios begin to occur. Long-term storage of large quantities of CO{sub 2} has been proposed, but the feasibility of large land and ocean disposal options remains to be established. Determining the fate of liquid CO{sub 2} injected into the ocean at depths greater than 500 m is complicated by uncertainties associated with the physical behavior of CO{sub 2} under these conditions, in particular the possible formation of the ice-like CO{sub 2} clathrate hydrate. Resolving this issue is key to establishing the technical feasibility of this option. Experimental and theoretical work in this area is reported.

  6. Distribution of Al atoms in the clathrate-I phase Ba8AlxSi46-x at x = 6.9.

    Science.gov (United States)

    Bobnar, Matej; Böhme, Bodo; Wedel, Michael; Burkhardt, Ulrich; Ormeci, Alim; Prots, Yurii; Drathen, Christina; Liang, Ying; Nguyen, Hong Duong; Baitinger, Michael; Grin, Yuri

    2015-07-28

    The clathrate-I phase Ba8AlxSi46-x has been structurally characterized at the composition x = 6.9 (space group Pm3[combining macron]n, no. 223, a = 10.4645(2) Å). A crystal structure model comprising the distribution of aluminium and silicon atoms in the clathrate framework was established: 5.7 Al atoms and 0.3 Si atoms occupy the crystallographic site 6c, while 1.2 Al atoms and 22.8 Si atoms occupy site 24k. The atomic distribution was established based on a combination of (27)Al and (29)Si NMR experiments, X-ray single-crystal diffraction and wavelength-dispersive X-ray spectroscopy. PMID:26085288

  7. 磺丁基醚-β-环糊精/格列本脲包合物的制备%Preparation of butyl ether - β - cyclodextrin and glibenclamide clathrate

    Institute of Scientific and Technical Information of China (English)

    刘凯; 何媛

    2015-01-01

    Objective To prepare butyl ether - β - cyclodextrin and glibenclamide clathrate,and explore their effect on improve the dissolution and stability of drug. Methods Phase solubility method was implemented to determine the ap-parent stability constant,neutralization was used to prepare butyl ether - β - cyclodextrin and glibenclamide clathrate;The dissolution of inclusion compounds was investigated. Results Compared with the glibenclamide bulk drug,butyl ether - β- cyclodextrin and Glibenclamide clathrate had increased the drug solubility significantly. Conclusion The preparation of butyl ether - β - cyclodextrin and glibenclamide clathrate had good practical application value.%目的:制备磺丁基醚-β-环糊精/格列本脲包合物,并对其提高药物溶解性和稳定性的作用进行考察。方法采用相溶解度法测定表观稳定常数,中和法制备磺丁基醚-β-环糊精/格列本脲包合物,并对包合物的溶出度进行了考察。结果与格列本脲原料药相比,磺丁基醚-β-环糊精/格列本脲包合物显著提高了药物的溶解度。结论制备格列本脲的环糊精包合物具有良好的实际应用价值。

  8. The Location of the CO2, Fundamental in Clathrate Hydrates and its Application to Infrared Spectra of Icy Solar System Objects

    Science.gov (United States)

    Sandford, S. A.; Mastrapa, R. M. E.; Bernstein, M. P.; Cruikshank, D. P.

    2006-01-01

    CO2 is present on the surface of many Solar System objects, but not always as a segregated, pure ice. In pure CO2-ice, the fundamental absorption is located near 4.268 micron (2343.3 wavenumbers). However, on several objects, the CO2 fundamental is shifted to higher frequency. This shift may be produced by CO2 gas trapped in another material, or adsorbed onto minerals. We have seen that a mixture of H2O, CH3OH4 and CO2 forms a type II clathrate when heated to 125 K and produces a CO2 fundamental near 4.26 micron. The exact location of the feature is strongly dependent on the initial ratio of the three components. We are currently exploring various starting ratios relevant to the Solar System to determine the minimum amount of CH3OH needed to convert all of the CO2 to the clathrate, i.e. eliminate the splitting of the CO2 fundamental. We are testing the stability of the clathrate to thermal processing and UV photolysis, and documenting the changes seen in the spectra in the wavelength range from 1-5 micron. We acknowledge financial support from the Origins of Solar Systems Program, the Planetary Geology and Geophysics and the NASA Postdoctoral Program.

  9. Ab initio computational study on the lattice thermal conductivity of Zintl clathrates [Si19P4] Cl4 and Na4[Al4Si19

    Science.gov (United States)

    Härkönen, Ville J.; Karttunen, Antti J.

    2016-08-01

    The lattice thermal conductivity of silicon clathrate framework Si23 and two Zintl clathrates, [Si19P4] Cl4 and Na4[Al4Si19] , is investigated by using an iterative solution of the linearized Boltzmann transport equation in conjunction with ab initio lattice dynamical techniques. At 300 K, the lattice thermal conductivities for Si23, [Si19P4] Cl4 , and Na4[Al4Si19] were found to be 43 W/(m K), 25 W/(m K), and 2 W/(m K), respectively. In the case of Na4[Al4Si19] , the order-of-magnitude reduction in the lattice thermal conductivity was found to be mostly due to relaxation times and group velocities differing from Si23 and [Si19P4] Cl4 . The difference in the relaxation times and group velocities arises primarily due to the phonon spectrum at low frequencies, resulting eventually from the differences in the second-order interatomic force constants (IFCs). The obtained third-order IFCs were rather similar for all materials considered here. The present findings are similar to those obtained earlier for some skutterudites. The predicted lattice thermal conductivity of Na4[Al4Si19] is in line with the experimentally measured thermal conductivity of recently synthesized type-I Zintl clathrate Na8[Al8Si38] (polycrystalline samples).

  10. Theoretical Study of the Properties of the Type II Clathrate A^xSn^136, (A = alkali atom; 0 <= x <= 24)

    Science.gov (United States)

    Xue, Dong; Higgins, Craig; Myles, Charley

    2012-10-01

    Motivated by recent experimental and theoretical interest in the x dependence of the properties of the Si and Ge-based Type II clathrate materials A^xSi^136 and A^xGe^136 (A = alkali atom) [1,2] we are carrying out a systematic theoretical study of the properties of the Sn-based Type II clathrate system A^xSn^136. Type II clathrates have cage-like lattices in which Si, Ge, or Sn atoms are tetrahedrally-coordinated and sp3 covalently bonded. The cages can contain ``guests''; usually alkali or alkaline earth atoms. These materials are particularly interesting because of their potential use as thermoelectrics. Recent powder X-ray diffraction experiments have found the very interesting result that, for increasing x in the range 0 10.1021/cg200756r[0pt] [2] M. Beekman, E. Nenghabi, K. Biswas, C. Myles, M. Baitinger, Y. Grin, G.S. Nolas, Inorg. Chem. 49 2010, DOI: 10.1021/ic1005049

  11. Bulk and surface structure and high-temperature thermoelectric properties of inverse clathrate-III in the Si-P-Te system.

    Science.gov (United States)

    Zaikina, Julia V; Mori, Takao; Kovnir, Kirill; Teschner, Detre; Senyshyn, Anatoliy; Schwarz, Ulrich; Grin, Yuri; Shevelkov, Andrei V

    2010-11-01

    The creation of thermoelectric materials for waste heat recovery and direct solar energy conversion is a challenge that forces the development of compounds that combine appreciable thermoelectric figure-of-merit with high thermal and chemical stability. Here we propose a new candidate for high-temperature thermoelectric materials, the type-III Si(172-x)P(x)Te(y) cationic clathrate, in which the framework is composed of partially ordered silicon and phosphorus atoms, whereas tellurium atoms occupy guest positions. We show that the utmost stability of this clathrate (up to 1500 K) in air is ensured by the formation of a nanosized layer of phosphorus-doped silica on the surface, which prevents further oxidation and degradation. As-cast (non-optimized) Si-P-Te clathrates display rather high values of the thermoelectric figure-of-merit (ZT=0.24-0.36) in the temperature range of 700-1100 K. These ZT values are comparable to the best values achieved for the properly doped transition-metal-oxide materials. The methods of the thermoelectric efficiency optimization are discussed.

  12. Structural, elastic, and electronic properties of sodium atoms encapsulated type-I silicon-clathrate compound under high pressure

    Science.gov (United States)

    Zhang, Wei; Chen, Qing-Yun; Zeng, Zhao-Yi; Cai, Ling-Cang

    2015-10-01

    We calculated the structural, elastic, and electronic properties of alkali metal Na atoms doped type-I silicon-clathrate compound (Na8Si46) under pressure using first-principles methods. The obtained dependencies of bond lengths and bond angles on pressure show heterogeneous behaviors which may bring out a structural transition. By using the elastic stability criteria from the calculated elastic constants, we confirm that the Na8Si46 is elastically unstable under high pressure. Some of the mechanical and thermal quantities include bulk modulus, shear modulus, Young’s modulus, Debye temperature, sound velocity, melting point, and hardness, which are also derived from the elastic constants. The calculated total and partial electron densities of states of Na8Si46 indicate a weak interaction between the encapsulated Na atoms and the silicon framework. Moreover, the effect of pressure on its electronic structure is also investigated, which suggests that pressure is not a good choice to enhance the thermoelectricity performance of Na8Si46. Project supported by National Natural Science Foundation of China (Grant Nos. 11347134 and 11304254) and the Doctor Foundation of Southwest University of Science and Technology, China (Grant No. 13zx7125).

  13. High-pressure studies on a new superconducting clathrate: Ba sub 6 Ge sub 2 sub 5

    CERN Document Server

    Yuan, H Q; Carrillo-Cabrera, W; Paschen, S; Sparn, G; Baenitz, M; Grin, Y; Steglich, F

    2002-01-01

    The effect of pressure on the low-temperature states of the newly discovered clathrate Ba sub 6 Ge sub 2 sub 5 is investigated by means of measurements of the electrical resistivity. At ambient pressure, Ba sub 6 Ge sub 2 sub 5 undergoes a two-step structural phase transition between 230 and 180 K from metallic behaviour to a high-resistivity state characterized by a mean free path of about 3 A. Interestingly, a Bardeen-Cooper-Schrieffer-like (BCS-like) superconducting transition occurs at T sub C approx 0.24 K from the resulting 'bad metal'. With increasing pressure, the structural phase transition is depressed but T sub C increases drastically. T sub C reaches a maximum value of 3.85 K at the critical pressure p sub C approx 2.8 GPa, where the structural distortion is completely suppressed and the system exhibits metallic behaviour. Higher pressures lead to a slight decrease of T sub C.

  14. Coloration and darkening of methane clathrate and other ices by charged particle irradiation - Applications to the outer solar system

    Science.gov (United States)

    Thompson, W. Reid; Murray, B. G. J. P. T.; Khare, B. N.; Sagan, Carl

    1987-01-01

    The results of laboratory experiments simulating the irradiation of hydrocarbon-H2O or hydrocarbon-H2O/NH3 clathrates by charged particles in the outer solar system are reported. Ices produced by condensing and boiling liquid CH4 on an H2O frost surface at 100 K or by cocondensing frosts from gaseous mixtures were exposed to coronal-discharge electron irradiation at 77 K, and the spectral properties of the irradiated surfaces were determined. Significant darkening of the initially white ices was observed at doses of 1 Gerg/sq cm, corresponding to 8-500 yrs of irradiation by Uranian magnetospheric electrons on the surfaces of the principal Uranian satellites, or to total destruction of CH4 in the upper 1 mm of the satellite surfaces after 0.05-3.0 Myr. It is estimated that 10 m or more of icy satellite or comet surfaces would be radiation-hardened to a CH4-free ice-tholin mixture over 4 Gyr.

  15. Intra-cage dynamics of molecular hydrogen confined in cages of two different dimensions of clathrate hydrates

    Science.gov (United States)

    Russina, Margarita; Kemner, Ewout; Mezei, Ferenc

    2016-06-01

    In porous materials the molecular confinement is often realized by means of weak Van der Waals interactions between the molecule and the pore surface. The understanding of the mechanism of such interactions is important for a number of applications. In order to establish the role of the confinement size we have studied the microscopic dynamics of molecular hydrogen stored in the nanocages of clathrate hydrates of two different dimensions. We have found that by varying the size of the pore the diffusive mobility of confined hydrogen can be modified in both directions, i.e. reduced or enhanced compared to that in the bulk solid at the same temperatures. In the small cages with a mean crystallographic radius of 3.95 Å the confinement reduces diffusive mobility by orders of magnitude. In contrast, in large cages with a mean radius of 4.75 Å hydrogen molecules displays diffusive jump motion between different equilibrium sites inside the cages, visible at temperatures where bulk H2 is solid. The localization of H2 molecules observed in small cages can promote improved functional properties valuable for hydrogen storage applications.

  16. Structural, elastic, and electronic properties of sodium atoms encapsulated type-I silicon-clathrate compound under high pressure

    Institute of Scientific and Technical Information of China (English)

    张伟; 陈青云; 曾召益; 蔡灵仓

    2015-01-01

    We calculated the structural, elastic, and electronic properties of alkali metal Na atoms doped type-I silicon–clathrate compound (Na8Si46) under pressure using first-principles methods. The obtained dependencies of bond lengths and bond angles on pressure show heterogeneous behaviors which may bring out a structural transition. By using the elastic stability criteria from the calculated elastic constants, we confirm that the Na8Si46 is elastically unstable under high pressure. Some of the mechanical and thermal quantities include bulk modulus, shear modulus ,Young’s modulus, Debye temperature, sound velocity, melting point, and hardness, which are also derived from the elastic constants. The calculated total and partial electron densities of states of Na8Si46 indicate a weak interaction between the encapsulated Na atoms and the silicon framework. Moreover, the effect of pressure on its electronic structure is also investigated, which suggests that pressure is not a good choice to enhance the thermoelectricity performance of Na8Si46.

  17. Theoretical and Experimental Study on Thermoelectric Properties of Ba8TM x Ga y Ge46- x- y (TM = Zn, Cu, Ag) Type I Clathrates

    Science.gov (United States)

    Leszczynski, Juliusz; Kolezynski, Andrzej; Juraszek, Jarosław; Wojciechowski, Krzysztof

    2016-10-01

    In the type I clathrates Ba8TM x Ga y Ge46- x- y (TM = group 10 to 12 elements) where some of the Ge framework atoms are substituted by Zn, Cu or Ag, the transition-metal elements prefer to occupy the 6 c site. Preliminary band-structure calculations showed that this substitution implies modification of the electronic bands in the vicinity of the energy gap. By appropriate tailoring of the band structure, improved thermoelectric properties can be obtained. More detailed full-potential linearized augmented plane wave (FP-LAPW) method calculations within density functional theory (DFT) were performed using the WIEN2k package for compositions where the transition element TM fully occupies the 6 c site. Additional analysis of the properties of the electron density topology within Bader's atoms-in-molecules approach was carried out to study the chemical bonding in intermetallic clathrates. To verify the theoretical predictions, polycrystalline samples of the type I clathrates Ba8TM x Ga y Ge46- x- y (TM = Zn, Cu, Ag) modified by transition-metal element substitution for Ge were obtained. The samples were characterized using powder x-ray diffraction analysis, scanning electron microscopy, and energy-dispersive x-ray spectroscopy. The electrical conductivity, Seebeck coefficient, and thermal conductivity were measured in the temperature range from 320 K to 720 K. Several models were used to fit the experimental results for the electronic transport properties and to estimate the energy gap. Vacancies at the Ge site were considered responsible for deviations from the desired properties, and appropriate defect equations correlating the vacancies and TM concentration are presented. Finally, the results of DFT calculations are compared with the experiments, showing good agreement with theoretically predicted cell parameters and general observations of the transport properties.

  18. Pre-combustion capture of carbon dioxide in a fixed bed reactor using the clathrate hydrate process

    International Nuclear Information System (INIS)

    Hydrate based gas separation (HBGS) process with silica sand and silica gel as contact medium was employed to capture CO2 from fuel gas mixture. Gas uptake measurement at three different pressures (7.5, 8.5 and 9.0 MPa) and 274.15 K were conducted for hydrate formation kinetics and overall conversion of water to hydrate, rate of hydrate formation were determined. Water conversion of up to 36% was achieved with silica sand bed compared to 13% conversion in the silica gel bed. Effect of driving force on the rate of hydrate formation and gas consumption was significant in silica sand bed whereas it was found to be insignificant in silica gel bed. Hydrate dissociation experiments by thermal stimulation (at constant pressure) alone and a combination of depressurization and thermal stimulation were carried out for complete recovery of the hydrated gas. A driving force of 23 K was found to be sufficient to recover all the hydrated gas within 1 h. This study indicates that silica sand can be an effective porous media for separation of CO2 from fuel gas when compared to silica gel. - Highlights: ► The clathrate process for pre-combustion capture of carbon dioxide in a novel fixed bed reactor is presented. ► Performance of two contact media (silica gel and silica sand) was investigated. ► Water to hydrate conversion was higher in a silica sand column. ► A pressure reduction and thermal stimulation approach is presented for a complete recovery of the hydrated gas

  19. Enhanced Selectivity of the Separation of CO2 from N2 during Crystallization of Semi-Clathrates from Quaternary Ammonium Solutions

    Directory of Open Access Journals (Sweden)

    Herri J.-M.

    2014-09-01

    Full Text Available CO2 mitigation is crucial environmental problem and a societal challenge for this century. CO2 capture and sequestration is a route to solve a part of the problem, especially for the industries in which the gases to be treated are well localized. CO2 capture by using hydrate is a process in which the cost of the separation is due to compression of gases to reach the gas hydrate formation conditions. Under pressure, the water and gas forms a solid that encapsulates preferentially CO2. The gas hydrate formation requires high pressures and low temperatures, which explains the use of thermodynamic promoters to decrease the operative pressure. Quaternary ammoniums salts represent an interesting family of components because of their thermodynamic effect, but also because they can generate crystals that are easily handled. In this work, we have made experiments concerning the equilibrium of (CO2, N2 in presence of Tetra-n-Butyl Ammonium Bromide (TBAB which form a semi-clathrate hydrate. We propose equilibrium data (pressure, temperature in presence of TBAB at different concentrations and we compare them to the literature. We have also measured the composition of the hydrate phase in equilibrium with the gas phase at different CO2 concentrations. We observe that the selectivity of the separation is dramatically increased in comparison to the selectivity of the pure water gas clathrate hydrate. We observe also a benefice on the operative pressure which can be dropped down to the atmospheric pressure.

  20. Electron spin resonance (ESR) of Eu{sup 2+} in type-I clathrate Eu{sub 8}Ga{sub 16}Ge{sub 30}

    Energy Technology Data Exchange (ETDEWEB)

    Holanda, L.M., E-mail: holandaj@ifi.unicamp.b [Instituto de Fisica Gleb Wataghin, Departamento de Eletronica Quantica UNICAMP, Campinas (Brazil); Vargas, J.M.; Rettori, C.; Pagliuso, P.G.; Bittar, E.M. [Instituto de Fisica Gleb Wataghin, Departamento de Eletronica Quantica UNICAMP, Campinas (Brazil); Avila, M.A.; Takabatake, T. [Department of Quantum Matter, ADSM, Hiroshima University, Higashi-Hiroshima 739-8530 (Japan)

    2009-10-15

    We report temperature dependent X-band (nuapprox9.5GHz) electron spin resonance (ESR) experiments in type-I clathrate Eu{sub 8}Ga{sub 16}Ge{sub 30}. This system presents interesting thermoelectric properties in its paramagnetic state and orders ferromagnetically below T{sub C}=35K. Although the Eu{sup 2+} ions sits on two inequivalent sites in the type-I clathrate structure, we found in the paramagnetic state a single Dysonian Eu{sup 2+} ESR line with a nearly temperature independent gapprox2 is observed, and its linewidth follows a Korringa-like behavior as a function of temperature. The microscopic details of the exchange coupling between the Eu{sup 2+} local moments and the conduction-electrons (c-e) in this compound are investigated through the obtained Korringa rate (DELTAH/DELTATapprox1(1)Oe/K) and g-shift (DELTAgapprox0.01(1)) from ESR experiments combined with the magnetic susceptibility and specific heat data.

  1. Lattice Dynamics Study of Phonon Instability and Thermal Properties of Type-I Clathrate K8Si46 under High Pressure

    Directory of Open Access Journals (Sweden)

    Wei Zhang

    2016-07-01

    Full Text Available For a further understanding of the phase transitions mechanism in type-I silicon clathrates K8Si46, ab initio self-consistent electronic calculations combined with linear-response method have been performed to investigate the vibrational properties of alkali metal K atoms encapsulated type-I silicon-clathrate under pressure within the framework of density functional perturbation theory. Our lattice dynamics simulation results showed that the pressure induced phase transition of K8Si46 was believed to be driven by the phonon instability of the calthrate lattice. Analysis of the evolution of the partial phonon density of state with pressure, a legible dynamic picture for both guest K atoms and host lattice, was given. In addition, based on phonon calculations and combined with quasi-harmonic approximation, the specific heat of K8Si46 was derived, which agreed very well with experimental results. Also, other important thermal properties including the thermal expansion coefficients and Grüneisen parameters of K8Si46 under different temperature and pressure were also predicted.

  2. Suggestions for Mitigation of Methane Clathrate Destabilization Along Continental Slopes Offshore and Discrimination Between Fossil and Recent Methane in the Atmosphere with Remote Sensing

    Science.gov (United States)

    Vincent, R. K.; Vincent, R. A.

    2010-12-01

    When a hydrocarbon-rich stratum intersects the outer edge of a continental shelf, at the continental slope, methane clathrates act as a partially impermeable barrier that prevents their easy escape at the end of the “layer cake” of continental sediments. If the clathrates on the continental slope melt because of rising sea bottom temperatures, hydrocarbons (natural gas and oil) can escape into the ocean, and finally into the atmosphere in the case of methane. A mitigation method is discussed that would drill vertically into the continental shelf, then horizontally toward the continental slope, and resulting production of oil and gas would reduce the pressure and the amount of methane escape to the ocean and the atmosphere. Remote sensing for lower tropospheric methane plumes will be needed to determine where drilling is needed, as well as to assess the effects of mitigation in reducing methane escape. A remote sensing method employing carbon isotopic ratios is proposed for discriminating fossil methane in natural gas from recent methane produced by decaying organic material. This is important because recent methane is recycled over decadal time frames and does not add greatly to global warming, whereas fossil methane releases carbon that has been sequestered for millions of years and is a principal cause of increased carbon dioxide in the atmosphere and its concomitant global warming.

  3. Synthesis and Characterization of Novel Copper(II 2D Coordination Polymers from a Fluorinated Flexible Ligand with Remarkable Clathration Ability

    Directory of Open Access Journals (Sweden)

    Kayoko Kasai

    2011-11-01

    Full Text Available Two-dimensional (2D grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyltetrafluorobenzene (bpf with Cu(NO32 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf2(NO32]·(biphenyl2}n (1, {[Cu(bpf2(NO32]·(m-C6H4(OMe22}n (2, {[Cu(bpf2(NO32]·PhtBu}n (3 and {[Cu(bpf2(NO3(H2O]NO3·(bpf0.5}n (4 were determined. The grid networks were held together by C–H···O and C–H···F hydrogen bonds via the NO3− anions and the tetrafluorophenylene rings of bpf, respectively. Biphenyl, m-dimethoxybenzene, t-butylbenzene, and bpf molecules were clathrated in cyclic cavities of the grid networks through arene-perfluoroarene interactions. These coordination networks have remarkable clathration ability for aromatic compounds.

  4. Lithium-ion induced conformational change of 5,17-bis(9-fluorenyl)-25,26,27,28-tetrapropoxy calix[4]arene resulting in an egg-shaped dimeric clathrate

    DEFF Research Database (Denmark)

    Faldt, A.; Krebs, Frederik C; Jørgensen, Mikkel

    2000-01-01

    Synthesis and structural investigation of a 5,17-bis(9-fluorenyl)-25,26,27,28-tetrapropoxy calix[4]arene and its lithium complex salt that forms a dimeric clathrate with a molecule of solvent inside a cavity. At least three different interactions were identified as being responsible for the...

  5. Fully quantal calculation of H2 translation-rotation states in (H2)4@5(12)6(4) clathrate sII inclusion compounds.

    Science.gov (United States)

    Felker, Peter M

    2013-05-01

    The quantal translation-rotation (TR) states of the (p-H2)4@5(12)6(4) and (o-D2)4@5(12)6(4) hydrate clathrate sII inclusion compounds have been computed by nuclear-orbital/configuration-interaction methods. The model of these compounds in a rigid, high-symmetry 5(12)6(4) cage is treated in detail. The low-energy TR level structures of both isotopomers within this model are found to consist of states that can be readily described in terms of a small number of single-H2 and double-H2 excitation modes. The use of the high-symmetry results to facilitate the calculation and interpretation of (p-H2)4 and (o-D2)4 TR states in low-symmetry physically realizable 5(12)6(4) cages is also reported.

  6. Interaction of L-alanyl-L-valine and L-valyl-L-alanine with organic vapors: thermal stability of clathrates, sorption capacity and the change in the morphology of dipeptide films.

    Science.gov (United States)

    Ziganshin, Marat A; Gubina, Nadezhda S; Gerasimov, Alexander V; Gorbatchuk, Valery V; Ziganshina, Sufia A; Chuklanov, Anton P; Bukharaev, Anastas A

    2015-08-21

    The strong effect of the amino acid sequence in L-alanyl-L-valine and L-valyl-L-alanine on their sorption properties toward organic compounds and water, and the thermal stability of the inclusion compounds of these dipeptides have been found. Generally, L-valyl-L-alanine has a greater sorption capacity for the studied compounds, but the thermal stability of the L-alanyl-L-valine clathrates is higher. Unusual selectivity of L-valyl-L-alanine for vapors of few chloroalkanes was observed. The correlation between the change in the surface morphology of thin film of dipeptides and stoichiometry of their clathrates with organic compounds was found. This discovery may be used to predict the influence of vapors on the morphology of films of short-chain oligopeptides.

  7. Thermodynamic modeling of phase equilibria of semi-clathrate hydrates of CO2, CH4, or N2+tetra-n-butylammonium bromide aqueous solution

    DEFF Research Database (Denmark)

    Eslamimanesh, Ali; Mohammadi, Amir H.; Richon, Dominique

    2012-01-01

    ) aqueous solution. For modeling the hydrate phase, the van der Waals–Platteeuw (vdW–P) solid solution theory is used, revised with two modifications for evaluations of Langmuir constants and vapor pressure of water in the empty hydrate lattice, in which these values are supposed to be a function of TBAB...... with the experimental semi-clathrate hydrate dissociation data investigated in this work....

  8. 水合物溶液分离技术研究进展%Progress in aqueous solution concentration by forming clathrate hydrate

    Institute of Scientific and Technical Information of China (English)

    李士凤; 谭哲; 申延明; 刘东斌; 樊丽辉; 白净

    2014-01-01

    水合物法溶液分离是一种新兴的分离技术。本文概述了水合物溶液分离技术的基本原理,指出水合物溶液分离技术的优缺点。重点回顾了水合物溶液分离技术在海水淡化、废水处理、果汁浓缩、生化分离等过程中的研究进展:尽管水合物海水淡化已经有工业化的报道,但是水合物生成压力较高,分离过程能耗较大,阻碍了该技术的推广应用;水合物法废水处理仅局限于制浆废水回收方面;水合物果汁浓缩以及生化分离方面的研究表明水合物法对于高附加值产品分离十分有效。分析表明,水合物溶液分离技术在上述应用过程中存在水合物生成压力大、水合物结晶夹带浓缩液等问题,指出未来水合物溶液分离技术的研究方向为寻找更加有效的水合物生成气体以及在高附加值产品分离回收过程中的应用。%The hydrate-based solution separation is a novel separation technology. This paper summarized the basic principle of aqueous concentration by forming hydrate,the benefits and drawbacks of hydrate technology. This paper emphasized the progress of seawater desalination, wastewater treatment,juice concentration,and biochemical separation by forming clathrate hydrate. Although forming hydrate desalination has been industrialized,the high and energy consumption of hydrate formation pressure limited its applications. The research on waste water treatment was only limited to pulping waste water recovery. Juice concentration and biochemical separation by forming hydrate were proven to be effective in recovery products with high added-value. The problems of high pressure of hydrate formation and hydrate crystal entrained concentrated solution by forming clathrate hydrate were also discussed. Future research directions of aqueous solution concentration by forming hydrate were proposed.

  9. Magnetic ordering of hyperfine-coupled nuclear and 4f-electron moments in the clathrate compound Pr3Pd20Ge6

    Science.gov (United States)

    Iwakami, O.; Namisashi, Y.; Abe, S.; Matsumoto, K.; Ano, G.; Akatsu, M.; Mitsumoto, K.; Nemoto, Y.; Takeda, N.; Goto, T.; Kitazawa, H.

    2014-09-01

    Complex ac susceptibility, χ =χ'-iχ'', measurements of the clathrate compound Pr3Pd20Ge6 were performed in static fields up to 10 mT for H ∥[001] and at temperatures down to 500 μK. Praseodymium (Pr) nuclear magnetic moments at the 8c site, where quadrupole moments of 4f electrons order at TQ1=250 mK, were found to order antiferromagnetically at 9 mK, as shown by a peak in χ' and a substantial increase in thermal relaxation time. The large enhancement factor (1+K8c) obtained by calculation of the hyperfine-enhanced nuclear susceptibility of Pr at the 8c site accounts for the high transition temperature of Pr nuclear magnetic moments and the large χ' below 30 mK. From analysis of the crystalline electric field and the mean-field approximation, we conclude that a χ peak at 77 mK can be ascribed to an antiferromagnetic ordering of magnetic moments of 4f electrons at the 4a site. We found that nuclear and f-electron moments order separately on two sublattices in this compound. The temperature and magnetic field dependence of χ' and χ'' between 30 and 60 mK are discussed in terms of dissipation phenomena.

  10. Effect of Transition Metal Substitution on the Structure and Properties of a Clathrate-Like Compound Eu7Cu44As23

    Directory of Open Access Journals (Sweden)

    Igor V. Plokhikh

    2016-07-01

    Full Text Available A series of substitutional solid solutions—Eu7Cu44−xTxAs23 (T = Fe, Co, Ni—based on a recently discovered clathrate-like compound (Eu7Cu44As23 were synthesized from the elements at 800 °C. Almost up to 50% of Cu can be substituted by Ni, resulting in a linear decrease of the cubic unit cell parameter from a = 16.6707(1 Å for the ternary compound to a = 16.3719(1 Å for the sample with the nominal composition Eu7Cu24Ni20As23. In contrast, Co and Fe can only substitute less than 20% of Cu. Crystal structures of six samples of different composition were refined from powder diffraction data. Despite very small differences in scattering powers of Cu, Ni, Co, and Fe, we were able to propose a reasonable model of dopant distribution over copper sites based on the trends in interatomic distances as well as on Mössbauer spectra for the iron-substituted compound Eu7Cu36Fe8As23. Ni doping increases the Curie temperature to 25 K with respect to the parent compound, which is ferromagnetically ordered below 17.5 K, whereas Fe doping suppresses the ferromagnetic ordering in the Eu sublattice.

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

    Directory of Open Access Journals (Sweden)

    Mohammadi A.H.

    2010-11-01

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

  12. Enhanced kinetics for the clathrate process in a fixed bed reactor in the presence of liquid promoters for pre-combustion carbon dioxide capture

    International Nuclear Information System (INIS)

    In this work, we present enhanced kinetics of hydrate formation for the clathrate process in the presence of two liquid promoters namely THF (tetrahydrofuran) and TBAB (tetra-n-butyl ammonium bromide) in a FBR (fixed bed reactor) for pre-combustion capture of CO2. Silica sand was used as a medium to capture CO2 from CO2/H2 gas mixture by hydrate crystallisation. Experiments were performed at different temperatures (274.2 K and 279.2 K) and 6.0 MPa to determine the total gas uptake, induction time and rate of hydrate formation. The observed trends indicated that higher driving force resulted in higher gas consumption and significantly reduced induction time. For the same driving force, higher gas consumption and shorter induction time was achieved by THF as compared to TBAB. 5.53 mol% THF attained higher gas consumption than 1.0 mol% THF whereas 3.0 mol% TBAB attained lower gas consumption than 0.3 mol% TBAB. A highest gas uptake of 51.95 (±5.183) mmol of gas/mol of water and a highest rate of 51.21(±8.91) mol.min−1.m−3 were obtained for 5.53 mol% THF at 6.0 MPa and 279.2 K. Overall, this study indicated better hydrate formation kinetics with the use of THF in an FBR configuration for CO2 capture from a fuel gas mixture. - Highlights: • Better kinetic performance with THF compared to TBAB for CO2 capture in a fixed bed reactor. • Highest CO2 uptake (126.99 ± 12.67 mg of gas/g of water) was obtained for 5.53 mol% THF. • Highest growth rate (51.21 ± 8.91 mol min−1.m−3) for 30 min was obtained for 5.53 mol% THF. • Waste heat (ΔT = 20) is sufficient to recover all the hydrated gas

  13. Thermoelectric properties of Au-containing type-I clathrates Ba{sub 8}Au{sub x}Ga{sub 16−3x}Ge{sub 30+2x}

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Zuxin; Cho, Jung Young; Tessema, Misle M. [Optimal Inc., Plymouth, MI 48170 (United States); Salvador, James R., E-mail: james.salvador@gm.com [Chemical and Materials Systems Laboratory, General Motors Global R and D, Warren, MI 48090 (United States); Waldo, Richard A. [Chemical and Materials Systems Laboratory, General Motors Global R and D, Warren, MI 48090 (United States); Yang, Jihui [Department of Materials, University of Washington (United States); Wang, Hsin; Cai, W.; Kirkham, M.J. [Materials Science and Technology Division, Oak Ridge National Laboratory (United States); Yang, Jiong; Zhang, Wenqing [Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai (China)

    2014-02-25

    Highlights: • Ba{sub 8}Au{sub x}Ga{sub 16−3x}Ge{sub 30+2x} were prepared, and the solubility limit of Au is x = 5.4. • Glass like thermal conduction at low temperature was found for p-type materials. • Higher DOS effective masses carriers were found in higher Au content samples. • Au was found to preferentially substitute at the 6c Wyckoff site. • ZT = 0.6 at 750 K was found for Ba{sub 8}Au{sub x}Ga{sub 16−3x}Ge{sub 30+2x} (x = 1, 5, and 5.33). -- Abstract: Type I clathrates, with compositions based on Ba{sub 8}Ga{sub 16}Ge{sub 30}, are a class of promising thermoelectric materials due to their intrinsically low thermal conductivity. It has been demonstrated previously that the thermoelectric performance can be improved by transition metal substitution of the framework atoms. In this study, the effects of Au substitution for Ga/Ge on thermal and electrical transport properties of type I clathrate compounds have been investigated. Polycrystalline samples with a large range of Au content have been synthesized using conventional solid state techniques with the actual compositions of resulting materials approximately following Zintl-Klemm rules. The charge carrier type changes from electrons (n) to holes (p) as the Au content increases. The Seebeck coefficient (S) and power factor (S{sup 2}/ρ where ρ is the electrical resistivity) were improved by Au substitution and the resulting overall thermoelectric properties were enhanced by Au substitution as compared to polycrystalline Ba{sub 8}Ga{sub 16}Ge{sub 30}. The thermoelectric figure of merit ZT attains a value of 0.63 at 740 K for the composition Ba{sub 8}Au{sub 5.47}Ge{sub 39.96}, a value that is somewhat lower than those reported previously. The results presented herein show that Au-containing type I clathrates are promising p-type thermoelectric materials for high temperature applications.

  14. Hydrated coefficient of clathrates and its applications in determination of aqueous inclusions with multivolatile components%气水化合物的水合常数及其在水溶液包裹体多组分挥发分测定中的应用

    Institute of Scientific and Technical Information of China (English)

    刘斌; 徐金明

    2007-01-01

    During the microthermometric measurement (cooling) of aqueous inclusions with multivolatile components, solid crystals of gas clathrates often occur with snow-flower- or soft-ice appearances. The structural formula of these solids is M · nH2O (where n ≥5.67 ). Many hydrocarbons, related compounds and their binary or multi-component mixtures may generate gas clathrates. This phenomenum is of fundamental importance to the study of inclusions with hydrocarbon aqueous solutions, because this is related to the determination of inclusion parameters and the computation of thermodynamic parameters.In the nature most aqueous inclusions contain not merely one volatile component but multi-volatile components. Therefore, the measurement of aqueous inclusions with multivolatile components is of universal significance and great importance. There have been many studies and available formula or figures about the computation of thermodynamic parameters for aqueous inclusions with one volatile component. Nevertheless, there are few studies concerning with multivolatile components and it is very difficult to computate thermodynamic parameters for aqueous inclusions with these components.In this paper, hydrated coefficient K is introduced. Ki is the ratio of molar fraction of component i in the gas phase to that in the gas clathrate, or Ki = yi/xi. Because K is a function of temperatures and pressures, it can be used to evaluate the temperature-pressure conditions on the phase behavior with multivolatile components.Based on the regression analysis of available experimental data, the authors have developed computational expression of hydrated coefficients in relation to temperature and pressure for most hydrocarbons and other volatile components, which is helpful to conveniently compute thermodynamic parameters on stability state for clathrates with volatile components. As aqueous inclusions with multivolatile components are common in the nature, by the use of final melting

  15. Synthesis and structures of type-I clathrates: Rb6Na2Ge44.89(1), Cs6Na2Zn4Ge42 and Cs6.40(1)Na1.60(1)Ga8Ge38

    Science.gov (United States)

    Zhang, Hui; Mu, Gang; Huang, Fuqiang; Xie, Xiaoming

    2016-10-01

    Type-I clathrates of Rb6Na2Ge44.89(1), Cs6Na2Zn4Ge42 and Cs6.40(1)Na1.60(1)Ga8Ge38 were synthesized via solid-state reaction. Rb6Na2Ge44.89(1), Cs6Na2Zn4Ge42 and Cs6.40(1)Na1.60(1)Ga8Ge38 were found to crystalize in the cubic space group of Pm 3 ̅ n with lattice parameters of a=10.72755(5) Å, a=10.79501(8) Å and a=10.79726(5) Å, respectively. Theoretical calculations indicated semiconducting features for the calculation models of Rb6Na2Ge44, Cs6Na2Zn4Ge42 and Cs6Na2Ga8Ge38 with band gaps of 0.002 eV, 0.297 eV and 0.221 eV, respectively.

  16. Thermodynamic model for predicting equilibrium conditions of clathrate hydrates of noble gases + light hydrocarbons: Combination of Van der Waals–Platteeuw model and sPC-SAFT EoS

    International Nuclear Information System (INIS)

    Highlights: • Applying sPC-SAFT for phase equilibrium calculations. • Determining Kihara potential parameters for hydrate formers. • Successful usage of the model for systems with hydrate azeotropes. - Abstract: In this communication, equilibrium conditions of clathrate hydrates containing mixtures of noble gases (Argon, Krypton and Xenon) and light hydrocarbons (C1–C3), which form structure I and II, are modeled. The thermodynamic model is based on the solid solution theory of Van der Waals–Platteeuw combined with the simplified Perturbed-Chain Statistical Association Fluid Theory equation of state (sPC-SAFT EoS). In dispersion term of sPC-SAFT EoS, the temperature dependent binary interaction parameters (kij) are adjusted; taking advantage of the well described (vapor + liquid) phase equilibria. Furthermore, the Kihara potential parameters are optimized based on the P–T data of pure hydrate former. Subsequently, these obtained parameters are used to predict the binary gas hydrate dissociation conditions. The equilibrium conditions of the binary gas hydrates predicted by this model agree well with experimental data (overall AAD P ∼ 2.17)

  17. Clathration Craft for β-Cyclodextrin in Essential Oil of Fructus Forsythiae in Fufang Yuxingcao Granules%复方鱼腥草颗粒中连翘挥发油β-环糊精包合工艺优化研究

    Institute of Scientific and Technical Information of China (English)

    施晓光

    2016-01-01

    目的:用β-环糊精对复方鱼腥草颗粒中的连翘挥发油进行包合。方法采用正交试验法选择包合工艺的最佳条件,并对包合物的质量进行分析。结果得出的最佳工艺条件为挥发油与β-环糊精的比为10 mL∶80 g,包合时间为4 h,包合温度为60℃,加水量为β-环糊精的8倍。结论该包合工艺简单可行,可有效防止挥发油有效成分的散失。%Objective To clathrate the essential oil of Fructus Forsythian in Fufang Yuxingcao Granules with β-cyclodextrin. Methods The optimum condition for clathration craft was chosen by orthogonal tests and the quality of clathrates was analyzed. Results The op-timum craft condition:the proposition of essential oil and β-cyclodextrin was 10 mL ∶80 g;the process was 4 h at 60 °C;8 times of water respect to β-cyclodextrin was added. Conclusion The craft is proved to be simple,operatable and effective to avoid active gra-dients in the essential oil.

  18. Full-dimensional, high-level ab initio potential energy surfaces for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2} with application to hydrogen clathrate hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Homayoon, Zahra; Conte, Riccardo; Qu, Chen; Bowman, Joel M., E-mail: jmbowma@emory.edu [Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322 (United States)

    2015-08-28

    New, full-dimensional potential energy surfaces (PESs), obtained using precise least-squares fitting of high-level electronic energy databases, are reported for intrinsic H{sub 2}(H{sub 2}O) two-body and H{sub 2}(H{sub 2}O){sub 2} three-body potentials. The database for H{sub 2}(H{sub 2}O) consists of approximately 44 000 energies at the coupled cluster singles and doubles plus perturbative triples (CCSD(T))-F12a/haQZ (aug-cc-pVQZ for O and cc-pVQZ for H) level of theory, while the database for the three-body interaction consists of more than 36 000 energies at the CCSD(T)-F12a/haTZ (aug-cc-pVTZ for O, cc-pVTZ for H) level of theory. Two precise potentials are based on the invariant-polynomial technique and are compared to computationally faster ones obtained via “purified” symmetrization. All fits use reduced permutational symmetry appropriate for these non-covalent interactions. These intrinsic potentials are employed together with existing ones for H{sub 2}, H{sub 2}O, and (H{sub 2}O){sub 2}, to obtain full PESs for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2}. Properties of these full PESs are presented, including a diffusion Monte Carlo calculation of the zero-point energy and wavefunction, and dissociation energy of the H{sub 2}(H{sub 2}O) dimer. These PESs together with an existing one for water clusters are used in a many-body representation of the PES of hydrogen clathrate hydrates, illustrated for H{sub 2}@(H{sub 2}O){sub 20}. An analysis of this hydrate is presented, including the electronic dissociation energy to remove H{sub 2} from the calculated equilibrium structure.

  19. Performance of local correlation methods for halogen bonding: The case of Br{sub 2}–(H{sub 2}O){sub n},n = 4,5 clusters and Br{sub 2}@5{sup 12}6{sup 2} clathrate cage

    Energy Technology Data Exchange (ETDEWEB)

    Batista-Romero, Fidel A.; Bernal-Uruchurtu, Margarita I.; Hernández-Lamoneda, Ramón, E-mail: ramon@uaem.mx [Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Cuernavaca, Morelos 62209 (Mexico); Pajón-Suárez, Pedro [Instituto Superior de Tecnologías y Ciencias Aplicadas (InSTEC), Habana 6163 (Cuba)

    2015-09-07

    The performance of local correlation methods is examined for the interactions present in clusters of bromine with water where the combined effect of hydrogen bonding (HB), halogen bonding (XB), and hydrogen-halogen (HX) interactions lead to many interesting properties. Local methods reproduce all the subtleties involved such as many-body effects and dispersion contributions provided that specific methodological steps are followed. Additionally, they predict optimized geometries that are nearly free of basis set superposition error that lead to improved estimates of spectroscopic properties. Taking advantage of the local correlation energy partitioning scheme, we compare the different interaction environments present in small clusters and those inside the 5{sup 12}6{sup 2} clathrate cage. This analysis allows a clear identification of the reasons supporting the use of local methods for large systems where non-covalent interactions play a key role.

  20. Tuning Thermoelectric Properties of Type I Clathrate K 8–x Ba x Al 8+x Si 38–x through Barium Substitution

    Energy Technology Data Exchange (ETDEWEB)

    Sui, Fan; Kauzlarich, Susan M.

    2016-05-10

    The thermal stability and thermoelectric properties of type I clathrate K8Al8Si38 up to 873 K are reported. K8Al8Si38 possesses a high absolute Seebeck coefficient value and high electrical resistivity in the temperature range of 323 to 873 K, which is consistent with previously reported low temperature thermoelectric properties. Samples with Ba partial substitution at the K guest atom sites were synthesized from metal hydride precursors. The samples with the nominal chemical formula of K8–xBaxAl8+xSi38–x (x = 1, 1.5, 2) possess type I clathrate structure (cubic, Pm3n), confirmed by X-ray diffraction. The guest atom site occupancies and thermal motions were investigated with Rietveld refinement of synchrotron powder X-ray diffraction. Transport properties of Ba-containing samples were characterized from 2 to 300 K. The K–Ba alloy phases showed low thermal conductivity and improved electrical conductivity compared to K8Al8Si38. Electrical resistivity and Seebeck coefficients were measured over the temperature range of 323 to 873 K. Thermal conductivity from 323 to 873 K was estimated from the Wiedemann–Franz relation and lattice thermal conductivity extrapolation from 300 to 873 K. K8–xBaxAl8+xSi38–x (x = 1, 1.5) synthesized with Al deficiency showed enhanced electrical conductivity, and the absolute Seebeck coefficients decrease with the increased carrier concentration. When x = 2, the Al content increases toward the electron balanced composition, and the electrical resistivity increases with the decreasing charge carrier concentration. Overall, K6.5Ba1.5Al9Si37 achieves an enhanced zT of 0.4 at 873 K.

  1. Preparation of Anti-mosquito Silk Fabric via Grafting β-cyclodextrin to Clathrate Natural Mosquito Repellent%利用接枝β-环糊精包合天然驱蚊剂制备防蚊真丝织物

    Institute of Scientific and Technical Information of China (English)

    刘建华; 许宏聪; 沈林; 陈瑞玉; 李超; 余志成

    2012-01-01

    采用1,2,3,4-丁烷四羧酸(BTCA)在催化剂次亚磷酸钠(SHP)的作用下将β-环糊精(β-CD)接枝到真丝纤维上,然后浸渍加入具有驱蚊功效的薰衣草精油使其包合在β-CD空腔中,制备出具有驱蚊功效的真丝织物.设计单因素试验优化β-CD接枝真丝织物的工艺参数,当BTCA和β-CD的质量浓度分别为100 g/L,SHP的质量浓度为60 g/L,170℃下焙烘3min或180℃下焙烘2 min,真丝织物的接枝增重率可达18.4%,红外光谱分析表明β-CD已成功接枝至真丝织物上,且可耐15次以上的水洗.接枝β-CD的真丝织物能够赋予薰衣草精油缓释的效果,且放置8d后对按蚊仍可保持75%以上的驱避率.此方法制备的防蚊真丝织物效果持久可重复使用,且具有对人体无毒害、环保的特点.%p-cyclodextrin (p-CD) was grafted onto silk fabric by using 1,2,3,4-butane tetracarboxylic acid (BTCA) un-der the catalysis of sodium hypophosphite (SHP),which enabled lavender essential oil,a natural mosquito repellent,to be clathrated into the cavity of β-CD for development of silk fabric with mosquito repellence.Single factor tests were designed to optimize technological parameters for grafting β-CD onto silk fabric.The results showed that the fabric weight gain rate could reach 18.4% when grafting was conducted with 100 g/Lβ-CD,100 g/L BTCA and 60 g/L SHP under 170℃for 3 min or 180℃for 2 min.Infrared spectrometric analysis demonstrated that β-CD had been grafted onto silk fabric successfully and could resist washing over 15 times.The β-CD grafted silk fabric endowed lavender essential oil a slow-release effect,which maintained an over 75% mosquito repellence rate after 8 days.The mosquito-repellence silk fabric prepared by this method not only had a long effective duration and many times of repeated use,but also had the characteristics of being safe to human body and being friendly to environment.

  2. Superconductive "sodalite"-like clathrate calcium hydride at high pressures

    CERN Document Server

    Wang, Hui; Tanaka, Kaori; Iitaka, Toshiaki; Ma, Yanming

    2012-01-01

    Hydrogen-rich compounds hold promise as high-temperature superconductors under high pressures. Recent theoretical hydride structures on achieving high-pressure superconductivity are composed mainly of H2 fragments. Through a systematic investigation of Ca hydrides with different hydrogen contents using particle-swam optimization structural search, we show that in the stoichiometry CaH6 a body-centred cubic structure with hydrogen that forms unusual "sodalite" cages containing enclathrated Ca stabilizes above pressure 150 GPa. The stability of this structure is derived from the acceptance by two H2 of electrons donated by Ca forming a "H4" unit as the building block in the construction of the 3-dimensional sodalite cage. This unique structure has a partial occupation of the degenerated orbitals at the zone centre. The resultant dynamic Jahn-Teller effect helps to enhance electron-phonon coupling and leads to superconductivity of CaH6. A superconducting critical temperature (Tc) of 220-235 K at 150 GPa obtained...

  3. Towards a green hydrate inhibitor: imaging antifreeze proteins on clathrates.

    Directory of Open Access Journals (Sweden)

    Raimond Gordienko

    Full Text Available The formation of hydrate plugs in oil and gas pipelines is a serious industrial problem and recently there has been an increased interest in the use of alternative hydrate inhibitors as substitutes for thermodynamic inhibitors like methanol. We show here that antifreeze proteins (AFPs possess the ability to modify structure II (sII tetrahydrofuran (THF hydrate crystal morphologies by adhering to the hydrate surface and inhibiting growth in a similar fashion to the kinetic inhibitor poly-N-vinylpyrrolidone (PVP. The effects of AFPs on the formation and growth rate of high-pressure sII gas mix hydrate demonstrated that AFPs are superior hydrate inhibitors compared to PVP. These results indicate that AFPs may be suitable for the study of new inhibitor systems and represent an important step towards the development of biologically-based hydrate inhibitors.

  4. Low barriers for hydrogen diffusion in sII clathrate.

    Science.gov (United States)

    Trinh, Thuat T; Waage, Magnus H; van Erp, Titus S; Kjelstrup, Signe

    2015-06-01

    The transport of gas molecules in hydrates is presently poorly understood. In sII structured hydrates with hydrogen guests there is, for instance, a mismatch between experimental and computed values for diffusion constants. We provide an explanation for the experimentally observed diffusion rates, using DFT-based molecular dynamics simulations at 100 K. By considering the effect of cage occupancy, as well as the flexibility of the water lattice, we show that barriers for hydrogen diffusing between cages, can approach values as low as 5 kJ mol(-1), which is very close to experimental values.

  5. Interaction Study of Guest with Host in Clathrate Hydrate

    Institute of Scientific and Technical Information of China (English)

    Lin Wang; Shunle Dong

    2007-01-01

    Lattice dynamical simulations of noble gas hydrate structures I and II have been performed. Potential energies were investigated to study the influence of guest species on the stability of the hydrate structure. Results show that when the diameter of inclusion molecules is between 3 A and 4.2 A, such as Ar and Kr, the critical role of the 512 cage in the stabilization of hydrates becomes effective. For Xe hydrates SI and SII, with the help of lattice dynamical calculations, the modes attributions are identified directly. We proposed the resonant effect of the fingerprint frequency at about 7 meV and 10 meV which arise from the coupling of Xe molecules in the 512 cage with the host lattice.

  6. Molecular Design Basis for Hydrogen Storage in Clathrate Hydrates

    Energy Technology Data Exchange (ETDEWEB)

    John, Vijay T [Tulane University; McPherson, Gary L [Tulane University; Ashbaugh, Hank [Tulane University; Johnes, Camille Y [Columbia University

    2013-06-28

    We attach a final technical report for the project. The report contains the list of all peer reviewed publications that have resulted from the contract. I will be happy to send the pdf files of the papers.

  7. CO₂ processing and hydration of fruit and vegetable tissues by clathrate hydrate formation.

    Science.gov (United States)

    Takeya, Satoshi; Nakano, Kohei; Thammawong, Manasikan; Umeda, Hiroki; Yoneyama, Akio; Takeda, Tohoru; Hyodo, Kazuyuki; Matsuo, Seiji

    2016-08-15

    CO2 hydrate can be used to preserve fresh fruits and vegetables, and its application could contribute to the processing of carbonated frozen food. We investigated water transformation in the frozen tissue of fresh grape samples upon CO2 treatment at 2-3 MPa and 3°C for up to 46 h. Frozen fresh bean, radish, eggplant and cucumber samples were also investigated for comparison. X-ray diffraction indicated that after undergoing CO2 treatment for several hours, structure I CO2 hydrate formed within the grape tissue. Phase-contrast X-ray imaging using the diffraction-enhanced imaging technique revealed the presence of CO2 hydrate within the intercellular spaces of these tissues. The carbonated produce became effervescent because of the dissociation of CO2 hydrate through the intercellular space, especially above the melting point of ice. In addition, suppressed metabolic activity resulting from CO2 hydrate formation, which inhibits water and nutrient transport through intercellular space, can be expected. PMID:27006222

  8. Optimizing the Interactions of Surfactants with Graphitic Surfaces and Clathrate Hydrates.

    Science.gov (United States)

    Di Crescenzo, Antonello; Di Profio, Pietro; Siani, Gabriella; Zappacosta, Romina; Fontana, Antonella

    2016-07-01

    Surfactants are amphiphilic molecules active at the surface/interface and able to self-assemble. Because of these properties, surfactants have been extensively used as detergents, emulsifiers, foaming agents, and wetting agents. New perspectives have been opened by the exploitation of surfactants for their capacity to interact as well with simple molecules or surfaces. This feature article gives an overview of significant contributions in the panorama of the current research on surfactants, partly accomplished as well by our research group. We look at several recent applications (e.g., adsorption to graphitic surfaces and interactions with hydrate crystals) with the eye of physical organic chemists. We demonstrate that, from the detailed investigation of the forces involved in the interactions with hydrophobic surfaces, it is possible to optimize the design of the surfactant that is able to form a stable and unbundled carbon nanotube dispersion as well as the best exfoliating agent for graphitic surfaces. By studying the effect of different surfactants on the capacity to favor or disfavor the formation of a gas hydrate, it is possible to highlight the main features that a surfactant should possess in order to be devoted to that specific application. PMID:27264111

  9. Clathrate hydrate equilibria in mixed monoethylene glycol and electrolyte aqueous solutions

    International Nuclear Information System (INIS)

    Highlights: ► New water activity of mixed salt(s) and MEG aqueous solutions were measured. ► New 3-phase H–Lw–V data for methane and a natural gas in equilibrium with MEG and NaCl solutions are reported. ► The CPA-EoS combined with a modified Debye Hückel electrostatic term is employed to model the phase equilibria. ► Water activity data were used to adjust parameters of the modified Debye Hückel electrostatic term. ► The modified model was independently validated using hydrate data. - Abstract: Monoethylene glycol (MEG) is commonly added in the formulation of hydraulic and drilling fluids and injected into pipelines to prevent the formation of gas hydrates. It is therefore necessary to establish the effect of a combination of salts and thermodynamic inhibitors on gas hydrate equilibria. In this communication, water activity of five ternary solutions (MEG–H2O–NaCl, MEG–H2O–CaCl2, MEG–H2O–MgCl2, MEG–H2O–KCl and MEG–H2O–NaBr) and four multicomponent solutions have been measured by a reliable resistive electrolytic humidity sensor. We also report new experimental measurements of the locus of incipient hydrate-liquid water–vapour curve for systems containing methane or natural gas with aqueous solution of ethylene glycol and NaCl over a wide range of concentrations, pressures and temperatures. A thermodynamic approach in which the Cubic-Plus-Association equation of state is combined with a modified Debye Hückel electrostatic term is employed to model the phase equilibria. These new data have been used to optimise binary interaction parameters between salts and MEG implemented in the modified Debye Hückel electrostatic term. The model developed has been evaluated using the new generated hydrate data and literature data. Good agreement between predictions of the modified model and experimental data is observed, supporting the reliability of the developed model.

  10. An Experimental Determination of Natural Clathrate Hydrate Dissolution Rates in the Deep Sea

    Science.gov (United States)

    Peltzer, E. T.; Walz, P. M.; Brewer, P. G.; Dunk, R. M.; Hester, K.; Sloan, E. D.

    2006-12-01

    In August of 2006 we carried out a series of geochemical experiments on the massive Structure II hydrate mounds in Barkley Canyon using MBARI's ROV Tiburon deployed from the R/V Western Flyer. One of the primary questions regarding the fate of this hydrate exposure at 850m depth is the temporal persistence of un-sedimented surfaces exposed to steady currents of seawater undersaturated with methane. Previous work on the dissolution rate of laboratory prepared methane hydrate (Rehder et al., 2004) showed diameter reduction rates of ~3 m/year. These formations appeared largely unchanged from the earlier descriptions and photographs contained in media reports released in 2002 and later (Chapman et al., 2004; Lu et al., 2005) leading us to speculate that these hydrates are far slower to dissolve. In order to quantify their dissolution rates, samples of the outcropping hydrate, both a pure white hydrate and a much harder yellow, oil-stained hydrate, were collected using an ROV operated coring device and hydraulically expelled into an open mesh container for time-lapse photography over the course of the next 48 hours. By exposing these samples of natural hydrate to the flow of ambient seawater we hoped to observe the dissolution rate consistent with the local environmental conditions. Initial analysis of the time-lapse photographs obtained using a Nikon Cool-pix camera revealed an apparent diameter reduction rate for the yellow hydrate of approximately 0.040 μm/s, corresponding to a volume loss rate of 1.3×10-6cm3/cm2/s. The observed dissolution rate of the white hydrate was significantly faster, consistent with the observed large-scale undercutting of the exposed layered structures. Assuming that the yellow hydrate has a density of 0.93 g/cm3 and an average hydration number near 6, this yields a guest gas loss rate of about 9.4×10-9 mol/cm2/s. This is approximately one-fourth the rate that was observed for the dissolution of synthetic Structure I methane hydrates under similar conditions in Monterey Bay. Thus the lifetime of the exposed surfaces must be short unless there is some form of active expulsion of fresh hydrates taking place. Chapman et al. (2004). Eos, Trans. Amer. Geophys. Union. 85: 361, 365. Lu et al. (2005). J. Geophys. Res. 110: B10204, doi:10.1029/2005JB003900. Rehder et al. (2004). Geochim. et Cosmochim. Acta 68: 285-292.

  11. Pressure-induced phase transformations in the Ba8Si46 clathrate

    DEFF Research Database (Denmark)

    Yang, Lirong; Ma, Y.M.; Iitaka, T.;

    2006-01-01

    parameters from Rietveld analysis. The results show that the first transition at 7 GPa is caused by the displacement of the Ba atoms in the Si-24 cages. The cause of the second transition at 15 GPa, characterized by a dramatic reduction of cell volume, is not as clear. Theoretical calculations predicted...

  12. Decomposition of Clathrate Hydrates by High Frequency in-Liquid Plasma

    OpenAIRE

    Putra, Andi Erwin Eka

    2008-01-01

    In recent years, 81% of total energy consumption is fossil fuel. Transportation, power generation, agriculture and industry activity is driven by oil and petroleum as a fossil fuel. Nevertheless, Petroleum prices are rising due to oil crisis in 1973, the Gulf War in 1991, and depletion of petroleum reserves. In addition, the environmental issues such as global warming, the Kyoto Protocol, and the emission of greenhouse gases are also a consideration to look for alternative energy fuel. Tod...

  13. Sponge Effect on Coal Mine Methane Separation Based on Clathrate Hydrate Method

    Institute of Scientific and Technical Information of China (English)

    ZHANG Baoyong; CHENG Yuanping; WU Qiang

    2011-01-01

    The findings were presented from laboratory investigations on the hydrate formation and dissociation processes employed to recover methane from coal mine gas.The separation process of coal mine methane(CMM) was carried out at 273.15K under 4.00 MPa.The key process variables of gas formation rate,gas volume stored in hydrate and separation concentration were closely investigated in twelve THF-SDS-sponge-gas systems to verify the sponge effect in these hydrate-based separation processes.The gas volume stored in hydrate is calculated based on the measured gas pressure.The CH4 mole fraction in hydrate phase is measured by gas chromatography to confirm the separation efficiency.Through close examination of the overall results,it was clearly verified that sponges with volumes of 40,60 and 80 cm 3 significantly increase gas hydrate formation rate and the gas volume stored in hydrate,and have little effect on the CH4 mole fraction in hydrate phase.The present study provides references for the application of the kinetic effect of porous sponge media in hydrate-based technology.This will contribute to CMM utilization and to benefit for local and global environment.

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

    Science.gov (United States)

    Yoshioki, Shuzo

    2012-07-01

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

  15. Facilitating guest transport in clathrate hydrates by tuning guest-host interactions

    Energy Technology Data Exchange (ETDEWEB)

    Moudrakovski, Igor L.; Udachin, Konstantin A.; Ratcliffe, Christopher I. [National Research Council of Canada, 100 Sussex Dr., Ottawa, Ontario K1A 0R6 (Canada); Alavi, Saman; Ripmeester, John A., E-mail: John.Ripmeester@nrc-cnrc.gc.ca [National Research Council of Canada, 100 Sussex Dr., Ottawa, Ontario K1A 0R6 (Canada); Department of Chemical and Biological Engineering, University of British Columbia, Vancouver, British Columbia V6T 1Z3 (Canada)

    2015-02-21

    The understanding and eventual control of guest molecule transport in gas hydrates is of central importance for the efficient synthesis and processing of these materials for applications in the storage, separation, and sequestration of gases and natural gas production. Previously, some links have been established between dynamics of the host water molecules and guest-host hydrogen bonding interactions, but direct observation of transport in the form of cage-to-cage guest diffusion is still lacking. Recent calculations have suggested that pairs of different guest molecules in neighboring cages can affect guest-host hydrogen bonding and, therefore, defect injection and water lattice motions. We have chosen two sets of hydrate guest pairs, tetrahydrofuran (THF)-CO{sub 2} and isobutane-CO{sub 2}, that are predicted to enhance or to diminish guest–host hydrogen bonding interactions as compared to those in pure CO{sub 2} hydrate and we have studied guest dynamics in each using {sup 13}C nuclear magnetic resonance (NMR) methods. In addition, we have obtained the crystal structure of the THF-CO{sub 2} sII hydrate using the combined single crystal X-ray diffraction and {sup 13}C NMR powder pattern data and have performed molecular dynamics-simulation of the CO{sub 2} dynamics. The NMR powder line shape studies confirm the enhanced and delayed dynamics for the THF and isobutane containing hydrates, respectively, as compared to those in the CO{sub 2} hydrate. In addition, from line shape studies and 2D exchange spectroscopy NMR, we observe cage-to-cage exchange of CO{sub 2} molecules in the THF-CO{sub 2} hydrate, but not in the other hydrates studied. We conclude that the relatively rapid intercage guest dynamics are the result of synergistic guest A–host water–guest B interactions, thus allowing tuning of the guest transport properties in the hydrates by choice of the appropriate guest molecules. Our experimental value for inter-cage hopping is slower by a factor of 10{sup 6} than a published calculated value.

  16. Dynamical and energetic properties of hydrogen and hydrogen–tetrahydrofuran clathrate hydrates

    OpenAIRE

    Gorman, Paul D.; English, Niall J.; MacElroy, J. M. Don

    2011-01-01

    Classical equilibrium molecular dynamics (MD) simulations have been performed to investigate the dynamical and energetic properties in hydrogen and mixed hydrogen-tetrahydrofuran sII hydrates at 30 and 200K and 0.05 kbar, and also at intermediate temperatures, using SPC/E and TIP4P-2005 water models. The potential model is found to have a large impact on overall density, with the TIP4P-2005 systems being on average 1 % more dense than their SPC/E counterparts, due to the greater guest-host in...

  17. Raman Spectroscopic Studies of Clathrate Hydrate Formation in the Presence of Hydrophobized Particles.

    Science.gov (United States)

    Li, Huijuan; Stanwix, Paul; Aman, Zachary; Johns, Michael; May, Eric; Wang, Liguang

    2016-01-28

    In the present work, Raman spectroscopy was used to study the structure of water molecules in the vicinity of glass particles with different hydrophobicity, immersed in water and in tetrahydrofuran and cyclopentane hydrates. The glass particle surfaces were clean (hydrophilic), coated with N,N-dimethyl-N-octadecyl-3-aminopropyl trimethoxysilyl chloride (partially hydrophobic), or coated with octadecyltrichlorosilane (hydrophobic). The Raman spectra indicate that, prior to nucleation, water molecules in the vicinity of hydrophobic surfaces are more ice-like ordered than those in the bulk liquid or near either hydrophilic or partially hydrophobic surfaces. Furthermore, the degree of hydrogen-bond ordering of water observed prior to hydrate nucleation, as measured by the ratio of the inter- and intramolecular Raman OH bands, was found to have an inverse relationship with the mean induction time for hydrate formation. Following hydration formation, no significant difference in the water molecule structure was observed in the hydrate phase based on their Raman OH bands, irrespective of surface hydrophobicity. These observations made with Raman spectroscopy provide the foundations for a quantitative link between hydrate nucleation promotion and water-ordering near solid surfaces, which could enable direct comparisons with results from corresponding molecular dynamics simulations. PMID:26731126

  18. Facilitating guest transport in clathrate hydrates by tuning guest-host interactions

    International Nuclear Information System (INIS)

    The understanding and eventual control of guest molecule transport in gas hydrates is of central importance for the efficient synthesis and processing of these materials for applications in the storage, separation, and sequestration of gases and natural gas production. Previously, some links have been established between dynamics of the host water molecules and guest-host hydrogen bonding interactions, but direct observation of transport in the form of cage-to-cage guest diffusion is still lacking. Recent calculations have suggested that pairs of different guest molecules in neighboring cages can affect guest-host hydrogen bonding and, therefore, defect injection and water lattice motions. We have chosen two sets of hydrate guest pairs, tetrahydrofuran (THF)-CO2 and isobutane-CO2, that are predicted to enhance or to diminish guest–host hydrogen bonding interactions as compared to those in pure CO2 hydrate and we have studied guest dynamics in each using 13C nuclear magnetic resonance (NMR) methods. In addition, we have obtained the crystal structure of the THF-CO2 sII hydrate using the combined single crystal X-ray diffraction and 13C NMR powder pattern data and have performed molecular dynamics-simulation of the CO2 dynamics. The NMR powder line shape studies confirm the enhanced and delayed dynamics for the THF and isobutane containing hydrates, respectively, as compared to those in the CO2 hydrate. In addition, from line shape studies and 2D exchange spectroscopy NMR, we observe cage-to-cage exchange of CO2 molecules in the THF-CO2 hydrate, but not in the other hydrates studied. We conclude that the relatively rapid intercage guest dynamics are the result of synergistic guest A–host water–guest B interactions, thus allowing tuning of the guest transport properties in the hydrates by choice of the appropriate guest molecules. Our experimental value for inter-cage hopping is slower by a factor of 106 than a published calculated value

  19. Phase Behaviour, Thermodynamics and Kinetics of Clathrate Hydrate Systems of Carbon Dioxide in Presence of Tetrahydrofuran and Electrolytes

    NARCIS (Netherlands)

    Mohamad Sabil, K. Bin

    2009-01-01

    In view of the possibilities for new development of carbon dioxide hydrate processes, this study focused on experimental measurements to obtain fundamental insight into the phase behaviour and the kinetic of formation of carbon dioxide hydrate forming systems. These data are essential for the develo

  20. About Some Of The Properties Of A Guest Molecule Confined In A Water Network, In Order To Form A Clathrate

    Science.gov (United States)

    Pérez, G. Bravo; Cruz-Torres, A.; Romero-Martínez, A.

    2008-03-01

    At conditions of high pressure and or low temperature, like a sea bottom from even 1 Km deep, hydrates formation may take place. Its presence is facilitated at the water/oil interface inside conducting oil pipelines. Once formed, the hydrates nucleate further to agglomerations, sticking to the inner surface of the tube. This represents a big problem to flow assurance. We present results contributing to a better understanding of the interaction of a guest molecule with a water cage confining it, that give rise to a hydrate formation. The hydrate structure, its formation energy, and the role that the H bond and its cooperative effect in the water network play in the electrostatic dipole moment of the hydrate, are presented. Molecular calculations using the HF/6-311g(d, p), B3LYP/6-311g(d, p), and B3LYP/6-311++g(d,p) methods, have been applied to compare three different hydrates, each one confining one, two CH4 molecules, and a CO2 molecule, requiring respectively n = 14, 35, and 15 water molecules for the confinement.

  1. Thermodynamic study of clathrates hydrates from hydrocarbon gas mixtures consequences for CO2 capture and flow assurance

    OpenAIRE

    Le, Quanq-Du; Le Quang, Duyen; Bouillot, Baptiste; Herri, Jean-Michel

    2014-01-01

    This work presents details on the experimental procedure to measure the composition of the hydrate that crystallizes from a hydrocarbon gas mixture. We show that the results are time dependent and tend to thermodynamic equilibrium as time tends to infinity. An immediate consequence concerns two major domains of applications, CO2 capture from power plants, as well as flow assurance in the oil and gas industry. In fact, in both the cases, the crystallization is under non equilibrium conditions,...

  2. Calculations of NMR properties for sI and sII clathrate hydrates of methane, ethane and propane.

    Science.gov (United States)

    Siuda, Paweł; Sadlej, Joanna

    2014-12-01

    Calculations of NMR parameters (the absolute shielding constants and the spin-spin coupling constants) for 5(12), 5(12)6(2) and 5(12)6(4) cages enclathrating CH4, C2H6 and C3H8 molecules are presented. The DFT/B3LYP/HuzIII-su3 level of theory was employed. The (13)C shielding constants of guest molecules are close to available experimental data. In two cases (the ethane in 5(12) and the propane in 5(12)6(2) cages) the (13)C shielding constants are reported for the first time. Inversion of the methyl/methylene (13)C and (1)H shielding constants order is found for propane in the 5(12)6(2) cage. Topological criteria are used to interpret the changes of values of NMR parameters of water molecules and they establish a connection between single cages and bulk crystal.

  3. 7,11,15,28-Tetrakis[(2-formylphenoxymethyl]-1,21,23,25-tetramethylresorcin[4]arene cavitand ethyl acetate clathrate at 173 K

    Directory of Open Access Journals (Sweden)

    Michael G. Mc Kay

    2009-04-01

    Full Text Available The title compound, C68H56O16, was synthesized as a novel synthetic intermediate towards deeper and more elaborate resorcin[4]arene cavitands. The structure is the first reported example of a resorcin[4]arene cavitand bearing aromatic aldehyde functional groups at the extra-annular rim of the molecule. The 2-formylphenoxy residues are found to assume two different orientations above the molecular cavity. One half of the resorcin[4]arene cavitand molecule appears in the asymmetric unit; the complete resorcin[4]arene cavitand structure was generated across a mirror plane. In addition, a highly disordered ethyl acetate solvent molecule is present within the molecular cavity.

  4. Communication: Librational dynamics in water, sI and sII clathrate hydrates, and ice Ih: Molecular-dynamics insights.

    Science.gov (United States)

    Burnham, Christian J; English, Niall J

    2016-02-01

    Equilibrium molecular-dynamics simulations have been performed for liquid water, and on metastable sI and sII polymorphs of empty hydrate lattices, in addition to ice Ih, in order to study the dynamical properties of librational motion (rotation oscillation) depicted by protons in water molecules. In particular, hydrate lattices were found to display prominent "bifurcated" features, or peaks, at circa 70 and 80-95 meV (or ∼560 and 640-760 cm(-1), respectively), also displayed by ice, in essentially quantitative agreement with experimental neutron-scattering data. However, observed differences in dispersion between these librational modes between these two structures (both hydrate polymorphs vis-à-vis ice), owing primarily to density effects, have been decomposed into contributions arising from angular-velocity dynamics about axes in the local molecular frame of water molecules, with in-plane "wagging" and "twisting" rationalising one mode at ∼70 meV, and out-of-plane motion for the higher-frequency band. This was confirmed explicitly by a type of de facto normal-mode analysis, in which only immediate layers of water molecules about the one under consideration were allowed to move. In contrast, liquid water displayed no marked preference for such local in- or out-of-plane modes characterising librational motion, owing to the marked absence of rigid, pentamers or hexamers therein.

  5. Hydrogen-bond vibrational and energetic dynamical properties in sI and sII clathrate hydrates and in ice Ih: Molecular dynamics insights.

    Science.gov (United States)

    Chakraborty, Somendra Nath; English, Niall J

    2015-10-21

    Equilibrium molecular dynamics (MD) simulations have been performed on cubic (sI and sII) polymorphs of methane hydrate, and hexagonal ice (ice Ih), to study the dynamical properties of hydrogen-bond vibrations and hydrogen-bond self-energy. It was found that hydrogen-bond energies are greatest in magnitude in sI hydrates, followed by sII, and their energies are least in magnitude in ice Ih. This is consistent with recent MD-based findings on thermal conductivities for these various materials [N. J. English and J. S. Tse, Phys. Rev. Lett. 103, 015901 (2009)], in which the lower thermal conductivity of sI methane hydrate was rationalised in terms of more strained hydrogen-bond arrangements. Further, modes for vibration and energy-transfer via hydrogen bonds in sI hydrate were found to occur at higher frequencies vis-à-vis ice Ih and sII hydrate in both the water-librational and OH⋯H regions because of the more strained nature of hydrogen bonds therein.

  6. Preparation, transport properties and structure analysis by resonant x-ray scattering of the type-I clathrate Cs8Cd4Sn42

    International Nuclear Information System (INIS)

    Structural and transport properties of Cs8Cd4SN42 are reported. Cs8Cd4Sn42 has a thermal conductivity that is unusually low for a cystalline solid (1 W m-1 K-1 at room temperature). This low lattice thermal conductivity is associated with the rattling of cesium in the tetrakaidecahedral cavities, as indicated by the large atomic displacement parameters of Cs in the tetrakaidecahedra. Resonant X-ray powder diffraction measuerments indicate that all of the cadmium is located on one of three inequivalent framework sites. There is no evidence for any framework vacancies in the material

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

    Science.gov (United States)

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

    2015-04-14

    One of the options suggested for methane recovery from natural gas hydrates is molecular replacement of methane by suitable guests like CO2 and N2. This approach has been found to be feasible through many experimental and molecular dynamics simulation studies. However, the long term stability of the resultant hydrate needs to be evaluated; the decomposition rate of these hydrates is expected to depend on the interaction between these guest and water molecules. In this work, molecular dynamics simulation has been performed to illustrate the effect of guest molecules with different sizes and interaction strengths with water on structure I (SI) hydrate decomposition and hence the stability. The van der Waals interaction between water of hydrate cages and guest molecules is defined by Lennard Jones potential parameters. A wide range of parameter spaces has been scanned by changing the guest molecules in the SI hydrate, which acts as a model gas for occupying the small and large cages of the SI hydrate. All atomistic simulation results show that the stability of the hydrate is sensitive to the size and interaction of the guest molecules with hydrate water. The increase in the interaction of guest molecules with water stabilizes the hydrate, which in turn shows a slower rate of hydrate decomposition. Similarly guest molecules with a reasonably small (similar to Helium) or large size increase the decomposition rate. The results were also analyzed by calculating the structural order parameter to understand the dynamics of crystal structure and correlated with the release rate of guest molecules from the solid hydrate phase. The results have been explained based on the calculation of potential energies felt by guest molecules in amorphous water, hydrate bulk and hydrate-water interface regions. PMID:25767053

  8. 基于β-环糊精包合作用的防蚊真丝织物研制%Preparation of mosquito repellence silk fabric based on the clathration of β-cyclodextrin

    Institute of Scientific and Technical Information of China (English)

    许宏聪; 陈瑞玉; 沈林; 李超; 刘建华; 余志成

    2012-01-01

    The P-CD was grafted onto silk fabric with BTCA as cross-linking agent and SHP as catalytic agent, then was treated with citronella essential oil to make mosquito repellent fabric. Determine the optimum grafting process of P-CD through orthogonal experiment as: mass concentration of BTCA is 110 g/L, mass concentration of p-CD is 70 g/L, and mass concentration of SHP is 40 g/L, and curing temperature is 170 °C for 3 min, and weight gain rate of real silk fabric under this process could reach 16.04 %. SEM test indicates that: P-CD had grafted onto silk fabric successfully; after that, K/S value of P-CD grafted silk fabric dyed with cationic dyeing is increased significantly, while K/S value of acid dyes and reactive dyes are significantly lowered. After placing grafted silk fabric dyed with citronella essential oil for once week, the repellent rate of the silk fabric against culex pipiens pallens could still stay higher than 75 %.%以丁烷四羧酸(BTCA)为交联剂,次亚磷酸钠(SHP)为催化剂,将β-环糊精(β-CD)接枝到真丝织物上,再经天然香茅草提取物整理,赋予真丝织物驱蚊效果.通过正交试验确定β-CD最佳接枝工艺为:BTCA质量浓度110g/L、β-CD质量浓度70 g/L、SHP质量浓度4g/L、焙烘条件170℃、3min,此工艺下真丝织物增重率可达16.04%.扫面电镜(SEM)测试表明:β-CD己成功接枝到真丝织物上;β-CD接枝后真丝织物阳离子染料染色的K/S明显提高,而酸性染料和活性染料染色的K/S值明显下降.经香茅草提取物整理的接枝真丝织物,放置一周后,对淡色库蚊驱避率仍可保持在75%以上.

  9. Molecular dynamics simulation of promotion mechanism of store hydrogen of clathrate hydrate%储氢笼型水合物生成促进机理的分子动力学模拟研究

    Institute of Scientific and Technical Information of China (English)

    颜克凤; 李小森; 孙丽华; 陈朝阳; 夏志明

    2011-01-01

    Molecular dynamics(MD) simulation is used to study the promotion mechanism of store hydrogen via the hydrate formation.The stable structures and the microcosmic properties of pure H2 hydrate,H2+tetrahydrofuran (THF) hydrate,H2+tetra-n-butylammonium bromide (TBAB) and H2+tetraisoamylammonium bromide (TiAAB) semiclathrate hydrates are investigated systematically.The stabilization energy,ΔEGH,between guest and cavity is calculated.It is shown that the large cavity of hydrate plays a main role of stabilizing hydrate.THF in large cavity can promote the stabilization of hydrogen hydrate and reduce the pressure of formation hydrogen hydrate,which are the same as the experimental results.Compared with the ΔEGH between guest and large cavity,the results are in the order of increase as TiAAB,TBAB,THF,H2.It is concluded that the stability of semiclathrate hydrate is better than the structure Ⅱ hydrate,and H2+TiAAB semiclathrate hydrate is stablest.MD simulation provides helpful information for future TiAAB semiclathrate as a new promoter of forming hydrate and a new hydrogen storage material.%用分子动力学(MD)模拟方法研究水合物法储氢的促进机理,系统研究纯H2水合物、H2+四氢呋喃(THF)水合物、H2+四丁基溴化铵(TBAB)半笼型水合物和H2+四异戊基溴化铵(TiAAB)半笼型水合物的微观结构及性质.模拟分析客体与笼子之间的稳定能ΔEGH,得出水合物中大笼子对稳定水合物起到主要作用.THF进入大笼子能促进H2水合物稳定,降低H2水合物形成压力,模拟结果与实验一致.模拟对比不同客体在大笼子中的ΔEGH值,得出从小到大的顺序依次为TiAAB,TBAB,THF,H2.模拟结果表明半笼型水合物的稳定性比结构Ⅱ型水合物强,同时得出H2+TiAAB半笼型水合物的结构最稳定.MD模拟为TiAAB成为一种水合物新型促进剂和新型储氢材料提供了理论依据.

  10. Non-solar noble gas abundances in the atmosphere of Jupiter

    Science.gov (United States)

    Lunine, Jonathan I.; Stevenson, David J.

    1986-01-01

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

  11. On the possible noble gas deficiency of Pluto's atmosphere

    OpenAIRE

    Mousis, Olivier; Lunine, Jonathan I.; Mandt, Kathleen E.; Schindhelm, Eric; Weaver, Harold A.; Stern, S. Alan; Waite, J. Hunter; Gladstone, Randy; Moudens, Audrey

    2013-01-01

    We use a statistical-thermodynamic model to investigate the formation and composition of noble-gas-rich clathrates on Pluto's surface. By considering an atmospheric composition close to that of today's Pluto and a broad range of surface pressures, we find that Ar, Kr and Xe can be efficiently trapped in clathrates if they formed at the surface, in a way similar to what has been proposed for Titan. The formation on Pluto of clathrates rich in noble gases could then induce a strong decrease in ...

  12. Method for solid state crystal growth

    Science.gov (United States)

    Nolas, George S.; Beekman, Matthew K.

    2013-04-09

    A novel method for high quality crystal growth of intermetallic clathrates is presented. The synthesis of high quality pure phase crystals has been complicated by the simultaneous formation of both clathrate type-I and clathrate type-II structures. It was found that selective, phase pure, single-crystal growth of type-I and type-II clathrates can be achieved by maintaining sufficient partial pressure of a chemical constituent during slow, controlled deprivation of the chemical constituent from the primary reactant. The chemical constituent is slowly removed from the primary reactant by the reaction of the chemical constituent vapor with a secondary reactant, spatially separated from the primary reactant, in a closed volume under uniaxial pressure and heat to form the single phase pure crystals.

  13. The Clathration Technology of Garlic Oil and Its Influence to the Blood Rheology of Experimental Hyperlipemia Rat%大蒜油的包合工艺及其对实验性高脂血症大鼠血液流变学影响

    Institute of Scientific and Technical Information of China (English)

    饶小勇; 何颖辉; 王珏; 林色奇; 张国松; 罗小建

    2006-01-01

    大蒜油为大蒜(Allium sativum L)的有效成分之一,通过对大蒜油进行β-环糊精(简称β-CD)包合工艺的考察,确定大蒜油的最佳包合工艺;大蒜油包合物能明显降低大蒜油对胃肠道粘膜的刺激性,比纯大蒜油更具有应用价值,为了深入研究大蒜油及其包合物的药效作用及毒性,我们做了大蒜油β—CD包合物对实验性高血脂症大鼠血液流变学的影响的试验研究。

  14. Phase behavior in the system tetrahydrofuran-water-ammonia from calorimetry and Raman spectroscopy

    Science.gov (United States)

    Munoz-Iglesias, Victoria; Vu, Tuan; Choukroun, Mathieu; Hodyss, Robert; Smythe, William; Sotin, Christophe

    2016-10-01

    From geochemical models and Cassini-Huygens mission data it can be postulated that the icy crust of Titan is composed by water ice, clathrate hydrates and ammonia hydrates. When the shell evolves thermically, the first minerals in dissociating are the ammonia hydrates. Ammonia is a powerful antifreeze, promoting the drop of the equilibrium curves of both water ice and clathrates to values as low as 170 K and 203 K respectively. Calorimetry, using a Setaram BT 2.15 Calvet calorimeter, has allowed to identify the different phases formed in the system THF-H2O-NH3 when the molar ratio H2O:THF is 1:X 17, which corresponds with the THF-clathrate stoichiometric ratio, and at NH3 concentrations up to 30 wt%. When X 17, the H2O is in excess; the formation of ammonia hydrates, water ice and THF-clathrate is observed. Since under this condition, all available THF is trapped in the clathrate, no THF-NH3 phase is observed. In all the scenarios, the release of NH3 (from the melting of THF-NH3 solid or ammonia hydrates) promotes partial dissociation of THF clathrates, which start at much lower temperature the equilibrium dissociation of the clathrates. This research is supported by an appointment to the NASA Postdoctoral Program at the Jet Propulsion Laboratory, California Institute of Technology, administered by Universities Space Research Association (USRA) through a contract with NASA. Support from the NASA Outer Planets Research program and government sponsorship acknowledged.

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

    Directory of Open Access Journals (Sweden)

    Span Roland

    2012-04-01

    Full Text Available 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.

  16. The fate of ethane in Titan's hydrocarbon lakes and seas

    CERN Document Server

    Mousis, Olivier; Hayes, Alexander G; Hofgartner, Jason D

    2015-01-01

    Ethane is expected to be the dominant photochemical product on Titan's surface and, in the absence of a process that sequesters it from exposed surface reservoirs, a major constituent of its lakes and seas. Absorption of Cassini's 2.2 cm radar by Ligeia Mare however suggests that this north polar sea is dominated by methane. In order to explain this apparent ethane deficiency, we explore the possibility that Ligeia Mare is the visible part of an alkanofer that interacted with an underlying clathrate layer and investigate the influence of this interaction on an assumed initial ethane-methane mixture in the liquid phase. We find that progressive liquid entrapment in clathrate allows the surface liquid reservoir to become methane-dominated for any initial ethane mole fraction below 0.75. If interactions between alkanofers and clathrates are common on Titan, this should lead to the emergence of many methane-dominated seas or lakes.

  17. The fate of ethane in Titan's hydrocarbon lakes and seas

    Science.gov (United States)

    Mousis, Olivier; Lunine, Jonathan I.; Hayes, Alexander G.; Hofgartner, Jason D.

    2016-05-01

    Ethane is expected to be the dominant photochemical product on Titan's surface and, in the absence of a process that sequesters it from exposed surface reservoirs, a major constituent of its lakes and seas. Absorption of Cassini's 2.2 cm radar by Ligeia Mare however suggests that this north polar sea is dominated by methane. In order to explain this apparent ethane deficiency, we explore the possibility that Ligeia Mare is the visible part of an alkanofer that interacted with an underlying clathrate layer and investigate the influence of this interaction on an assumed initial ethane-methane mixture in the liquid phase. We find that progressive liquid entrapment in clathrate allows the surface liquid reservoir to become methane-dominated for any initial ethane mole fraction below 0.75. If interactions between alkanofers and clathrates are common on Titan, this should lead to the emergence of many methane-dominated seas or lakes.

  18. A $\\sim$32-70 K formation temperature range for the ice grains agglomerated by comet 67P/Churyumov-Gerasimenko

    CERN Document Server

    Lectez, S; Mousis, O; Picaud, S; Altwegg, K; Rubin, M; Salazar, J M

    2015-01-01

    Grand Canonical Monte Carlo simulations are used to reproduce the N$_2$/CO ratio ranging between 1.7 $\\times$ 10$^{-3}$ and 1.6 $\\times$ 10$^{-2}$ observed {\\it in situ} in the Jupiter family comet 67P/Churyumov-Gerasimenko by the ROSINA mass spectrometer aboard the Rosetta spacecraft, assuming that this body has been agglomerated from clathrates in the protosolar nebula. Simulations are done using an elaborated interatomic potentials for investigating the temperature dependence of the trapping within a multiple guest clathrate formed from a gas mixture of CO and N$_2$ in proportions corresponding to those expected for the protosolar nebula. By assuming that 67P/Churyumov-Gerasimenko agglomerated from clathrates, our calculations suggest the cometary grains must have been formed at temperatures ranging between $\\sim$31.8 and 69.9 K in the protosolar nebula to match the N$_2$/CO ratio measured by the ROSINA mass spectrometer. The presence of clathrates in Jupiter family comets could then explain the potential ...

  19. Liquid Water Structure from Anomalous Density under Ambient Condition

    Institute of Scientific and Technical Information of China (English)

    SUN Qiang; ZHENG Hai-Fei

    2006-01-01

    @@ From discussion of the structure of liquid water, we deduce that water under ambient condition is mainly composed of ice Ih-like molecular clusters and clathrate-like molecular clusters. The water molecular clusters remain in a state of chemical equilibrium (reversible clustering reactions). This structural model can be demonstrated by quantitative study on anomalous density with increasing temperature at ambient pressure.

  20. 21 CFR 316.3 - Definitions.

    Science.gov (United States)

    2010-04-01

    ... or ion, excluding those appended portions of the molecule that cause the drug to be an ester, salt (including a salt with hydrogen or coordination bonds), or other noncovalent derivative (such as a complex... hydrogen or coordination bonds) or other noncovalent derivative such as a complex, chelate or clathrate...

  1. 21 CFR 516.3 - Definitions.

    Science.gov (United States)

    2010-04-01

    ... definitions of terms apply to all subparts of part 516: Active moiety means the molecule or ion, excluding... hydrogen or coordination bonds), or other noncovalent derivative (such as a complex, chelate, or clathrate... salt (including a salt with hydrogen or coordination bonds) or other noncovalent derivative such as...

  2. β-Cyclodextrin inclusion complex: preparation, characterization, and its aspirin release in vitro

    Science.gov (United States)

    Zhou, Hui-Yun; Jiang, Ling-Juan; Zhang, Yan-Ping; Li, Jun-Bo

    2012-09-01

    In this work, the optimal clathration condition was investigated for the preparation of aspirin-β-cyclodextrin (Asp-β-CD) inclusion complex using design of experiment (DOE) methodology. A 3-level, 3-factor Box-Behnken design with a total of 17 experimental runs was used. The Asp-β-CD inclusion complex was prepared by saturated solution method. The influence on the embedding rate was investigated, including molar ratio of β-CD to Asp, clathration temperature and clathration time, and the optimum values of such three test variables were found to be 0.82, 49°C and 2.0 h, respectively. The embedding rate could be up to 61.19%. The formation of the bonding between -COOH group of Asp and O-H group of β-CD might play an important role in the process of clathration according to FT-IR spectra. Release kinetics of Asp from inclusion complex was studied for the evaluation of drug release mechanism and diffusion coefficients. The results showed that the drug release from matrix occurred through Fickian diffusion mechanism. The cumulative release of Asp reached only 40% over 24 h, so the inclusion complex could potentially be applied as a long-acting delivery system.

  3. Determination of the minimum masses of heavy elements in the envelopes of Jupiter and Saturn

    CERN Document Server

    Mousis, Olivier; Lunine, Jonathan I; Alibert, Yann; Fletcher, Leigh N; Orton, Glenn S; Pauzat, Francoise; Ellinger, Yves

    2008-01-01

    We calculate the minimum mass of heavy elements required in the envelopes of Jupiter and Saturn to match the observed oversolar abundances of volatiles. Because the clathration efficiency remains unknown in the solar nebula, we have considered a set of sequences of ice formation in which the fraction of water available for clathration is varied between 0 and 100 %. In all the cases considered, we assume that the water abundance remains homogeneous whatever the heliocentric distance in the nebula and directly derives from a gas phase of solar composition. Planetesimals then form in the feeding zones of Jupiter and Saturn from the agglomeration of clathrates and pure condensates in proportions fixed by the clathration efficiency. A fraction of Kr and Xe may have been sequestrated by the H3+ ion in the form of stable XeH3+ and KrH3+ complexes in the solar nebula gas phase, thus implying the formation of at least partly Xe- and Kr-impoverished planetesimals in the feeding zones of Jupiter and Saturn. These planet...

  4. On the possible noble gas deficiency of Pluto's atmosphere

    CERN Document Server

    Mousis, Olivier; Mandt, Kathleen E; Schindhelm, Eric; Weaver, Harold A; Stern, S Alan; Waite, J Hunter; Gladstone, Randy; Moudens, Audrey

    2013-01-01

    We use a statistical-thermodynamic model to investigate the formation and composition of noble-gas-rich clathrates on Pluto's surface. By considering an atmospheric composition close to that of today's Pluto and a broad range of surface pressures, we find that Ar, Kr and Xe can be efficiently trapped in clathrates if they formed at the surface, in a way similar to what has been proposed for Titan. The formation on Pluto of clathrates rich in noble gases could then induce a strong decrease in their atmospheric abundances relative to their initial values. A clathrate thickness of order of a few centimeters globally averaged on the planet is enough to trap all Ar, Kr and Xe if these noble gases were in protosolar proportions in Pluto's early atmosphere. Because atmospheric escape over an extended period of time (millions of years) should lead to a noble gas abundance that either remains constant or increases with time, we find that a potential depletion of Ar, Kr and Xe in the atmosphere would best be explained ...

  5. On the abundances of noble and biologically relevant gases in Lake Vostok, Antarctica

    CERN Document Server

    Mousis, Olivier; Picaud, Sylvain; Pasek, Matthew; Chassefière, Eric

    2013-01-01

    Motivated by the possibility of comparing theoretical predictions of Lake Vostok's composition with future in situ measurements, we investigate the composition of clathrates that are expected to form in this environment from the air supplied to the lake by melting ice. In order to establish the best possible correlation between the lake water composition with that of air clathrates formed in situ, we use a statistical thermodynamic model based on the description of the guest-clathrate interaction by a spherically averaged Kihara potential with a nominal set of potential parameters. We determine the fugacities of the different volatiles present in the lake by defining a "pseudo" pure substance dissolved in water owning the average properties of the mixture and by using the Redlich-Kwong equation of state to mimic its thermodynamic behavior. Irrespective of the clathrate structure considered in our model, we find that xenon and krypton are strongly impoverished in the lake water (a ratio in the 0.04--0.1 range ...

  6. Sulfurization of Iron in the Dynamic Solar Nebula and Implications for Planetary Compositions

    CERN Document Server

    Ciesla, Fred J

    2015-01-01

    One explanation for the enhanced ratio of volatiles to hydrogen in Jupiter's atmosphere compared to a a gas of solar composition is that the planet accreted volatile-bearing clathrates during its formation. Models, however, suggest that S would be over abundant if clathrates were the primary carrier of Jupiter's volatiles. This led to the suggestion that S was depleted in the outer nebula due to the formation troilite (FeS). Here, this depletion is quantitatively explored by modeling the coupled dynamical and chemical evolution of Fe grains in the solar nebula. It is found that disks that undergo rapid radial expansion from an initially compact state may allow sufficient production of FeS and carry H$_{2}$S-depleted gas outward where ices would form, providing the conditions needed for S-depleted clathrates to form. However, this expansion would also carry FeS grains to this region, which could also be incorporated into planetesimals. Thus for clathrates to be a viable source of volatiles, models must account...

  7. SULFURIZATION OF IRON IN THE DYNAMIC SOLAR NEBULA AND IMPLICATIONS FOR PLANETARY COMPOSITIONS

    Energy Technology Data Exchange (ETDEWEB)

    Ciesla, Fred J., E-mail: fciesla@uchicago.edu [Department of the Geophysical Sciences, The University of Chicago, 5734 South Ellis Avenue, Chicago, IL 60637 (United States)

    2015-02-10

    One explanation for the enhanced ratio of volatiles to hydrogen in Jupiter’s atmosphere compared to a a gas of solar composition is that the planet accreted volatile-bearing clathrates during its formation. Models, however, suggest that S would be over abundant if clathrates were the primary carrier of Jupiter’s volatiles. This led to the suggestion that S was depleted in the outer nebula due to the formation troilite (FeS). Here, this depletion is quantitatively explored by modeling the coupled dynamical and chemical evolution of Fe grains in the solar nebula. It is found that disks that undergo rapid radial expansion from an initially compact state may allow sufficient production of FeS and carry H{sub 2}S-depleted gas outward where ices would form, providing the conditions needed for S-depleted clathrates to form. However, this expansion would also carry FeS grains to this region, which could also be incorporated into planetesimals. Thus for clathrates to be a viable source of volatiles, models must account for the presence of both H{sub 2}S in FeS in the outer solar nebula.

  8. A ∼32–70 K FORMATION TEMPERATURE RANGE FOR THE ICE GRAINS AGGLOMERATED BY COMET 67 P/CHURYUMOV–GERASIMENKO

    Energy Technology Data Exchange (ETDEWEB)

    Lectez, S.; Simon, J.-M.; Salazar, J. M. [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303, CNRS-Université de Bourgogne Franche Comté, Dijon (France); Mousis, O. [Aix Marseille Université, CNRS, Laboratoire d’Astrophysique de Marseille (LAM), UMR 7326, F-13388 Marseille (France); Picaud, S. [Institut UTINAM, UMR 6213, CNRS-Université de Bourgogne Franche Comté, Besançon (France); Altwegg, K.; Rubin, M., E-mail: jmsimon@u-bourgogne.fr [Physikalisches Institut, University of Bern, Sidlerstrasse 5, CH-3012 Bern (Switzerland)

    2015-05-20

    Grand Canonical Monte Carlo simulations are used to reproduce the N{sub 2}/CO ratio ranging between 1.7 × 10{sup −3} and 1.6 × 10{sup −2} observed in situ in the Jupiter-family comet 67 P/Churyumov–Gerasimenko (67 P) by the ROSINA mass spectrometer on board the Rosetta spacecraft. By assuming that this body has been agglomerated from clathrates in the protosolar nebula (PSN), simulations are developed using elaborated interatomic potentials for investigating the temperature dependence of the trapping within a multiple-guest clathrate formed from a gas mixture of CO and N{sub 2} in proportions corresponding to those expected for the PSN. By assuming that 67 P agglomerated from clathrates, our calculations suggest the cometary grains must have been formed at temperatures ranging between ∼31.8 and 69.9 K in the PSN to match the N{sub 2}/CO ratio measured by the ROSINA mass spectrometer. The presence of clathrates in Jupiter-family comets could then explain the potential N{sub 2} depletion (factor of up to ∼87 compared to the protosolar value) measured in 67 P.

  9. EXPERIMENT ON METHANE GAS HYDRATE FORMATION%甲烷水合物储气实验研究

    Institute of Scientific and Technical Information of China (English)

    郑新; 樊栓狮

    2003-01-01

    @@ 1 INTRODUCTION Methane gas hydrates (MGH) are solid phase crystalline inclusion compounds (also called clathrates) that consist of a host water lattice with cavities in which methane gas is caged as a guest gas.Methane gas hydrate might contain 164 volumes (at standard pressure and temperature)of methane and 0.87 volumes of water per volume hydrate.

  10. In situ product removal during enzymatic cephalexin synthesis by complexation

    NARCIS (Netherlands)

    Schroën, C.G.P.H.; Nierstrasz, V.A.; Bosma, R.; Kemperman, G.J.; Strubel, M.; Ooijkaas, L.P.; Beeftink, H.H.; Tramper, J.

    2002-01-01

    In this paper, ‘complexation’ indicates the formation of clathrate type inclusion compounds of cephalexin with naphthalene derivatives. These inclusion compounds readily crystallise in solution, resulting in specific co-crystals of complexing agent and cephalexin with a set ratio between both compon

  11. In situ product removal during enzymatic cephalexin synthesis by complexation

    NARCIS (Netherlands)

    Schroën, C.G.P.H.; Nierstrasz, V.A.; Bosma, R.; Kemperman, G.J.; Strubel, M.; Ooijkaas, L.P.; Beeftink, H.H.; Tramper, J.

    2002-01-01

    In this paper, `complexation' indicates the formation of clathrate type inclusion compounds of cephalexin with naphthalene derivatives. These inclusion compounds readily crystallise in solution, resulting in specific co-crystals of complexing agent and cephalexin with a set ratio between both compon

  12. Phase equilibrium modeling of gas hydrate systems for CO2 capture

    DEFF Research Database (Denmark)

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

    2012-01-01

    Two thermodynamic models capable of describing dissociation pressures of mixed gas clathrate hydrates formed from ternary mixtures of CO2, N2 and liquid water, are presented. Both of the models utilize the Cubic-Plus-Association (CPA) equation of state (EOS) for the thermodynamic description of t...

  13. Defining the Thermal Stability of Ba8Ga16Ge30 and its Future in Thermoelectrics

    DEFF Research Database (Denmark)

    Reardon, Hazel; Iversen, Bo Brummerstedt; Blichfeld, Anders Bank

    The majority of research on the auspicious n/p-Ba8Ga16-xGe30+x (BGG) Type-I thermoelectric clathrates has been focused on property measurements at low temperature. High temperature property measurements have also been reported for BGG, although they have not yet been fully explained. Therefore...

  14. Phase equilibrium conditions of semi-calthrate hydrates of (tetra-n-butyl ammonium chloride + carbon dioxide)

    International Nuclear Information System (INIS)

    Highlights: • Carbon dioxide hydrate stability zone was enlarged with the help of TBAC. • Carbon dioxide uptake into TBAC semi-clathrate hydrates is confirmed. • Equilibrium pressure of hydrate decreased with the increase of TBAC mass concentration. • The addition of TBAC reduces the formation pressures of carbon dioxide hydrate by 2.5 MPa. - Abstract: In the present work, hydrate equilibrium conditions for (tetra-n-butyl ammonium chloride (TBAC) + carbon dioxide + water) mixtures were investigated. Tetra-n-butyl ammonium chloride was reported to form a semi-clathrate hydrate. The experiments were carried out within the TBAC mass fraction range of (0.05 to 0.3). The experimental results showed that the presence of TBAC decreased the formation pressure of carbon dioxide double hydrate within the experimental temperature range. Moreover, pressure reduction was dependent on the TBAC concentration

  15. Low-density silicon allotropes for photovoltaic applications

    Science.gov (United States)

    Amsler, Maximilian; Botti, Silvana; Marques, Miguel A. L.; Lenosky, Thomas J.; Goedecker, Stefan

    2015-07-01

    Silicon materials play a key role in many technologically relevant fields, ranging from the electronic to the photovoltaic industry. A systematic search for silicon allotropes was performed by employing a modified ab initio minima hopping crystal structure prediction method. The algorithm was optimized to specifically investigate the hitherto barely explored low-density regime of the silicon phase diagram by imitating the guest-host concept of clathrate compounds. In total, 44 metastable phases are presented, of which 11 exhibit direct or quasidirect band gaps in the range of ≈1.0-1.8 eV, close to the optimal Shockley-Queisser limit of ≈1.4 eV, with a stronger overlap of the absorption spectra with the solar spectrum compared to conventional diamond silicon. Due to the structural resemblance to known clathrate compounds it is expected that the predicted phases can be synthesized.

  16. Intermolecular Interactions at high pressure

    DEFF Research Database (Denmark)

    Eikeland, Espen Zink

    2016-01-01

    . High-pressure crystallography is the perfect method for studying intermolecular interactions, by forcing the molecules closer together. In all three studied hydroquinone clathrates, new pressure induced phase transitions have been discovered using a mixture of pentane and isopentane as the pressure...... transformation is therefore most likely kinetically hindered when surrounded by solidified silicone oil. The calculated intermolecular energies in all three hydroquinone clathrates show the anticipated strong interactions in the host framework and the weaker host-guest interactions. As the pressure is raised...... illustrates how important it is to quantify all intermolecular interactions in structures. This enables researchers to see a more complete picture and not focus only on a few interactions deemed particularly important....

  17. astrophysical significance

    Directory of Open Access Journals (Sweden)

    Dartois E.

    2014-02-01

    Full Text Available Clathrate hydrates, ice inclusion compounds, are of major importance for the Earth’s permafrost regions and may control the stability of gases in many astrophysical bodies such as the planets, comets and possibly interstellar grains. Their physical behavior may provide a trapping mechanism to modify the absolute and relative composition of icy bodies that could be the source of late-time injection of gaseous species in planetary atmospheres or hot cores. In this study, we provide and discuss laboratory-recorded infrared signatures of clathrate hydrates in the near to mid-infrared and the implications for space-based astrophysical tele-detection in order to constrain their possible presence.

  18. Structure of water + acetonitrile solutions from acoustic and positron annihilation measurements

    Energy Technology Data Exchange (ETDEWEB)

    Jerie, Kazimierz [Institute of Experimental Physics, University of WrocIaw, WrocIaw (Poland); Baranowski, Andrzej [Institute of Experimental Physics, University of WrocIaw, WrocIaw (Poland); Koziol, Stan [Waters Corp., 34 Maple St., Milford, MA 01757 (United States); Glinski, Jacek [Faculty of Chemistry, University of WrocIaw, WrocIaw (Poland)]. E-mail: glin@wchuwr.chem.uni.wroc.pl; Burakowski, Andrzej [Faculty of Chemistry, University of WrocIaw, WrocIaw (Poland)

    2005-03-14

    We report the results of acoustic and positron annihilation measurements in aqueous solutions of acetonitrile (CH{sub 3}CN). Hydrophobicity of the solute is discussed, as well as the possibility of describing the title system in terms of hydrophobic solvation. A new method of calculating the 'ideal' positronium lifetimes is proposed, based on the mean volume of cavities (holes) in liquid structure available for positronium pseudoatom. The results are almost identical with those obtained from molar volumes using the concept of Levay et al. On the other hand, the same calculations performed using the 'bubble' model of annihilation yield very different results. It seems that either acetonitrile forms with water clathrate-like hydrates of untypical architecture, or it is too weak hydrophobic agent to form clathrate-like hydrates at all. The former interpretation seems to be more probable.

  19. Structure of Aqueous Solutions of Acetonitrile Investigated by Acoustic and Positron Annihilation Measurements

    Science.gov (United States)

    Jerie, K.; Baranowski, A.; Koziol, S.; Burakowski, A.

    2005-05-01

    We report the results of acoustic and positron annihilation measurements in aqueous solutions of acetonitrile (CH3CN). Hydrophobicity of the solute is discussed, as well as the possibility of describing the title system in terms of hydrophobic solvation. The concept of Levay et al. of calculating the "ideal positronium lifetimes is applied, basing on the mean volume of cavities (holes) in liquid structure available for positronium pseudoatom. The same calculations performed using the Tao model of annihilation yield very different results. It can be concluded that either acetonitrile forms with water clathrate-like hydrates of untypical architecture, or it is too weak hydrophobic agent to form clathrate-like hydrates at all. The former interpretation seems to be more probable.

  20. Structure of water + acetonitrile solutions from acoustic and positron annihilation measurements

    Science.gov (United States)

    Jerie, Kazimierz; Baranowski, Andrzej; Koziol, Stan; Gliński, Jacek; Burakowski, Andrzej

    2005-03-01

    We report the results of acoustic and positron annihilation measurements in aqueous solutions of acetonitrile (CH 3CN). Hydrophobicity of the solute is discussed, as well as the possibility of describing the title system in terms of hydrophobic solvation. A new method of calculating the "ideal" positronium lifetimes is proposed, based on the mean volume of cavities (holes) in liquid structure available for positronium pseudoatom. The results are almost identical with those obtained from molar volumes using the concept of Levay et al. On the other hand, the same calculations performed using the "bubble" model of annihilation yield very different results. It seems that either acetonitrile forms with water clathrate-like hydrates of untypical architecture, or it is too weak hydrophobic agent to form clathrate-like hydrates at all. The former interpretation seems to be more probable.

  1. Investigating Molecular Interactions

    DEFF Research Database (Denmark)

    Clausen, Henrik Fanø

    2010-01-01

    the thesis to the two types of structures. The first chapter is a brief introduction to the theory used in this dissertation, where diffraction theory, the aspherical atom model, and the Atom in Molecules theory will be presented. Physical properties, such as thermal stability and magnetic susceptibility......-clathrate of hydroquinone has been determined using data from a powerful third generation synchrotron source. Multipole models using both isotropic and estimated anisotropic thermal parameters for the hydrogen atoms have been refined and compared, revealing significant differences in the obtained electrostatic potential...... were used to determine the positional and thermal parameters of the hydrogen atoms. The electrostatic potential from the obtained multipole model has been compared with the empty β-clathrate of hydroquinone, revealing significant differences due to the enclathrated acetonitrile molecule....

  2. Formation of porous gas hydrates

    CERN Document Server

    Salamatin, Andrey N

    2015-01-01

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

  3. Accelerated nucleation of tetrahydrofuran (THF) hydrate in presence of ZIF-61

    Institute of Scientific and Technical Information of China (English)

    Yanhong Wang; Xuemei Lang; Shuanshi Fan

    2012-01-01

    Clathrate hydrate can be used in energy gas storage and transportation,CO2 capture and cool storage etc.However,these technologies are difficult to be used due to the low formation rate and long induction time of hydrate formation.In this paper,ZIF-61 (zeolite imidazolate framework,ZIF) was first used in hydrate formation to stimulate hydrate nucleation.As an additive of clathrate hydrate,ZIF-61 promoted obviously the acceleration of tetrahydrofuran (THF) hydrate nucleation.It shortened the induction time of THF hydrate formation from 2-5 h to 0.3-1 h mainly due to the template function of ZIF-61 by which the nucleation of THF hydrate has been promoted.

  4. On the origin of Triton and Pluto

    International Nuclear Information System (INIS)

    A simple hypothesis on the origin of Triton and Pluto is that Triton and Pluto are independent representatives of large outer Solar System planetesimals. Triton is simply captured, with potentially spectacular consequences that include runaway melting of interior ices and release to the surface of clathrated CH4, CO and N2. Condensed remnants of this proto-atmosphere could account for features in Triton's unique spectrum. (author)

  5. Influence d'additifs anti-agglomérants sur l'agrégation et les propriétés de transport des hydrates de méthane cristallisant dans des émulsions eau/dodécane

    OpenAIRE

    FIDEL-DUFOUR, Annie

    2004-01-01

    The gas hydrates are solid compounds of clathrate type which can be formed starting from cold water and hydrocarbon gas molecules under pressure. These conditions are met in certain oil conduits and can lead to a problem of production. Indeed, the oil effluent which leaves a well of production always contains light water and hydrocarbon molecules (methane, ethane, propane) suitable form a gas hydrate. The methane hydrates are not naturally present in the layers of production because the tempe...

  6. Destabilization kinetics of polyvinylpyrrolidone-iodine in a field of low frequency impacts

    Science.gov (United States)

    Fadeev, G. N.; Ermolaeva, V. I.; Boldyrev, V. S.; Sinkevich, V. V.

    2016-09-01

    Experimental results on the destabilization kinetics of compounds with chelate structure (polyvinylpyrrolidone-iodine) in the field of the impact of low-frequency vibrations (from 2 to 45 Hz) are presented. The optimum frequencies at which the process rate is greatest are found for different impact modes. Based on the experimental data, conclusions are drawn as to the effect the energy of low-frequency impacts has on the studied clathrate and chelate structures.

  7. Fuel traps: mapping stability via water association.

    Energy Technology Data Exchange (ETDEWEB)

    Rempe, Susan L.; Clawson, Jacalyn S.; Greathouse, Jeffery A.; Alam, Todd M; Leung, Kevin; Varma, Sameer; Sabo, Dubravko; Martin, Marcus Gary; Cygan, Randall Timothy

    2007-03-01

    Hydrogen storage is a key enabling technology required for attaining a hydrogen-based economy. Fundamental research can reveal the underlying principles controlling hydrogen uptake and release by storage materials, and also aid in characterizing and designing novel storage materials. New ideas for hydrogen storage materials come from exploiting the properties of hydrophobic hydration, which refers to water s ability to stabilize, by its mode of association, specific structures under specific conditions. Although hydrogen was always considered too small to support the formation of solid clathrate hydrate structures, exciting new experiments show that water traps hydrogen molecules at conditions of low temperatures and moderate pressures. Hydrogen release is accomplished by simple warming. While these experiments lend credibility to the idea that water could form an environmentally attractive alternative storage compound for hydrogen fuel, which would advance our nation s goals of attaining a hydrogen-based economy, much work is yet required to understand and realize the full potential of clathrate hydrates for hydrogen storage. Here we undertake theoretical studies of hydrogen in water to establish a firm foundation for predictive work on clathrate hydrate H{sub 2} storage capabilities. Using molecular simulation and statistical mechanical theories based in part on quantum mechanical descriptions of molecular interactions, we characterize the interactions between hydrogen and liquid water in terms of structural and thermodynamic properties. In the process we validate classical force field models of hydrogen in water and discover new features of hydrophobic hydration that impact problems in both energy technology and biology. Finally, we predict hydrogen occupancy in the small and large cages of hydrogen clathrate hydrates, a property unresolved by previous experimental and theoretical work.

  8. Colossal magnetocapacitance effect at room temperature

    Science.gov (United States)

    Bishchaniuk, T. M.; Grygorchak, I. I.

    2014-05-01

    First nano-hybridized clathrate/cavitant structure of hierarchical architecture was synthesized. The results of investigations of the properties of initial nanoporous silica matrices MCM-41, with encapsulated in its pores of β-cyclodextrin in cavitand and cavitat (with FeSO4) states and change at room temperature in a constant magnetic field intensity of 2.75 kOe, have been presented. Phenomenon of enormous magnetocapacitance and giant negative variable-current magnetoresistance has been discovered.

  9. Coupled multiphysics modeling of gas hydrate bearing sediments

    OpenAIRE

    Sanchez, Marcelo; Gai, Xuerui; Santamarina, J. Carlos

    2014-01-01

    Gas hydrates are crystalline clathrate compounds made of water and a low molecular gas like methane (Sloan 1998). 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...

  10. The mysteries of memory effect and its elimination with antifreeze proteins

    Energy Technology Data Exchange (ETDEWEB)

    Walker, V.; Gordienko, R.; Kuiper, M.; Huva, E.; Wu, Z. [Queen' s Univ., Kingston, ON (Canada). Dept. of Biology; Zeng, H.; Ripmeester, J. [Queen' s Univ., Kingston, ON (Canada). Dept. of Biology]|[National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences

    2008-07-01

    With the decline in easily accessible and conventional hydrocarbon supplies, exploration will focus on hydrocarbons in deep offshore waters, in permafrost or in crystalline water as gas hydrates. Crystallization of water or water-encaged gas molecules takes place when nuclei reach a critical size, but the crystal growth may be inhibited by certain antifreeze proteins (AFPs). In this study, the authors hypothesized that the crystal lattice of gas hydrates may act as an alternative for substrate antifreeze proteins (AFPs). AFP-mediated inhibition of ice and clathrate hydrate crystallization was examined. Since the AFPs had a notable ability to eliminate the memory effect (ME) or the faster reformation of clathrate hydrates after melting, the authors were prompted to examine heterogeneous nucleation. Silica, served as a model nucleator hydrophilic surface. Quartz crystal microbalance-dissipation (QCM-D) experiments showed that an active AFP was tightly adsorbed to the silica surface. However, polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap), 2 commercial hydrate kinetic inhibitors that do not eliminate ME, were not as tightly adsorbed. A mutant AFP inhibited tetrahydrofuran clathrate hydrate growth, but not ME. QCM-D analysis showed that adsorption of the mutant AFP was more similar to PVCap than the active AFP. It was concluded that although there is no evidence for memory in ice reformation, the crystallization of ice and hydrates, and the elimination of the more rapid recrystallization of hydrates, can be mediated by the same proteins. The properties of adsorbed layers can be effectively monitored by QCM-D. These study results provided useful information about the inhibition mechanism of heterogeneous nucleation of clathrate hydrate. The technique facilitates the screening of potential low dose hydrate inhibitors and residues in AFPs that are involved in silica adsorption. 24 refs., 1 tab., 4 figs.

  11. Scattering and Optical Properties of Water Ice

    Science.gov (United States)

    Yanamandra-Fisher, P. A.

    2003-01-01

    Light scattering by planetary ices of interest such as water, methane, clathrated species, will provide insight into the nature of the Jovian moons targeted by the JIMO mission - Europa, Callisto and Ganymede - composition, surface properties and thickness of ice mantles. Although much remote sensing data exists, theoretical models lag the data. We highlight the current state of theoretical and experimental models for water ice and highlight areas of study necessary to address the JIMO goals regarding surface and subsurface properties.

  12. Review of Solid State Hydrogen Storage Methods Adopting Different Kinds of Novel Materials

    OpenAIRE

    Renju Zacharia; Sami ullah Rather

    2015-01-01

    Overview of advances in the technology of solid state hydrogen storage methods applying different kinds of novel materials is provided. Metallic and intermetallic hydrides, complex chemical hydride, nanostructured carbon materials, metal-doped carbon nanotubes, metal-organic frameworks (MOFs), metal-doped metal organic frameworks, covalent organic frameworks (COFs), and clathrates solid state hydrogen storage techniques are discussed. The studies on their hydrogen storage properties are in pr...

  13. Coupled models of free methane gas and anaerobic oxidation of methane : from core to regional scales. Geologica Ultraiectina (339)

    OpenAIRE

    Mogollón, J.M.

    2011-01-01

    Methane is a potent greenhouse gas that is produced in marine sediments containing high amounts of degrading organic carbon. It is therefore not surprising that marine sediments contain vast amounts of methane (500-5000 gigatons) present in dissolved (aqueous), free gas (gaseous), and solid (clathrate) forms. Nevertheless, very little methane ultimately escapes into the atmosphere (circa 10 - 15 Tg/yr, or 2% of the total methane emissions into the atmosphere) due, for the most part, to the an...

  14. 微小重力下におけるエアロゾル・デポジション法による薄膜形成

    OpenAIRE

    Watanabe, Masahito; Nakano, Shizuka; Akedo, Jun; 渡邉 匡人; 中野 禅; 明渡 純

    2007-01-01

    In this research, we clarify the aerosol dynamics during thin film formation by using the Aerosol Deposition (AD) technique under the microgravity conditions. The aerosol deposition technique is useful for making thin film of ceramics materials. We are now trying this technique to make thin film of thermally unstable materials, such as clathrate compounds and/or amorphous materials. However, it is difficult to make homogeneously the aerosol of these materials in the terrestrial conditions, be...

  15. Atmospheric Impact of Large Methane Emissions and the Gulf Oil Spill

    Science.gov (United States)

    Bhattacharyya, S.; Cameron-Smith, P. J.; Bergmann, D. J.

    2010-12-01

    A vast quantity of a highly potent greenhouse gas, methane, is locked in the solid phase as methane clathrates in ocean sediments and underneath permafrost regions. Clathrates are ice-like deposits containing a mixture of water and gas (mostly methane) which are stable under high pressure and low temperatures. Current estimates are about 1600 - 2000 GtC present in oceans and about 400GtC in Arctic permafrost (Archer et al. 2009). This is about 4000 times that of current annual emissions. In a warming climate, increase in ocean temperatures could rapidly destabilize the geothermal gradient which in turn could lead to dissociation of the clathrates and release of methane into the ocean and subsequently into the atmosphere as well. This could result in a number of effects including strong greenhouse heating, increased surface ozone, reduced stratospheric ozone, and intensification of the Arctic ozone hole. Many of the effects in the chemistry of the atmosphere are non-linear. In this paper, we present a parametric study of the effect of large scale methane release to the atmosphere. To that end we use the CESM (Community Earth System Model) version 1 with fully active coupled atmosphere-ocean-land model together with super-fast atmospheric chemistry module to simulate the response to increasing CH4 by 2, 3, 10 and 100 times that of the present day. We have also conducted a parametric study of the possible impact of gaseous emissions from the oil spill in the Gulf of Mexico, which is a proxy for future clathrate releases. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

  16. Coexistence of structure I and II gas hydrates in Lake Baikal suggesting gas sources from microbial and thermogenic origin

    OpenAIRE

    Kida, M; Khlystov, O.; Zemskaya, T.; Takahashi, N; Minami, H.; Sakagami, H; Krylov, A.; Hachikubo, A.; YAMASHITA, S.; Shoji, H; J. Poort; L. Naudts

    2006-01-01

    We report the field observation of hydrate deposits of different crystal structures in the same cores of a mud volcano in the Kukuy Canyon. We link those deposits to chemical fractionation during gas hydrate crystallization. Gas composition and crystallographic analyses of hydrate samples reveal involvement of two distinct gas source types in gas hydrate formation at present or in the past: microbial (methane) and thermogenic (methane and ethane) gas types. The clathrate structure II, observe...

  17. Origin of Molecular Oxygen in Comet 67P/Churyumov–Gerasimenko

    Science.gov (United States)

    Mousis, O.; Ronnet, T.; Brugger, B.; Ozgurel, O.; Pauzat, F.; Ellinger, Y.; Maggiolo, R.; Wurz, P.; Vernazza, P.; Lunine, J. I.; Luspay-Kuti, A.; Mandt, K. E.; Altwegg, K.; Bieler, A.; Markovits, A.; Rubin, M.

    2016-06-01

    Molecular oxygen has been detected in the coma of comet 67P/Churyumov–Gerasimenko with abundances in the 1%–10% range by the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis-Double Focusing Mass Spectrometer instrument on board the Rosetta spacecraft. Here we find that the radiolysis of icy grains in low-density environments such as the presolar cloud may induce the production of large amounts of molecular oxygen. We also show that molecular oxygen can be efficiently trapped in clathrates formed in the protosolar nebula (PSN), and that its incorporation as crystalline ice is highly implausible, because this would imply much larger abundances of Ar and N2 than those observed in the coma. Assuming that radiolysis has been the only O2 production mechanism at work, we conclude that the formation of comet 67P/Churyumov–Gerasimenko is possible in a dense and early PSN in the framework of two extreme scenarios: (1) agglomeration from pristine amorphous icy grains/particles formed in ISM and (2) agglomeration from clathrates that formed during the disk’s cooling. The former scenario is found consistent with the strong correlation between O2 and H2O observed in comet 67P/Churyumov-Gerasimenko’s coma while the latter scenario requires that clathrates formed from ISM icy grains that crystallized when entering the PSN.

  18. Application of gas hydrate formation in separation processes: A review of experimental studies

    International Nuclear Information System (INIS)

    Highlights: ► Review of gas hydrate technology applied to separation processes. ► Gas hydrates have potential to be a future sustainable separation technology. ► More theoretical, simulation, and economic studies needed. - Abstract: There has been a dramatic increase in gas hydrate research over the last decade. Interestingly, the research has not focussed on only the inhibition of gas hydrate formation, which is of particular relevance to the petroleum industry, but has evolved into investigations on the promotion of hydrate formation as a potential novel separation technology. Gas hydrate formation as a separation technology shows tremendous potential, both from a physical feasibility (in terms of effecting difficult separations) as well as an envisaged lower energy utilization criterion. It is therefore a technology that should be considered as a future sustainable technology and will find wide application, possibly replacing a number of current commercial separation processes. In this article, we focus on presenting a brief description of the positive applications of clathrate hydrates and a comprehensive survey of experimental studies performed on separation processes using gas hydrate formation technology. Although many investigations have been undertaken on the positive application of gas hydrates to date, there is a need to perform more theoretical, experimental, and economic studies to clarify various aspects of separation processes using clathrate/semi-clathrate hydrate formation phenomena, and to conclusively prove its sustainability.

  19. Exotic Forms of Silicon for Energy Applications

    Science.gov (United States)

    Taylor, P. Craig

    2015-03-01

    Over the last few decades many exotic forms of carbon, such as carbon-60, carbon nanotubes, and graphene, have generated novel scientific discoveries and revolutionized many important applications. Similar potentially transformative breakthroughs may be expected with exotic forms of silicon. Such structures include, but are not necessarily limited to, (1) those formed under high pressure that are metastable at ambient pressure, (2) single layers of Si (silicene), (2) clathrate Si, which has been studied for superconducting and thermoelectric properties but not in any detail for semiconductor applications, (3) nanostructured forms of Si (nanodots and nanowires), including those composed of diamond Si, (4) porous Si, and (5) any other structures that differ in their structural, optical or electronic properties from bulk diamond Si. Silicon is an abundant, non-toxic element around which an advanced technology exists for semiconducting devices based on diamond Si. One of these exotic forms of Si could form the basis for the next revolution in electronics or even opto-electronics, since some forms exhibit direct, or nearly direct, band gaps. Recent results toward producing pure and dopable semiconductors out of Si nanodots imbedded in amorphous matrices and in clathrate Si and clathrate Si-Ge alloys will be discussed. The author acknowledges important collaborations with R. T. Collins, C. A. Koh, L. Krishna, M. Lusk, and P. Stradins. DOE SUNSHOT program, under Contract DE-EE0005326 and by the NSF MRSEC program under Grant DMR-0820518.

  20. Advanced heat pumps and their economic aspects. The case for super heat pump

    International Nuclear Information System (INIS)

    The results of the economic evaluation of the Super Heat Pump Energy Accumulation System project in Japan are reviewed. It is reported that although the initial costs of super heat pumps are higher than those of conventional systems, the calculated operating costs of a unit thermal energy produced by a super heat pump is reduced considerably. All the various system concepts with thermal/chemical storage were evaluated economically with the exception of the high temperature thermal storage systems using salt ammonia complexes and solvation. These latter systems were not further developed as pilot plants. It is advocated to accelerate the introduction of super heat pumps by facilitating their market introduction. Actual clathrate chemical storage systems have shown that the annual costs are comparable to those of an ice storage system. Clathrate systems will find their way in the market. It is concluded that most of the super heat pump systems and clathrate storage systems will be economic in the future. A big challenge however still exists in further improving the cost effectiveness of heat storage in tanks by reducing their size dramatically (to 1/10th)

  1. The radiometric analysis of non-radioactive materials by chemical exchange

    International Nuclear Information System (INIS)

    The use of radioisotopes to measure the composition of different materials via chemical exchange within an instrument is described. The product of the reaction is a radioactive gas which is counted and serves as the indicator of measurement. This method has been applied to a number of different liquids and gases for their specific and sensitive determination. The chief limiting condition on sensitivity is imposed by the specific activity of the radiochemical component. Where high specific activities are available, sensitivity in terms of chemical quantity will be very great. The recent development of quinol- Kr85 clathrate compounds has provided a basic radiochemical source which not only provides high specific activities at low cost but also excellent half-life and energy characteristics. These clathrate compounds can be oxidized only by very strong oxidizing agents, such as ozone to release Kr85. When coupled with a salt, such as sodium chlorite, the sensing of reducing materials such as SO2 may be accomplished. Two applications of the radiometric technique employing clathrates are described. The first is the development of a balloon-borne sonde for the meteorological analysis of ozone in the upper atmosphere. The other is its use in air pollution and process control work in the form of a portable analyser. Different gases may be analysed by this device by merely changing the radiochemical reaction cell. (author)

  2. Early Mars volcanic sulfur storage in the cryosphere and formation of transient SO2-rich atmospheres during the Hesperian

    CERN Document Server

    Schmidt, F; Tian, F; Dartois, E; Herri, J -M; Mousis, O

    2016-01-01

    In a previous paper (Chassefi\\`ere et al., Icarus 223, 878-891, 2013), we have shown that most volcanic sulfur released to early Mars atmosphere could have been trapped in the cryosphere under the form of CO2-SO2 clathrates. Huge amounts of sulfur, up to the equivalent of a ~1 bar atmosphere of SO2, would have been stored in the Noachian cryosphere, then massively released to the atmosphere during Hesperian due to rapidly decreasing CO2 pressure. It would have resulted in the formation of the large sulfate deposits observed mainly in Hesperian terrains, whereas no or little sulfates are found at the Noachian. In the present paper, we first clarify some aspects of our previous work. We discuss the possibility of a smaller cooling effect of sulfur particles, or even of a net warming effect. We point out the fact that CO2-SO2 clathrates formed through a progressive enrichment of a preexisting reservoir of CO2 clathrates and discuss processes potentially involved in the slow formation of a SO2-rich upper cryosphe...

  3. Photoluminescence properties of S2 molecule trapped in Melanophlogite

    Science.gov (United States)

    Messina, Fabrizio; Todaro, Michela; Buscarino, Gianpiero; Vaccaro, Lavinia; Cannas, Marco; Gelardi, Franco M.

    2016-03-01

    We studied the photoluminescence properties of a sample of SiO2-clathrate Melanophlogite, a crystalline microporous material which is found in nature as a rare mineral. Upon β irradiation, the material displays an intense light emission under near-UV illumination. We studied in detail this optical activity by steady-state and time-resolved photoluminescence measurements as a function of temperature. The spectroscopic properties we find can be ascribed to a population of quasi-free molecules trapped within each of the two different types of cage available in the structure of this clathrate, although the spectroscopic properties of the guest molecules are affected by their interactions with the host matrix. Based on the available data, we attribute the observed photoluminescence to trapped S2 molecules, emitting from their excited 3Σ u - or 3Π u electronic states, depending on the cage they are trapped in and on temperature. Our results have an impact on the fundamental understanding of host-guest interactions characteristic of microporous systems such as clathrates. Indeed, the data highlight that even a relatively weak coupling between quasi-free S2 molecules and the two types of cages provided by the Melanophlogite host has a surprisingly complex influence on the optical properties of the guest.

  4. Marine methane cycle simulations for the period of early global warming

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-01-02

    Geochemical environments, fates, and effects are modeled for methane released into seawater by the decomposition of climate-sensitive clathrates. A contemporary global background cycle is first constructed, within the framework of the Parallel Ocean Program. Input from organics in the upper thermocline is related to oxygen levels, and microbial consumption is parameterized from available rate measurements. Seepage into bottom layers is then superimposed, representing typical seabed fluid flow. The resulting CH{sub 4} distribution is validated against surface saturation ratios, vertical sections, and slope plume studies. Injections of clathrate-derived methane are explored by distributing a small number of point sources around the Arctic continental shelf, where stocks are extensive and susceptible to instability during the first few decades of global warming. Isolated bottom cells are assigned dissolved gas fluxes from porous-media simulation. Given the present bulk removal pattern, methane does not penetrate far from emission sites. Accumulated effects, however, spread to the regional scale following the modeled current system. Both hypoxification and acidification are documented. Sensitivity studies illustrate a potential for material restrictions to broaden the perturbations, since methanotrophic consumers require nutrients and trace metals. When such factors are considered, methane buildup within the Arctic basin is enhanced. However, freshened polar surface waters act as a barrier to atmospheric transfer, diverting products into the deep return flow. Uncertainties in the logic and calculations are enumerated including those inherent in high-latitude clathrate abundance, buoyant effluent rise through the column, representation of the general circulation, and bacterial growth kinetics.

  5. The dual origin of the nitrogen deficiency in comets: selective volatile trapping in the nebula and postaccretion radiogenic heating

    CERN Document Server

    Mousis, Olivier; Lunine, Jonathan I; Cochran, Anita L; Waite, J Hunter; Petit, Jean-Marc; Rousselot, Philippe

    2012-01-01

    We propose a scenario that explains the apparent nitrogen deficiency in comets in a way consistent with the fact that the surfaces of Pluto and Triton are dominated by nitrogen-rich ice. We use a statistical thermodynamic model to investigate the composition of the successive multiple guest clathrates that may have formed during the cooling of the primordial nebula from the most abundant volatiles present in the gas phase. These clathrates agglomerated with the other ices (pure condensates or stoichiometric hydrates) and formed the building blocks of comets. We report that molecular nitrogen is a poor clathrate former, when we consider a plausible gas phase composition of the primordial nebula. This implies that its trapping into cometesimals requires a low disk temperature ($\\sim$20 K) in order to allow the formation of its pure condensate. We find that it is possible to explain the lack of molecular nitrogen in comets as a consequence of their postformation internal heating engendered by the decay of short-...

  6. Geodetic data support trapping of ethane in Titan's polar crust

    Science.gov (United States)

    Sotin, Christophe; Rambaux, Nicolas

    2016-04-01

    Titan's surface is characterized by polar depressions that strongly influence interpretations of the gravity data. This study investigates several geodynamical models that can explain these depressions. For each model, the values of the three moments of inertia are computed numerically by discretizing the interior in spherical coordinates. The study shows that a Pratt model where the polar subsurface is made of ethane clathrates can explain the polar depression, the abrupt jump in altitude at about 60 degrees latitude, and the values of the degree 2 gravity coefficients. This model, proposed by Choukroun and Sotin [1], is based on the stability of ethane clathrate hydrates relative to methane clathrate hydrates. In addition to fitting the geodetic data, it explains the absence of ethane in Titan's atmosphere although ethane is the main product of the photolysis of methane. Other geophysical models based on latitudinal variations in the tidal heating production or in the heat flux at the base of the icy crust do not provide such a good match to the gravity and topographic observations. The ethane-clathrate model predicts that all the ethane produced by photolysis of methane at the present rate during the last billion years could be stored in the polar subsurface. It is consistent with the age of Titan's surface and that of Titan's atmospheric methane inferred from geological and geochemical observations by the Cassini/Huygens mission. The present study also emphasizes the role of mass anomalies on the interpretation of the degree 2 gravity coefficients. It shows that for Titan, a slow rotator, the values of the two equatorial moments of inertia (MoI) are largely affected by the polar depressions whereas the value of polar MoI is not. Therefore, as pointed out by previous calculations [2], calculating the moment of inertia (MoI) factor from the value of J2 could lead to major errors. This is not the case for our preferred Titan's model for which the negative polar

  7. A sublimation technique for high-precision measurements of δ13CO2 and mixing ratios of CO2 and N2O from air trapped in ice cores

    Directory of Open Access Journals (Sweden)

    H. Fischer

    2011-07-01

    Full Text Available In order to provide high precision stable carbon isotope ratios (δ13CO2 or δ13C of CO2 from small bubbly, partially and fully clathrated ice core samples we developed a new method based on sublimation coupled to gas chromatography-isotope ratio mass spectrometry (GC-IRMS. In a first step the trapped air is quantitatively released from ~30 g of ice and CO2 together with N2O are separated from the bulk air components and stored in a miniature glass tube. In an off-line step, the extracted sample is introduced into a helium carrier flow using a minimised tube cracker device. Prior to measurement, N2O and organic sample contaminants are gas chromatographically separated from CO2. Pulses of a CO2/N2O mixture are admitted to the tube cracker and follow the path of the sample through the system. This allows an identical treatment and comparison of sample and standard peaks. The ability of the method to reproduce δ13C from bubble and clathrate ice is verified on different ice cores. We achieve reproducibilities for bubble ice between 0.05 ‰ and 0.07 ‰ and for clathrate ice between 0.05 ‰ and 0.09 ‰ (dependent on the ice core used. A comparison of our data with measurements on bubble ice from the same ice core but using a mechanical extraction device shows no significant systematic offset. In addition to δ13C, the CO2 and N2O mixing ratios can be volumetrically derived with a precision of 2 ppmv and 8 ppbv, respectively.

  8. A sublimation technique for high-precision measurements of δ13CO2 and mixing ratios of CO2 and N2O from air trapped in ice cores

    Directory of Open Access Journals (Sweden)

    H. Fischer

    2011-03-01

    Full Text Available In order to provide high precision stable carbon isotope ratios (δ13CO2 or δ13C on CO2 from small bubble and clathrate ice core samples we developed a new method based on vacuum sublimation extraction of the CO2 and gas chromatography-isotope ratio mass spectrometry (GC-IRMS. In a first step the trapped air is quantitatively released from ~30 g of ice and CO2 together with N2O are separated from the bulk air components and stored in a miniature glass tube. In an off-line step, the extracted sample is introduced into a helium carrier flow using a minimised tube cracker device. Prior to measurement, N2O and organic sample contaminants are gas chromatographically separated from CO2. Pulses of a CO2/N2O mixture are admitted to the tube cracker and follow the path of the sample through the system. This allows an identical treatment and comparison of sample and standard peaks. The ability of the method to reproduce δ13C from bubble and clathrate ice is verified on different ice cores. We achieve reproducibilities for bubble ice between 0.05‰ and 0.07‰ and for clathrate ice between 0.05‰ and 0.09‰ (dependent on the ice core used. A comparison of our data with measurements on bubble ice from the same ice core but using a mechanic extraction device shows no significant systematic offset. In addition to δ13C, the CO2 and N2O mixing ratios can be volumetrically derived with a precision of 2 ppmv and 8 ppbv, respectively.

  9. Cadence and cause of lake-forming climates on Mars

    Science.gov (United States)

    Kite, Edwin; Goldblatt, Colin; Gao, Peter; Mayer, David; Sneed, Jonathan

    2016-10-01

    Paleolakes on Mars record a sustained hydrologic cycle, but soils upstream record a largely dry past, so lake-forming climates were intermittent. The cadence of lakes on Mars is constrained by relatively young (~3 Ga) deltas and alluvial fans. Deposit build-up required lakes to persist for >2 Kyr (assuming dilute flow), but the watersheds' little-weathered soils indicate a swift return to dry conditions. The lake-forming climates' duty cycle and trigger mechanism remain unknown. Here we show that these data are inconsistent with many previously-proposed triggers for lake-forming climates, but consistent with a novel CH4-burst mechanism. Assuming runoff was sourced from snowmelt, SO2- and impact-triggered warming are too brief, and H2-enabled warming too persistent, to match data. However, chaotic transitions in mean obliquity are a potential trigger with suitable cadence. Mean-obliquity transitions drive latitudinal shifts in temperature and ice loading that destabilize CH4 clathrate. For achievable hydrate stability zone occupancy fractions, CH4 builds up to levels whose direct radiative forcing is comparable to a quadrupling of CO2 (20 W/m2), and sufficient to modulate lake-forming climates. Sub-lake CH4 destabilization provides positive feedback. Photolysis of CH4 curtails individual lake-forming climates to 105-106 yr duration, and depletion of CH4-clathrate limits lake-forming climates to 1-3 in number, consistent with intermittency data. We further propose that Mars' first atmospheric collapse could drive ice sheets from highlands to poles, destabilizing sub-ice clathrate and triggering the formation of the ~4 Ga-old valley networks. Our results show how a warmer early Mars can undergo intermittent orbitally-triggered excursions to a warm, wet climate state.

  10. TITAN'S BULK COMPOSITION CONSTRAINED BY CASSINI-HUYGENS: IMPLICATION FOR INTERNAL OUTGASSING

    Energy Technology Data Exchange (ETDEWEB)

    Tobie, G. [Universite de Nantes, LPGNantes, UMR 6112, F-44322 Nantes (France); Gautier, D. [LESIA, Observatoire de Paris, F-92195 Meudon Cedex (France); Hersant, F. [Universite Bordeaux, LAB, UMR 5804, F-33270, Floirac (France)

    2012-06-20

    In the present report, by using a series of data gathered by the Cassini-Huygens mission, we constrain the bulk content of Titan's interior for various gas species (CH{sub 4}, CO{sub 2}, CO, NH{sub 3}, H{sub 2}S, Ar, Ne, Xe), and we show that most of the gas compounds (except H{sub 2}S and Xe) initially incorporated within Titan are likely stored dissolved in the subsurface water ocean. CO{sub 2} is likely to be the most abundant gas species (up to 3% of Titan's total mass), while ammonia should not exceed 1.5 wt%. We predict that only a moderate fraction of CH{sub 4}, CO{sub 2}, and CO should be incorporated in the crust in the form of clathrate hydrates. By contrast, most of the H{sub 2}S and Xe should be incorporated at the base of the subsurface ocean, in the form of heavy clathrate hydrates within the high-pressure ice layer. Moreover, we show that the rocky phase of Titan, assuming a composition similar to CI carbonaceous chondrites, is a likely source for the noble gas isotopes ({sup 40}Ar, {sup 36}Ar, {sup 22}Ne) that have been detected in the atmosphere. A chondritic core may also potentially contribute to the methane inventory. Our calculations show that a moderate outgassing of methane containing traces of neon and argon from the subsurface ocean would be sufficient to explain the abundance estimated by the Gas Chromatograph Mass Spectrometer. The extraction process, implying partial clathration in the ice layers and exsolvation from the water ocean, may explain why the {sup 22}Ne/{sup 36}Ar ratio in Titan's atmosphere appears higher than the ratio in carbonaceous chondrites.

  11. Neutron conversion and cascaded cooling in paramagnetic systems for a high-flux source of very cold neutrons

    Science.gov (United States)

    Zimmer, Oliver

    2016-03-01

    A new neutron-cooling mechanism is proposed with potential benefits for novel intense sources of very cold neutrons with wavelengths >2 nm, and for enhancing the production of ultracold neutrons. It employs inelastic magnetic scattering in weakly absorbing, cold paramagnetic systems. Kinetic energy is removed from the neutron stepwise in constant decrements determined by the Zeeman energy of paramagnetic atoms or ions in an external magnetic field, or by zero-field level splittings in magnetic molecules. The stationary neutron transport equation is analyzed for an infinite, homogeneous medium with Maxwellian neutron sources, using inelastic scattering cross sections derived in an appendix. Nonmagnetic inelastic scattering processes are neglected. The solution therefore still underestimates very cold neutron densities that should be achievable in a real medium. Molecular oxygen with its triplet ground state appears particularly promising, notably as a host in fully deuterated O2-clathrate hydrate. Other possibilities are dry O2-4He van der Waals clusters and O2 intercalated in fcc-C60. For conversion of cold to ultracold neutrons, where an incident neutron imparts only a single energy quantum to the medium, the paramagnetic scattering in the clathrate system is found to be stronger, by more than an order of magnitude, than the single-phonon emission in superfluid helium, when evaluated for an incident neutron spectrum with the optimum temperature for the respective medium. Moreover, the multistep paramagnetic cooling cascade leads to further strong enhancements of very cold neutron densities, e.g., by a factor 14 (57) for an initial neutron temperature of 30 K (100 K ), for the moderator held at about 1.3 K . Due to a favorable Bragg cutoff of the O2 clathrate, the cascade-cooling can take effect in a moderator with linear extensions smaller than a meter.

  12. Coronene-based charge-transfer complexes.

    Science.gov (United States)

    Yoshida, Yukihiro; Isomura, Kazuhide; Kumagai, Yoshihide; Maesato, Mitsuhiko; Kishida, Hideo; Mizuno, Motohiro; Saito, Gunzi

    2016-08-01

    Recent developments in the arena of charge-transfer complexes composed of the D 6h-symmetric polycyclic aromatic hydrocarbon, coronene, are highlighted with emphasis on the structural and physical properties of these complexes. Because of the dual electron-donating and -accepting abilities of coronene, this group involves structurally-defined four cation salts and three anion salts. The Jahn-Teller distortions and in-plane motion of coronene molecules in the solids, both of which are closely associated with the high symmetry of coronene molecules, and syntheses of clathrate-type complexes are also presented. PMID:27294380

  13. Thermodynamic Stability of Structure H Hydrates Based on the Molecular Properties of Large Guest Molecules

    Directory of Open Access Journals (Sweden)

    Ryo Ohmura

    2012-02-01

    Full Text Available This paper report analyses of thermodynamic stability of structure-H clathrate hydrates formed with methane and large guest molecules in terms of their gas phase molecular sizes and molar masses for the selection of a large guest molecule providing better hydrate stability. We investigated the correlation among the gas phase molecular sizes, the molar masses of large molecule guest substances, and the equilibrium pressures. The results suggest that there exists a molecular-size value for the best stability. Also, at a given molecule size, better stability may be available when the large molecule guest substance has a larger molar mass.

  14. Theoretical Study of the Structural and Electronic Properties of KxSi136, (x = 1, 8, 18)

    Science.gov (United States)

    Higgins, Craig; Myles, Charles

    2012-10-01

    Type II clathrate semiconductors have cage-like lattices in which Group IV atoms are tetrahedrally-coordinated and sp^3 covalently bonded. The cages can contain ``guest'' atoms; usually alkali or alkaline earth atoms. These materials are of interest because of their thermoelectric properties. Measurements of the lattice constant [1] as a function of Na concentration x in NaxSi136 (0 DOI: 10.1021/ic1005049[0pt] [2] S. Stefanoski and G. Nolas, Cryst. Growth Des. 2011, dx.doi.org/10.1021/cg200756r

  15. I8As21Ge25

    Directory of Open Access Journals (Sweden)

    2009-03-01

    Full Text Available Single crystals of octaiodine henacosarsenic pentacosagermanium were grown by chemical transport reactions. The structure is isotypic with the analogous clathrates-I. In this structure, the statistically occupied clathrand atoms (As,Ge46 form bonds in a distorted tetrahedral coordination and their arrangement can define two polyhedra of different sizes; one is an (As,Ge20 pentagonal dodecahedron, and the other is an (As,Ge24 tetrakaidecahedron. The guest atom (iodine resides inside these polyhedra with site symmetry m3 (Wyckoff position 2a and overline{4}2m (Wyckoff position 6d, respectively.

  16. Coexistence of structure I and II gas hydrates in Lake Baikal suggesting gas sources from microbial and thermogenic origin

    Science.gov (United States)

    Kida, Masato; Khlystov, Oleg; Zemskaya, Tamara; Takahashi, Nobuo; Minami, Hirotsugu; Sakagami, Hirotoshi; Krylov, Alexey; Hachikubo, Akihiro; Yamashita, Satoshi; Shoji, Hitoshi; Poort, Jeffrey; Naudts, Lieven

    2006-12-01

    We report the field observation of hydrate deposits of different crystal structures in the same cores of a mud volcano in the Kukuy Canyon. We link those deposits to chemical fractionation during gas hydrate crystallization. Gas composition and crystallographic analyses of hydrate samples reveal involvement of two distinct gas source types in gas hydrate formation at present or in the past: microbial (methane) and thermogenic (methane and ethane) gas types. The clathrate structure II, observed for the first time in fresh water sediments, is believed to be formed by higher mixing of thermogenic gas.

  17. Origin of molecular oxygen in Comet 67P/Churyumov-Gerasimenko

    CERN Document Server

    Mousis, O; Brugger, B; Ozgurel, O; Pauzat, F; Ellinger, Y; Maggiolo, R; Wurz, P; Vernazza, P; Lunine, J I; Luspay-Kuti, A; Mandt, K E; Altwegg, K; Bieler, A; Markovits, A; Rubin, M

    2016-01-01

    Molecular oxygen has been detected in the coma of comet 67P/Churyumov-Gerasimenko with abundances in the 1-10% range by the ROSINA-DFMS instrument on board the Rosetta spacecraft. Here we find that the radiolysis of icy grains in low-density environments such as the presolar cloud may induce the production of large amounts of molecular oxygen. We also show that molecular oxygen can be efficiently trapped in clathrates formed in the protosolar nebula, and that its incorporation as crystalline ice is highly implausible because this would imply much larger abundances of Ar and N2 than those observed in the coma. Assuming that radiolysis has been the only O2 production mechanism at work, we conclude that the formation of comet 67P/Churyumov-Gerasimenko is possible in a dense and early protosolar nebula in the framework of two extreme scenarios: (1) agglomeration from pristine amorphous icy grains/particles formed in ISM and (2) agglomeration from clathrates that formed during the disk's cooling. The former scenar...

  18. From Kelvin problem to Kelvin carbons.

    Science.gov (United States)

    Zhao, Hui-Yan; Wang, Jing; Ma, Qing-Min; Liu, Ying

    2013-04-28

    As children's toys, soap bubbles also underpin many important scientific questions. What is the most efficient structure for foam? - the "Kelvin problem," has been one of the most intriguing science and widely discussed over the past hundred years. Soap bubbles' frameworks have similar topology with sp(3)-bonded carbon or silicon allotropes, e.g., Weaire-Phelan foam and superconducting clathrate Na8Si46. By looking at the most efficient structure for foams, we construct a series of new carbon allotropes, named "Kelvin carbons." Unexpectedly, all 11 Kelvin carbons are structurally stable wide-bandgap semiconductors, and their densities and their intrinsic hardnesses are both about 81%-87% that of diamond. The seventh state of Kelvin carbons, K(VII), is a very low energy carbon structure after graphite, diamond, lonsdaleite, and type-II carbon clathrate. Kelvin carbons, which constitute a "bridge" between macro-foams and micro-carbons, together with recently proposed novel carbon phases can enrich the study of carbon allotropes. PMID:23635161

  19. Gas Hydrate Research Database and Web Dissemination Channel

    Energy Technology Data Exchange (ETDEWEB)

    Micheal Frenkel; Kenneth Kroenlein; V Diky; R.D. Chirico; A. Kazakow; C.D. Muzny; M. Frenkel

    2009-09-30

    To facilitate advances in application of technologies pertaining to gas hydrates, a United States database containing experimentally-derived information about those materials was developed. The Clathrate Hydrate Physical Property Database (NIST Standard Reference Database {number_sign} 156) was developed by the TRC Group at NIST in Boulder, Colorado paralleling a highly-successful database of thermodynamic properties of molecular pure compounds and their mixtures and in association with an international effort on the part of CODATA to aid in international data sharing. Development and population of this database relied on the development of three components of information-processing infrastructure: (1) guided data capture (GDC) software designed to convert data and metadata into a well-organized, electronic format, (2) a relational data storage facility to accommodate all types of numerical and metadata within the scope of the project, and (3) a gas hydrate markup language (GHML) developed to standardize data communications between 'data producers' and 'data users'. Having developed the appropriate data storage and communication technologies, a web-based interface for both the new Clathrate Hydrate Physical Property Database, as well as Scientific Results from the Mallik 2002 Gas Hydrate Production Research Well Program was developed and deployed at http://gashydrates.nist.gov.

  20. The search for green inhibitors : perturbing hydrate growth with bugs

    Energy Technology Data Exchange (ETDEWEB)

    Huva, E.; Gordienko, R. [Queen' s Univ., Kingston, ON (Canada). Dept. of Biology; Ripmeester, J.; Zeng, H. [Queen' s Univ., Kingston, ON (Canada). Dept. of Biology]|[National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences; Walker, V.K. [Queen' s Univ., Kingston, ON (Canada). Dept. of Biology]|[Queen' s Univ., Kingston, ON (Canada). Dept. of Microbiology and Immunology

    2008-07-01

    The ability of some organisms, such as insects and microbes, to survive low temperatures can be attributed to the production of either ice nucleating proteins (INPs) or antifreeze proteins (AFPs). INPs can direct crystal growth by inducing rapid ice formation. AFPs adsorb to ice embryos and decrease the temperature at which the ice grows. Certain AFPs can also inhibit the crystallization of clathrate hydrates and eliminate more rapid recrystallization or memory effect. This paper presented a study that involved the examination of bacterial species with ice-associating properties for their effect on tetrahydrofuran (THF) hydrate crystallization. As part of the study, THF hydrate formation was inhibited in the presence of cultures containing the ice-associating bacterium chryseobacterium C14. The paper discussed the methods used for the study, including hydrate formation and reformation in the presence of ice-associating bacteria and the development of a clathrate hydrate affinity purification technique. A 40 per cent reduction in crystallization was observed, indicating their potential as a commercial green inhibitor for hydrates. In addition, there was no elimination of memory effect, and little supporting evidence was seen for nucleation inhibition by any of the bacteria. 17 refs., 1 tab., 3 figs.

  1. Structural Basis for the Inhibition of Gas Hydrates by α-Helical Antifreeze Proteins.

    Science.gov (United States)

    Sun, Tianjun; Davies, Peter L; Walker, Virginia K

    2015-10-20

    Kinetic hydrate inhibitors (KHIs) are used commercially to inhibit gas hydrate formation and growth in pipelines. However, improvement of these polymers has been constrained by the lack of verified molecular models. Since antifreeze proteins (AFPs) act as KHIs, we have used their solved x-ray crystallographic structures in molecular modeling to explore gas hydrate inhibition. The internal clathrate water network of the fish AFP Maxi, which extends to the protein's outer surface, is remarkably similar to the {100} planes of structure type II (sII) gas hydrate. The crystal structure of this water web has facilitated the construction of in silico models for Maxi and type I AFP binding to sII hydrates. Here, we have substantiated our models with experimental evidence of Maxi binding to the tetrahydrofuran sII model hydrate. Both in silico and experimental evidence support the absorbance-inhibition mechanism proposed for KHI binding to gas hydrates. Based on the Maxi crystal structure we suggest that the inhibitor adsorbs to the gas hydrate lattice through the same anchored clathrate water mechanism used to bind ice. These results will facilitate the rational design of a next generation of effective green KHIs for the petroleum industry to ensure safe and efficient hydrocarbon flow. PMID:26488661

  2. Feasibility of Large-Scale Ocean CO2 Sequestration

    Energy Technology Data Exchange (ETDEWEB)

    Peter Brewer

    2008-08-31

    Scientific knowledge of natural clathrate hydrates has grown enormously over the past decade, with spectacular new findings of large exposures of complex hydrates on the sea floor, the development of new tools for examining the solid phase in situ, significant progress in modeling natural hydrate systems, and the discovery of exotic hydrates associated with sea floor venting of liquid CO{sub 2}. Major unresolved questions remain about the role of hydrates in response to climate change today, and correlations between the hydrate reservoir of Earth and the stable isotopic evidence of massive hydrate dissociation in the geologic past. The examination of hydrates as a possible energy resource is proceeding apace for the subpermafrost accumulations in the Arctic, but serious questions remain about the viability of marine hydrates as an economic resource. New and energetic explorations by nations such as India and China are quickly uncovering large hydrate findings on their continental shelves. In this report we detail research carried out in the period October 1, 2007 through September 30, 2008. The primary body of work is contained in a formal publication attached as Appendix 1 to this report. In brief we have surveyed the recent literature with respect to the natural occurrence of clathrate hydrates (with a special emphasis on methane hydrates), the tools used to investigate them and their potential as a new source of natural gas for energy production.

  3. Competition between intermolecular interaction and configuration entropy as the structure-determining factor for inclusion compounds

    Energy Technology Data Exchange (ETDEWEB)

    Subbotin, O.; Belosludov, V.; Adamova, T. [Russian Academy of Science, Novosibirsk (Russian Federation). Nikolaev Inst. of Inorganic Chemistry; Belosludov, R.; Kawazoe, Y. [Tohoku Univ., Aoba-ku, Sendai (Japan). Inst. for Materials Research; Kudoh, J.I. [Tohoku Univ., Aoba-ku, Sendai (Japan). Center for Northeast Asia Studies

    2008-07-01

    This paper presented a newly developed method to accurately predict the thermodynamic properties of clathrate hydrates, particularly their structural phase transitions under pressure. The method is based on the theory of Van-der-Waals and Platteeuw with some modifications that include the influence of guest molecules on the host lattice. The model was used to explain the exception from the established rule that small guest molecules form structure s1 and large molecules form structure s2 hydrates. In this study, the thermodynamic properties of argon (Ar) hydrate and methane hydrate, each in both cubic structure s1 and s2 were modelled. The model showed that two competing factors play a role in the formation of inclusions, notably the intermolecular interaction of guest molecules with water molecules, and the configuration entropy. Competition of these 2 factors determines the structure of hydrate formed at different pressures. The model provides an accurate description of the thermodynamic properties of gas hydrates and how they behave under pressure. For the argon hydrates, the structural phase transition from structure s2 to s1 at high pressure was predicted, while methane hydrates were predicted to be metastable in the s2 structure. The model can be used for other inclusion compounds with the same type of composition such as clathrate silicon, zeolites, and inclusion compounds of semiconductor elements. 17 refs., 5 figs.

  4. Water dynamics on ice and hydrate lattices studied by second-order central-line stimulated-echo oxygen-17 nuclear magnetic resonance

    International Nuclear Information System (INIS)

    Oxygen-17 stimulated-echo spectroscopy is a novel nuclear magnetic resonance (NMR) technique that allows one to investigate the time scale and geometry of ultraslow molecular motions in materials containing oxygen. The method is based on detecting orientationally encoded frequency changes within oxygen’s central-transition NMR line that are caused by second-order quadrupolar interactions. In addition to the latter, the present theoretical analysis of various two-pulse echo and stimulated-echo pulse sequences takes also heteronuclear dipolar interactions into account. As an experimental example, the ultraslow water motion in polycrystals of tetrahydrofuran clathrate hydrate is studied via two-time oxygen-17 stimulated-echo correlation functions. The resulting correlation times and those of hexagonal ice are similar to those from previous deuteron NMR measurements. Calculations of the echo functions’ final-state correlations for various motional models are compared with the experimental data of the clathrate hydrate. It is found that a six-site model including the oxygen-proton dipolar interaction describes the present results

  5. Novel dimeric β-helical model of an ice nucleation protein with bridged active sites

    Directory of Open Access Journals (Sweden)

    Walker Virginia K

    2011-09-01

    Full Text Available Abstract Background Ice nucleation proteins (INPs allow water to freeze at high subzero temperatures. Due to their large size (>120 kDa, membrane association, and tendency to aggregate, an experimentally-determined tertiary structure of an INP has yet to be reported. How they function at the molecular level therefore remains unknown. Results Here we have predicted a novel β-helical fold for the INP produced by the bacterium Pseudomonas borealis. The protein uses internal serine and glutamine ladders for stabilization and is predicted to dimerize via the burying of a solvent-exposed tyrosine ladder to make an intimate hydrophobic contact along the dimerization interface. The manner in which PbINP dimerizes also allows for its multimerization, which could explain the aggregation-dependence of INP activity. Both sides of the PbINP structure have tandem arrays of amino acids that can organize waters into the ice-like clathrate structures seen on antifreeze proteins. Conclusions Dimerization dramatically increases the 'ice-active' surface area of the protein by doubling its width, increasing its length, and presenting identical ice-forming surfaces on both sides of the protein. We suggest that this allows sufficient anchored clathrate waters to align on the INP surface to nucleate freezing. As PbINP is highly similar to all known bacterial INPs, we predict its fold and mechanism of action will apply to these other INPs.

  6. Water dynamics on ice and hydrate lattices studied by second-order central-line stimulated-echo oxygen-17 nuclear magnetic resonance

    Science.gov (United States)

    Adjei-Acheamfour, Mischa; Tilly, Julius F.; Beerwerth, Joachim; Böhmer, Roland

    2015-12-01

    Oxygen-17 stimulated-echo spectroscopy is a novel nuclear magnetic resonance (NMR) technique that allows one to investigate the time scale and geometry of ultraslow molecular motions in materials containing oxygen. The method is based on detecting orientationally encoded frequency changes within oxygen's central-transition NMR line that are caused by second-order quadrupolar interactions. In addition to the latter, the present theoretical analysis of various two-pulse echo and stimulated-echo pulse sequences takes also heteronuclear dipolar interactions into account. As an experimental example, the ultraslow water motion in polycrystals of tetrahydrofuran clathrate hydrate is studied via two-time oxygen-17 stimulated-echo correlation functions. The resulting correlation times and those of hexagonal ice are similar to those from previous deuteron NMR measurements. Calculations of the echo functions' final-state correlations for various motional models are compared with the experimental data of the clathrate hydrate. It is found that a six-site model including the oxygen-proton dipolar interaction describes the present results.

  7. Inter-cage dynamics in structure I, II, and H fluoromethane hydrates as studied by NMR and molecular dynamics simulations

    International Nuclear Information System (INIS)

    Prospective industrial applications of clathrate hydrates as materials for gas separation require further knowledge of cavity distortion, cavity selectivity, and defects induction by guest-host interactions. The results presented in this contribution show that under certain temperature conditions the guest combination of CH3F and a large polar molecule induces defects on the clathrate hydrate framework that allow intercage guest dynamics. 13C NMR chemical shifts of a CH3F/CH4/TBME sH hydrate and a temperature analysis of the 2H NMR powder lineshapes of a CD3F/THF sII and CD3F/TBME sH hydrate, displayed evidence that the populations of CH4 and CH3F in the D and D′ cages were in a state of rapid exchange. A hydrogen bonding analysis using molecular dynamics simulations on the TBME/CH3F and TBME/CH4 sH hydrates showed that the presence of CH3F enhances the hydrogen bonding probability of the TBME molecule with the water molecules of the cavity. Similar results were obtained for THF/CH3F and THF/CH4 sII hydrates. The enhanced hydrogen bond formation leads to the formation of defects in the water hydrogen bonding lattice and this can enhance the migration of CH3F molecules between adjacent small cages

  8. Towards a fundamental understanding of natural gas hydrates.

    Science.gov (United States)

    Koh, Carolyn A

    2002-05-01

    Gas clathrate hydrates were first identified in 1810 by Sir Humphrey Davy. However, it is believed that other scientists, including Priestley, may have observed their existence before this date. They are solid crystalline inclusion compounds consisting of polyhedral water cavities which enclathrate small gas molecules. Natural gas hydrates are important industrially because the occurrence of these solids in subsea gas pipelines presents high economic loss and ecological risks, as well as potential safety hazards to exploration and transmission personnel. On the other hand, they also have technological importance in separation processes, fuel transportation and storage. They are also a potential fuel resource because natural deposits of predominantly methane hydrate are found in permafrost and continental margins. To progress with understanding and tackling some of the technological challenges relating to natural gas hydrate formation, inhibition and decomposition one needs to develop a fundamental understanding of the molecular mechanisms involved in these processes. This fundamental understanding is also important to the broader field of inclusion chemistry. The present article focuses on the application of a range of physico-chemical techniques and approaches for gaining a fundamental understanding of natural gas hydrate formation, decomposition and inhibition. This article is complementary to other reviews in this field, which have focused more on the applied, engineering and technological aspects of clathrate hydrates. PMID:12122641

  9. How to link the relative abundances of gas species in coma of comets to their initial chemical composition ?

    CERN Document Server

    Marboeuf, Ulysse

    2014-01-01

    The chemical composition of comets is frequently assumed to be directly provided by the observations of the abundances of volatile molecules in the coma. The present work aims to determine the relationship between the chemical composition of the coma, the outgassing profile of volatile molecules and the internal chemical composition, and water ice structure of the nucleus, and physical assumptions on comets. To do this, we have developed a quasi 3D model of a cometary nucleus which takes into account all phase changes and water ice structures (amorphous, crystalline, clathrate, and a mixture of them); we have applied this model to the comet 67P/Churyumov-Gerasimenko, the target of the Rosetta mission. We find that the outgassing profile of volatile molecules is a strong indicator of the physical and thermal properties (water ice structure, thermal inertia, abundances, distribution, physical differentiation) of the solid nucleus. Day/night variations of the rate of production of species helps to distinguish th...

  10. Chaotic obliquity and the nature of the Martian climate

    Science.gov (United States)

    Jakosky, Bruce M.; Henderson, Bradley G.; Mellon, Michael T.

    1995-01-01

    Recent calculations of the Martian obliquity suggests that it varies chaotically on timescales longer than about 10(exp 7) years and varies between about 0 and 60 deg. We examine the seasonal water behavior at obliquities between 40 and 60 deg. Up to several tens of centimeters of water may sublime from the polar caps each year, and possibly move to the equator, where it is more stable. The CO2 frost and CO2-H2O clathrate hydrate are stable in thepolar deposits below a few tens of meters depth, so that the polar cap could contain a significant CO2 reservoir. If CO2 is present, it could be left over from the early history of Mars; also, it could be released into the atmosphere during periods of high obliquity, causing occasional periods of more-clement climate.

  11. (2,3,5,10,12,13,15,20-Octaphenylporphinatocopper(II 1,1,2,2-tetrachloroethane solvate

    Directory of Open Access Journals (Sweden)

    Babu Varghese

    2008-02-01

    Full Text Available The title complex, [Cu(C68H44N4]·C2H2Cl4, exhibits nearly square-planar geometry around the CuII centre and the macrocyclic ring is almost planar. The porphyrin molecule has an approximate non-crystallographic inversion centre (Ci, and a non-crystallographic twofold rotation axis (C2 within the CuII–porphyrin ring plane. Further, it has non-crystallographic twofold rotation axis and mirror plane (Cs symmetry perpendicular to the molecular plane. The molecular packing of the complexes and the solvent molecules shows weak intermolecular C—H...π, C—H...Cl and C—H...N interactions, forming a clathrate-like structure.

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

    Science.gov (United States)

    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.

  13. Large methane releases lead to strong aerosol forcing and reduced cloudiness

    DEFF Research Database (Denmark)

    Kurten, T.; Zhou, L.; Makkonen, R.;

    2011-01-01

    contributions from the associated carbon dioxide or ozone increases. Here, we study the effect of strongly elevated methane (CH4) levels on oxidant and aerosol particle concentrations using a combination of chemistry-transport and general circulation models. A 10-fold increase in methane concentrations is......The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller...... forcing that is comparable in magnitude to the long-wave radiative forcing ("enhanced greenhouse effect") of the added methane. Together, the indirect CH4-O-3 and CH4-OHaerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously...

  14. Cooling neutrons using non-dispersive magnetic excitations

    CERN Document Server

    Zimmer, Oliver

    2014-01-01

    A new method is proposed for cooling neutrons by inelastic magnetic scattering in weakly absorbing, cold paramagnetic systems. Kinetic neutron energy is removed in constant decrements determined by the Zeeman energy of paramagnetic atoms or ions in an external magnetic field, or by zero-field level splittings in magnetic molecules. Analytical solutions of the stationary neutron transport equation are given using inelastic neutron scattering cross sections derived in an appendix. They neglect any inelastic process except the paramagnetic scattering and hence still underestimate very-cold neutron densities. Molecular oxygen with its triplet ground state appears particularly promising, notably as a host in fully deuterated oxygen-clathrate hydrate, or more exotically, in dry oxygen-He4 van der Waals clusters. At a neutron temperature about 6 K, for which neutron conversion to ultra-cold neutrons by single-phonon emission in pure superfluid He4 works best, conversion rates due to paramagnetic scattering in the cl...

  15. Thermodynamics of a post combustion hydrate-based carbon dioxide capture process

    International Nuclear Information System (INIS)

    Hydrates selectivity towards carbon dioxide is offering a promising route for carbon dioxide removal from flue gases. Hydrate-based CO2 capture process could substitute amine facilities widely implemented in gas treatment plants but suffering from oxidative degradation problems and high energy demand. In the framework of this thesis, we focus on phase equilibria that are involved in such process. Experimental dissociation conditions for clathrate hydrates of carbon dioxide and nitrogen, in the presence of some promoting molecules (Tetrahydrofuran, Tetrabutyl ammonium bromide and Tetrabutyl ammonium Fluoride ) are reported in the experimental section of this work. The data generated in this work along with literature data are compared to the model predictions. The developed model is based on the Cubic Plus Association (CPA) equation of state (EoS) for fluid phases combined to the van der Waals and Platteeuw's theory for the hydrate phase. (author)

  16. Quantum Effects in Cosmochemistry: Complexation Energy and Van Der Waals Radii

    Science.gov (United States)

    Mittlefehldt, D. W.; Wilson, T. L.

    2007-01-01

    The subject of quantum effects in cosmochemistry was recently addressed with the goal of understanding how they contribute to Q-phase noble gas abundances found in meteorites. It was the pursuit of the Q-phase carrier of noble gases and their anomalous abundances that ultimately led to the identification, isolation, and discovery of presolar grains. In spite of its importance, Q-phase investigations have led a number of authors to reach conclusions that do not seem to be supported by quantum chemistry. In view of the subject's fundamental significance, additional study is called for. Two quantum properties of Q-phase candidates known as endohedral carbon-cage clathrates such as fullerenes will be addressed here. These are complexation energy and instability induced by Pauli blocking (exclusion principle).

  17. Initial estimation of hydrate formation temperature of sweet natural gases based on new empirical correlation

    Institute of Scientific and Technical Information of China (English)

    Mohammad Mahdi Ghiasi

    2012-01-01

    Production,processing and transportation of natural gases can be significantly affected by clathrate hydrates.Knowing the gas analysis is crucial to predict the right conditions for hydrate formation.Nevertheless,Katz gas gravity method can be used for initial estimation of hydrate formation temperature (HFT) under the circumstances of indeterminate gas composition.So far several correlations have been proposed for gas gravity method,in which the most accurate and reliable one has belonged to Bahadori and Vuthaluru.The main objective of this study is to present a simple and yet accurate correlation for fast prediction of sweet natural gases HFT based on the fit to Katz gravity chart.By reviewing the error analysis results,one can discover that the new proposed correlation has the best estimation capability among the widely accepted existing correlations within the investigated range.

  18. STUDY FOR NATURAL GAS HYDRATE CONVERSED FROM ICE

    Institute of Scientific and Technical Information of China (English)

    WANG Shengjie; SHEN Jiandong; HAO Miaoli; LIU Furong

    2003-01-01

    Natural gas hydrates are crystalline clathrate compounds composed of water and gases of small molecular diameters that can be used for storage and transport of natural gas as a novel method. In the paper a series of experiments of aspects and kinetics for hydrate formed from natural gas and ice were carried out on the industrial small scale production apparatus. The experimental results show that formation conditions of hydrate conversed from ice are independent of induction time, and bigger degrees of supersaturation and supercooling improved the driving force and advanced the hydrate formation.Superpressure is also favorable for ice particle conversion to hydrate. In addition, it was found there have an optimal reaction time during hydrate formation.

  19. Martian zeolites as a source of atmospheric methane

    CERN Document Server

    Mousis, Olivier; Bellat, Jean-Pierre; Schmidt, Frédéric; Bouley, Sylvain; Chassefière, Eric; Sautter, Violaine; Quesnel, Yoann; Picaud, Sylvain; Lectez, Sébastien

    2016-01-01

    The origin of the martian methane is still poorly understood. A plausible explanation is that methane could have been produced either by hydrothermal alteration of basaltic crust or by serpentinization of ultramafic rocks producing hydrogen and reducing crustal carbon into methane. Once formed, methane storage on Mars is commonly associated with the presence of hidden clathrate reservoirs. Here, we alternatively suggest that chabazite and clinoptilolite, which belong to the family of zeolites, may form a plausible storage reservoir of methane in the martian subsurface. Because of the existence of many volcanic terrains, zeolites are expected to be widespread on Mars and their Global Equivalent Layer may range up to more than $\\sim$1 km, according to the most optimistic estimates. If the martian methane present in chabazite and clinoptilolite is directly sourced from an abiotic source in the subsurface, the destabilization of a localized layer of a few millimeters per year may be sufficient to explain the curr...

  20. Glycine Betaine Recognition through Cation−π Interactions in Crystal Structures of Glycine Betaine Complexes with C-Ethyl-pyrogallol[4]arene and C-Ethyl-resorcin[4]arene as Receptors

    Directory of Open Access Journals (Sweden)

    Ikuhide Fujisawa

    2013-04-01

    Full Text Available The glycine betaine (betaine, interacts with several types of proteins with diverse structures in vivo, and in the contact regions, the aromatic rings of protein residues are frequently found beside the trimethylammonium group of betaine, implying the importance of the cation−π interactions in recognition of this molecule. The crystal structures determined by X-ray crystallography of the complexes of betaine and C-ethyl-pyrogallol[4]arene (pyrogallol cyclic tetramer: PCT and betaine and C-ethyl-resorcin[4]arene (resorcinol cyclic tetramer: RCT mimic the conformations of betaine and protein complexes and show that the clathrate conformations are retained by the cation−π interactions. The difference of the conformation feature of betaine in the Protein Data Bank and in the Cambridge Structural Database was found by chance during the research and analyzed with the torsion angles.

  1. Structural studies on inclusion compounds and solvent sorption behavior of gradually elongated wheel-and-axle-type diol hosts featuring lateral benzo[b]thiophene units

    Science.gov (United States)

    Katzsch, Felix; Gruber, Tobias; Weber, Edwin

    2016-06-01

    Based on the wheel-and-axle design strategy, a series of six new clathrate hosts featuring two di(benzo[b]thien-2-yl)hydroxymethyl units attached to both ends of a central linear building element of varying length have been synthesized and their capability to form crystalline inclusion compounds with a fixed range of organic solvents are reported. X-ray crystal structures of relevant inclusion compounds have been determined and are comparatively discussed involving structural modification of the host molecules. Organic vapor sorption behavior of the host compounds coated as solid films on the quartz crystal of a QCM device has been studied. Significant differences in the affinities towards solvent vapors dependent both on structural and polarity properties of host and solvent are observed, indicating potential application as mass sensitive materials.

  2. Novel Magnetic Materials for Sensing and Cooling Applications

    Science.gov (United States)

    Chaturvedi, Anurag

    2011-12-01

    field is of topical interest. In this project, we have systematically studied the ferromagnetism and magnetocaloric effect in Eu 8Ga16Ge30 clathrate materials, which are better known for their thermoelectric applications. We have discovered the GMC effect in the type-VIII clathrate and enhanced refrigerant capacity in the type-I clathrate. We have successfully used the clathrates as excellent host matrices to produce novel Eu8Ga16Ge30-EuO composite materials with desirable properties for active magnetic refrigeration technologies. A large refrigerant capacity of 794 J/kg for a field change of 5 T over a temperature interval of 70 K has been achieved in the Eu8Ga 16Ge30-EuO composite with a 40%--60% weight ratio. This is the largest value ever achieved among existing magnetocaloric materials for magnetic refrigeration in the temperature range 10 K--100 K. The excellent magnetocaloric properties of the Eu8Ga 16Ge30-EuO composites make them attractive for active magnetic refrigeration in the liquid nitrogen temperature range.

  3. I8Sb10Ge36

    Directory of Open Access Journals (Sweden)

    Mohammed Kars

    2010-06-01

    Full Text Available Single crystals of the title compound, octaiodide decaantimonate hexatriacontagermanide, were grown by chemical transport reactions. The structure is isotypic with the analogous clathrates-I. In this structure, the (Ge,Sb46 framework consists of statistically occupied Ge and Sb sites that atoms form bonds in a distorted tetrahedral arrangement. They form polyhedra that are covalently bonded to each other by shared faces. There are two polyhedra of different sizes, viz. a (Ge,Sb20 dodecahedron and a (Ge,Sb24 tetracosahedron in a 1:3 ratio. The guest atom (iodine resides inside these polyhedra with symmetry m3 (Wyckoff position 2a and overline{4}2m (Wyckoff position 2d, respectively.

  4. Large methane releases lead to strong aerosol forcing and reduced cloudiness

    DEFF Research Database (Denmark)

    Kurten, T.; Zhou, L.; Makkonen, R.;

    2011-01-01

    The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller...... is predicted to significantly decrease hydroxyl radical (OH) concentrations, while moderately increasing ozone (O-3). These changes lead to a 70% increase in the atmospheric lifetime of methane, and an 18% decrease in global mean cloud droplet number concentrations (CDNC). The CDNC change causes a radiative...... forcing that is comparable in magnitude to the long-wave radiative forcing ("enhanced greenhouse effect") of the added methane. Together, the indirect CH4-O-3 and CH4-OHaerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously...

  5. VOLATILE TRANSPORT INSIDE SUPER-EARTHS BY ENTRAPMENT IN THE WATER-ICE MATRIX

    International Nuclear Information System (INIS)

    Whether volatiles can be entrapped in a background matrix composing planetary envelopes and be dragged via convection to the surface is a key question in understanding atmospheric fluxes, cycles, and composition. In this paper, we consider super-Earths with an extensive water mantle (i.e., water planets), and the possibility of entrapment of methane in their extensive water-ice envelopes. We adopt the theory developed by van der Waals and Platteeuw for modeling solid solutions, often used for modeling clathrate hydrates, and modify it in order to estimate the thermodynamic stability field of a new phase called methane filled ice Ih. We find that in comparison to water ice VII the filled ice Ih structure may be stable not only at the high pressures but also at the high temperatures expected at the core-water mantle transition boundary of water planets.

  6. Novel inclusion compounds with urea/thiourea/selenourea-anion host lattices

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ The chemistry of inclusion compounds has a long history and is nowadays a subject of wide-ranging and intense study. With the awarding of the 1987 Nobel Prize in Chemistry to Donald J. Cram, Jean-Marie Lehn and Charles J. Pedersen for their fundamental work on "host-guest" or "supramolecular" systems, inclusion chemistry has come to the fore front in contemporary researches. Increasing varieties of novel inclusion compounds and new host molecules have been synthesized recently. The term "crystal engineering" was coined by Schmidt to describe the rational design and control of molecular packing arrangements in the solid state, and the structural study of clathrates has contributed substantially to our understanding of the problem. Generalizations concerning the preferred structural motifs generated by hydrogen bonding and weaker non-covalent interactions between specific functional groups or molecular fragments have led to the realization of some impressive predictions about the construction of supramolecular networks.

  7. MODELLING EARTH SYSTEM CHANGES THROUGH THE SHURUM-WONOKA ANOMALY

    DEFF Research Database (Denmark)

    Bjerrum, Christian J.; Canfield, D. E.

    -amplitude fluctuations in the isotopic composition of marine carbonate carbon (d13CIC ) and oxygen (d18O) and more subdued changes in the isotope composition of marine organic carbon. Normally, carbon isotope changes are considered to reflect the burial history of inorganic and organic carbon into sediments, while...... and organic carbon at lower values of d13CIC, with a cross-plot slope of about 1. This unit slope seems to be unique to the Neoproterozoic in Earth history and not easily explained. In our model, the carbon isotope excursions were driven by methane from sediment-hosted clathrate hydrate deposits. Being...... a powerful greenhouse gas, methane increased temperature and melted icecaps. These combined to produce a negative 18O anomaly, while the higher temperatures also accelerated the weathering of continental rocks, drawing down atmospheric CO2. Lower CO2, in turn, reduced the isotope fractionation between DIC...

  8. 3种熊果苷的研究进展%Progress in development of three kinds of arbutin product

    Institute of Scientific and Technical Information of China (English)

    刘彩云; 吴培诚; 梁高卫; 罗欣茹; 周丹曼

    2015-01-01

    The preparation method,mechanism of whitening action,as well as the application status and the product stability of three kinds of arbutin were summarized and compared. The new product types and new technologies such as liposomes,microemulsions and clathrates were put forward for providing orientation for development of new applications in the future.%重点综述了α-熊果苷、β-熊果苷和脱氧熊果苷的制备方法、美白机制及应用现状和稳定性,并对它们进行了比较,提出新剂型和新技术如脂质体、微乳、包合物的开发为3种熊果苷提供了新的应用方向。

  9. One-hundred-km-scale basins on Enceladus: Evidence for an active ice shell

    Science.gov (United States)

    Schenk, Paul M.; McKinnon, William B.

    2009-08-01

    Stereo-derived topographic mapping of ˜50% of Enceladus reveals at least 6 large-scale, ovoid depressions (basins) 90-175 km across and 800-to-1500 m deep and uncorrelated with geologic boundaries. In contrast, the south polar depression is larger and apparently shallower and correlates with active resurfacing. The shape and scale of the basins is inconsistent with impact, geoid surface deflections, or with dynamically supported topography. Isostatic thinning of Enceladus' ice shell associated with upwellings (and tidally-driven ice melting) can plausibly account for these basins. Thinning implies upwarping of the base of the shell of ˜10-20 km beneath the depressions, depending on total shell thickness; loss of near-surface porosity due to enhanced heat flow may also contribute to basin lows. Alternatively, the basins may overly cold, inactive, and hence denser ice, but thermal isostasy alone requires thermal expansion more consistent with clathrate hydrate than water ice.

  10. Thermal transport property of Ge34 and d-Ge investigated by molecular dynamics and the Slack's equation

    International Nuclear Information System (INIS)

    In this study, we evaluate the values of lattice thermal conductivity κL of type II Ge clathrate (Ge34) and diamond phase Ge crystal (d-Ge) with the equilibrium molecular dynamics (EMD) method and the Slack's equation. The key parameters of the Slack's equation are derived from the thermodynamic properties obtained from the lattice dynamics (LD) calculations. The empirical Tersoff's potential is used in both EMD and LD simulations. The thermal conductivities of d-Ge calculated by both methods are in accordance with the experimental values. The predictions of the Slack's equation are consistent with the EMD results above 250 K for both Ge34 and d-Ge. In a temperature range of 200–1000 K, the κL value of d-Ge is about several times larger than that of Ge34. (condensed matter: structure, thermal and mechanical properties)

  11. Global Energy Issues and Alternate Fueling

    Science.gov (United States)

    Hendricks, Robert C.

    2007-01-01

    This viewgraph presentation describes world energy issues and alternate fueling effects on aircraft design. The contents include: 1) US Uses about 100 Quad/year (1 Q = 10(exp 15) Btu) World Energy Use: about 433 Q/yr; 2) US Renewable Energy about 6%; 3) Nuclear Could Grow: Has Legacy Problems; 4) Energy Sources Primarily NonRenewable Hydrocarbon; 5) Notes; 6) Alternate Fuels Effect Aircraft Design; 7) Conventional-Biomass Issue - Food or Fuel; 8) Alternate fuels must be environmentally benign; 9) World Carbon (CO2) Emissions Problem; 10) Jim Hansen s Global Warming Warnings; 11) Gas Hydrates (Clathrates), Solar & Biomass Locations; 12) Global Energy Sector Response; 13) Alternative Renewables; 14) Stratospheric Sulfur Injection Global Cooling Switch; 15) Potential Global Energy Sector Response; and 16) New Sealing and Fluid Flow Challenges.

  12. Pseudogap and anharmonic phonon behavior in Ba8Ga16Ge30: An NMR study

    Science.gov (United States)

    Sirusi, Ali A.; Ross, Joseph H.

    2016-08-01

    We have performed 69Ga, 71Ga, and 137Ba NMR on Ba8Ga16Ge30, a clathrate semiconductor which has been of considerable interest due to its large figure of merit for thermoelectric applications. In measurements from 4 K to 450 K, we used measurements on the two Ga nuclei to separate the magnetic and electric quadrupole hyperfine contributions and thereby gain information about the metallic and phonon behavior. The results show the presence of a pseudogap in the Ga electronic states within the conduction band, superposed upon a large Ba contribution to the conduction band. Meanwhile the phonon contributions to the Ga relaxation rates are large and increase more rapidly with temperature than typical semiconductors. These results provide evidence for enhanced anharmonicity of the propagative phonon modes over a wide range, providing experimental evidence for enhanced phonon-phonon scattering as a mechanism for the reduced thermal conductivity.

  13. Thermodynamic and Process Modelling of Gas Hydrate Systems in CO2 Capture Processes

    DEFF Research Database (Denmark)

    Herslund, Peter Jørgensen

    A novel gas separation technique based on gas hydrate formation (solid precipitation) is investigated by means of thermodynamic modeling and experimental investigations. This process has previously been proposed for application in post-combustion carbon dioxide capture from power station flue gases...... on thermodynamic gas hydrate promotion by hydrate formers stabilising the classical gas clathrate hydrate structures (sI, sII and sH) at low to moderate pressures. Much literature is available on this subject. Both experimental and theoretical studies presented in the literature have pointed out cyclopentane...... and tetrahydrofuran as the two most efficient pressure reducing additives in classical hydrate forming systems. The thermodynamic promoting effects reported in the literature for the two classical sII hydrate formers, tetrahydrofuran and cyclopentane are experimentally confirmed in the present work. Data presented...

  14. Theoretical study of methanol as inhibitor and cyclopentane as stabilizer of dodecahedron methane hydrate cage

    Science.gov (United States)

    Pal, Snehanshu; Kundu, T. K.

    2015-02-01

    Density Functional Theory (DFT) based simulations have been performed to explain the role of methanol as an inhibitor and the role of cyclopentane as a promoter for methane hydrate. Interaction energy, Mullikan charges and electrostatic potential parameters for combined system of methanol and dodecahedron methane hydrate as well as cyclopentane and dodecahedron (512) methane hydrate cage are calculated using B3LYP functional (with and without dispersion function) and 6-31G(d) basis set. Methane hydrate formation inhibition by methanol and methane hydrate stabilization by cyclopentane is critically analyzed based on electrostatic potential and Mullikan charge. It is observed that hydrogen bond between water molecules of clathrate 512 cages become stronger in presence of cyclopentane and weaker in presence of methanol. It is also found that methanol breaks some hydrogen bonds of water molecules.

  15. Review of Solid State Hydrogen Storage Methods Adopting Different Kinds of Novel Materials

    Directory of Open Access Journals (Sweden)

    Renju Zacharia

    2015-01-01

    Full Text Available Overview of advances in the technology of solid state hydrogen storage methods applying different kinds of novel materials is provided. Metallic and intermetallic hydrides, complex chemical hydride, nanostructured carbon materials, metal-doped carbon nanotubes, metal-organic frameworks (MOFs, metal-doped metal organic frameworks, covalent organic frameworks (COFs, and clathrates solid state hydrogen storage techniques are discussed. The studies on their hydrogen storage properties are in progress towards positive direction. Nevertheless, it is believed that these novel materials will offer far-reaching solutions to the onboard hydrogen storage problems in near future. The review begins with the deficiencies of current energy economy and discusses the various aspects of implementation of hydrogen energy based economy.

  16. Subsurface Characterization of 67P/Churyumov–Gerasimenko’s Abydos Site

    Science.gov (United States)

    Brugger, B.; Mousis, O.; Morse, A.; Marboeuf, U.; Jorda, L.; Guilbert-Lepoutre, A.; Andrews, D.; Barber, S.; Lamy, P.; Luspay-Kuti, A.; Mandt, K.; Morgan, G.; Sheridan, S.; Vernazza, P.; Wright, I. P.

    2016-05-01

    On 2014 November 12, the ESA/Rosetta descent module Philae landed on the Abydos site of comet 67P/Churyumov–Gerasimenko. Aboard this module, the Ptolemy mass spectrometer measured a CO/CO2 ratio of 0.07 ± 0.04, which differs substantially from the value obtained in the coma by the Rosetta/ROSINA instrument, suggesting a heterogeneity in the comet nucleus. To understand this difference, we investigated the physicochemical properties of the Abydos subsurface, leading to CO/CO2 ratios close to that observed by Ptolemy at the surface of this region. We used a comet nucleus model that takes into account different water ice phase changes (amorphous ice, crystalline ice, and clathrates) as well as diffusion of molecules throughout the pores of the matrix. The input parameters of the model were optimized for the Abydos site, and the ROSINA CO/CO2 measured ratio is assumed to correspond to the bulk value in the nucleus. We find that all considered structures of water ice are able to reproduce the Ptolemy observation with a time difference not exceeding ˜50 days, i.e., lower than ˜2% on 67P/Churyumov–Gerasimenko’s orbital period. The suspected heterogeneity of 67P/Churyumov–Gerasimenko’s nucleus is also found possible only if it is constituted of crystalline ices. If the icy phase is made of amorphous ice or clathrates, the difference between Ptolemy and ROSINA’s measurements would rather originate from the spatial variations in illumination on the nucleus surface. An eventual new measurement of the CO/CO2 ratio at Abydos by Ptolemy could be decisive to distinguish between the three water ice structures.

  17. Revealing Surface Waters on an Antifreeze Protein by Fusion Protein Crystallography Combined with Molecular Dynamic Simulations.

    Science.gov (United States)

    Sun, Tianjun; Gauthier, Sherry Y; Campbell, Robert L; Davies, Peter L

    2015-10-01

    Antifreeze proteins (AFPs) adsorb to ice through an extensive, flat, relatively hydrophobic surface. It has been suggested that this ice-binding site (IBS) organizes surface waters into an ice-like clathrate arrangement that matches and fuses to the quasi-liquid layer on the ice surface. On cooling, these waters join the ice lattice and freeze the AFP to its ligand. Evidence for the generality of this binding mechanism is limited because AFPs tend to crystallize with their IBS as a preferred protein-protein contact surface, which displaces some bound waters. Type III AFP is a 7 kDa globular protein with an IBS made up two adjacent surfaces. In the crystal structure of the most active isoform (QAE1), the part of the IBS that docks to the primary prism plane of ice is partially exposed to solvent and has clathrate waters present that match this plane of ice. The adjacent IBS, which matches the pyramidal plane of ice, is involved in protein-protein crystal contacts with few surface waters. Here we have changed the protein-protein contacts in the ice-binding region by crystallizing a fusion of QAE1 to maltose-binding protein. In this 1.9 Å structure, the IBS that fits the pyramidal plane of ice is exposed to solvent. By combining crystallography data with MD simulations, the surface waters on both sides of the IBS were revealed and match well with the target ice planes. The waters on the pyramidal plane IBS were loosely constrained, which might explain why other isoforms of type III AFP that lack the prism plane IBS are less active than QAE1. The AFP fusion crystallization method can potentially be used to force the exposure to solvent of the IBS on other AFPs to reveal the locations of key surface waters.

  18. Arguments for a Comprehensive Laboratory Research Subprogram on Hydrocarbon Gas Hydrates and Hydrate-Sediment Aggregates in the 2005-2010 DOE Methane Hydrate R & D Program

    Science.gov (United States)

    Kirby, S. H.

    2005-12-01

    Field observations of natural hydrocarbon clathrate hydrates, including responses to drilling perturbations of hydrates, well logging and analysis of drill core, and field geophysics are, combined with theoretical modeling, justifiably key activities of the authorized 2005-2010 DOE Methane Hydrate Program. It is argued in this presentation that sustained fundamental laboratory research amplifies, extends and verifies results obtained from field and modeling investigations and does so in a cost-effective way. Recent developments of hydrocarbon clathrate hydrate and sediment aggregate synthesis methods, applications of in-situ optical cell, Raman, NMR, x-ray tomography and neutron diffraction techniques, and cryogenic x-ray and SEM methods re-enforce the importance of such lab investigations. Moreover, there are large data gaps for hydrocarbon-hydrate and hydrate-sediment-aggregate properties. We give three examples: 1) All natural hydrocarbon hydrates in sediment core have been altered to varying degrees by their transit, storage, depressurization, and subsequent lab investigations, as are well-log observations during drilling operations. Interpretation of drill core properties and structure and well logs are also typically not unique. Emulations of the pressure-temperature-deformation-time histories of synthetic samples offer a productive way of gaining insight into how natural samples and logging measurements may be compositionally and texturally altered during sampling and handling. 2) Rock physics models indicate that the effects of hydrates on sediment properties depend on the manner in which hydrates articulate with the sediment matrix (their conformation). Most of these models have not been verified by direct testing using hydrocarbon hydrates with conformation checked by optical cell observations or cryogenic SEM. Such tests are needed and technically feasible. 3) Modeling the effects of exchanges of heat, multiphase fluid fluxes, and deformation involve

  19. A PROTOSOLAR NEBULA ORIGIN FOR THE ICES AGGLOMERATED BY COMET 67P/CHURYUMOV–GERASIMENKO

    Energy Technology Data Exchange (ETDEWEB)

    Mousis, O.; Vernazza, P. [Aix Marseille Université, CNRS, LAM (Laboratoire d’Astrophysique de Marseille) UMR 7326, F-13388 Marseille (France); Lunine, J. I. [Center For Radiophysics And Space Research, Space Sciences Building Cornell University, Ithaca, NY 14853 (United States); Luspay-Kuti, A.; Hässig, M.; Waite, J. H. [Department of Space Research, Southwest Research Institute, 6220 Culebra Road, San Antonio, TX 78228 (United States); Guillot, T. [Laboratoire J.-L. Lagrange, Université de Nice-Sophia Antipolis, CNRS, Observatoire de la Côte d’Azur, BP 4229, F-06304 Nice (France); Marty, B. [CRPG-CNRS, Nancy-Université, 15 rue Notre Dame des Pauvres, F-54501 Vandoeuvre-lès-Nancy (France); Ali-Dib, M. [Université de Franche-Comté, Institut UTINAM, CNRS/INSU, UMR 6213, Besançon Cedex (France); Wurz, P.; Altwegg, K.; Bieler, A.; Rubin, M., E-mail: olivier.mousis@lam.fr [Physikalisches Institut, University of Bern, Sidlerstrasse 5, CH-3012 Bern (Switzerland)

    2016-03-10

    The nature of the icy material accreted by comets during their formation in the outer regions of the protosolar nebula (PSN) is a major open question in planetary science. Some scenarios of comet formation predict that these bodies agglomerated from crystalline ices condensed in the PSN. Concurrently, alternative scenarios suggest that comets accreted amorphous ice originating from the interstellar cloud or from the very distant regions of the PSN. On the basis of existing laboratory and modeling data, we find that the N{sub 2}/CO and Ar/CO ratios measured in the coma of the Jupiter-family comet 67P/Churyumov–Gerasimenko by the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis instrument on board the European Space Agency’s Rosetta spacecraft match those predicted for gases trapped in clathrates. If these measurements are representative of the bulk N{sub 2}/CO and Ar/CO ratios in 67P/Churyumov–Gerasimenko, it implies that the ices accreted by the comet formed in the nebula and do not originate from the interstellar medium, supporting the idea that the building blocks of outer solar system bodies have been formed from clathrates and possibly from pure crystalline ices. Moreover, because 67P/Churyumov–Gerasimenko is impoverished in Ar and N{sub 2}, the volatile enrichments observed in Jupiter’s atmosphere cannot be explained solely via the accretion of building blocks with similar compositions and require an additional delivery source. A potential source may be the accretion of gas from the nebula that has been progressively enriched in heavy elements due to photoevaporation.

  20. Lattice constants and expansivities of gas hydrates from 10 K up to the stability limit

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, T. C. [Institut Laue-Langevin, 71 Avenue des Martyrs, 38000 Grenoble (France); Falenty, A.; Kuhs, W. F. [GZG, Abt. Kristallographie, Universität Göttingen, Goldschmidtstrasse 1, 37077 Göttingen (Germany)

    2016-02-07

    The lattice constants of hydrogenated and deuterated CH{sub 4}-, CO{sub 2}-, Xe- (clathrate structure type I) and N{sub 2}-hydrates (clathrate structure type II) from 10 K up to the stability limit were established in neutron- and synchrotron diffraction experiments and were used to derive the related thermal expansivities. The following results emerge from this analysis: (1) The differences of expansivities of structure type I and II hydrates are fairly small. (2) Despite the larger guest-size of CO{sub 2} as compared to methane, CO{sub 2}-hydrate has the smaller lattice constants at low temperatures, which is ascribed to the larger attractive guest-host interaction of the CO{sub 2}-water system. (3) The expansivity of CO{sub 2}-hydrate is larger than for CH{sub 4}-hydrate which leads to larger lattice constants for the former at temperatures above ∼150 K; this is likely due to the higher motional degrees of freedom of the CO{sub 2} guest molecules. (4) The cage occupancies of Xe- and CO{sub 2}-hydrates affect significantly the lattice constants. (5) Similar to ice Ih, the deuterated compounds have generally slightly larger lattice constants which can be ascribed to the somewhat weaker H-bonding. (6) Compared to ice Ih, the high temperature expansivities are about 50% larger; in contrast to ice Ih and the empty hydrate, there is no negative thermal expansion at low temperature. (7) A comparison of the experimental results with lattice dynamical work, with models based on an Einstein oscillator model, and results from inelastic neutron scattering suggest that the contribution of the guest atoms’ vibrational energy to thermal expansion is important, most prominently for CO{sub 2}- and Xe-hydrates.

  1. A Protosolar Nebula Origin for the Ices Agglomerated by Comet 67P/Churyumov-Gerasimenko

    Science.gov (United States)

    Mousis, O.; Lunine, J. I.; Luspay-Kuti, A.; Guillot, T.; Marty, B.; Ali-Dib, M.; Wurz, P.; Altwegg, K.; Bieler, A.; Hässig, M.; Rubin, M.; Vernazza, P.; Waite, J. H.

    2016-03-01

    The nature of the icy material accreted by comets during their formation in the outer regions of the protosolar nebula (PSN) is a major open question in planetary science. Some scenarios of comet formation predict that these bodies agglomerated from crystalline ices condensed in the PSN. Concurrently, alternative scenarios suggest that comets accreted amorphous ice originating from the interstellar cloud or from the very distant regions of the PSN. On the basis of existing laboratory and modeling data, we find that the N2/CO and Ar/CO ratios measured in the coma of the Jupiter-family comet 67P/Churyumov-Gerasimenko by the Rosetta Orbiter Spectrometer for Ion and Neutral Analysis instrument on board the European Space Agency’s Rosetta spacecraft match those predicted for gases trapped in clathrates. If these measurements are representative of the bulk N2/CO and Ar/CO ratios in 67P/Churyumov-Gerasimenko, it implies that the ices accreted by the comet formed in the nebula and do not originate from the interstellar medium, supporting the idea that the building blocks of outer solar system bodies have been formed from clathrates and possibly from pure crystalline ices. Moreover, because 67P/Churyumov-Gerasimenko is impoverished in Ar and N2, the volatile enrichments observed in Jupiter’s atmosphere cannot be explained solely via the accretion of building blocks with similar compositions and require an additional delivery source. A potential source may be the accretion of gas from the nebula that has been progressively enriched in heavy elements due to photoevaporation.

  2. A hydrothermal origin for isotopically anomalous cap dolostone cements from south China.

    Science.gov (United States)

    Bristow, Thomas F; Bonifacie, Magali; Derkowski, Arkadiusz; Eiler, John M; Grotzinger, John P

    2011-06-01

    The release of methane into the atmosphere through destabilization of clathrates is a positive feedback mechanism capable of amplifying global warming trends that may have operated several times in the geological past. Such methane release is a hypothesized cause or amplifier for one of the most drastic global warming events in Earth history, the end of the Marinoan 'snowball Earth' ice age, ∼635 Myr ago. A key piece of evidence supporting this hypothesis is the occurrence of exceptionally depleted carbon isotope signatures (δ(13)C(PDB) down to -48‰; ref. 8) in post-glacial cap dolostones (that is, dolostone overlying glacial deposits) from south China; these signatures have been interpreted as products of methane oxidation at the time of deposition. Here we show, on the basis of carbonate clumped isotope thermometry, (87)Sr/(86)Sr isotope ratios, trace element content and clay mineral evidence, that carbonates bearing the (13)C-depleted signatures crystallized more than 1.6 Myr after deposition of the cap dolostone. Our results indicate that highly (13)C-depleted carbonate cements grew from hydrothermal fluids and suggest that their carbon isotope signatures are a consequence of thermogenic methane oxidation at depth. This finding not only negates carbon isotope evidence for methane release during Marinoan deglaciation in south China, but also eliminates the only known occurrence of a Precambrian sedimentary carbonate with highly (13)C-depleted signatures related to methane oxidation in a seep environment. We propose that the capacity to form highly (13)C-depleted seep carbonates, through biogenic anaeorobic oxidation of methane using sulphate, was limited in the Precambrian period by low sulphate concentrations in sea water. As a consequence, although clathrate destabilization may or may not have had a role in the exit from the 'snowball' state, it would not have left extreme carbon isotope signals in cap dolostones.

  3. Revealing Surface Waters on an Antifreeze Protein by Fusion Protein Crystallography Combined with Molecular Dynamic Simulations.

    Science.gov (United States)

    Sun, Tianjun; Gauthier, Sherry Y; Campbell, Robert L; Davies, Peter L

    2015-10-01

    Antifreeze proteins (AFPs) adsorb to ice through an extensive, flat, relatively hydrophobic surface. It has been suggested that this ice-binding site (IBS) organizes surface waters into an ice-like clathrate arrangement that matches and fuses to the quasi-liquid layer on the ice surface. On cooling, these waters join the ice lattice and freeze the AFP to its ligand. Evidence for the generality of this binding mechanism is limited because AFPs tend to crystallize with their IBS as a preferred protein-protein contact surface, which displaces some bound waters. Type III AFP is a 7 kDa globular protein with an IBS made up two adjacent surfaces. In the crystal structure of the most active isoform (QAE1), the part of the IBS that docks to the primary prism plane of ice is partially exposed to solvent and has clathrate waters present that match this plane of ice. The adjacent IBS, which matches the pyramidal plane of ice, is involved in protein-protein crystal contacts with few surface waters. Here we have changed the protein-protein contacts in the ice-binding region by crystallizing a fusion of QAE1 to maltose-binding protein. In this 1.9 Å structure, the IBS that fits the pyramidal plane of ice is exposed to solvent. By combining crystallography data with MD simulations, the surface waters on both sides of the IBS were revealed and match well with the target ice planes. The waters on the pyramidal plane IBS were loosely constrained, which might explain why other isoforms of type III AFP that lack the prism plane IBS are less active than QAE1. The AFP fusion crystallization method can potentially be used to force the exposure to solvent of the IBS on other AFPs to reveal the locations of key surface waters. PMID:26371748

  4. Self-Organization of +-Crown Ether Derivatives into Double-Columnar Arrays Controlled by Supramolecular Isomers of Hydrogen-Bonded Anionic Biimidazolate Ni Complexes

    Directory of Open Access Journals (Sweden)

    Makoto Tadokoro

    2012-01-01

    Full Text Available Anionic tris (biimidazolate nickelate (II ([Ni(Hbim3]−, which is a hydrogen-bonding (H-bonding molecular building block, undergoes self-organization into honeycomb-sheet superstructures connected by complementary intermolecular H-bonds. The crystal obtained from the stacking of these sheets is assembled into channel frameworks, approximately 2 nm wide, that clathrate two cationic K+-crown ether derivatives organised into one-dimensional (1D double-columnar arrays. In this study, we have shown that all five cationic guest-included crystals form nanochannel structures that clathrate the 1-D double-columnar arrays of one of the four types of K+-crown ether derivatives, one of which induces a polymorph. This is accomplished by adaptably fitting two types of anionic [Ni(Hbim3]− host arrays. One is a ΔΛ−ΔΛ−ΔΛ⋯ network with H-bonded linkages alternating between the two different optical isomers of the Δ and Λ types with flexible H-bonded [Ni(Hbim3]−. The other is a ΔΔΔ−ΛΛΛ⋯ network of a racemate with 1-D H-bonded arrays of the same optical isomer for each type. Thus, [Ni(Hbim3]− can assemble large cations such as K+ crown-ether derivatives into double-columnar arrays by highly recognizing flexible H-bonding arrangements with two host networks of ΔΛ−ΔΛ−ΔΛ⋯ and ΔΔΔ−ΛΛΛ⋯.

  5. Formation of natural gas hydrates in marine sediments 1. Conceptual model of gas hydrate growth conditioned by host sediment properties

    Science.gov (United States)

    Clennell, M.B.; Hovland, M.; Booth, J.S.; Henry, P.; Winters, W.J.

    1999-01-01

    The stability of submarine gas hydrates is largely dictated by pressure and temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of deep marine sediments may also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our conceptual model presumes that gas hydrate behaves in a way analogous to ice in a freezing soil. Hydrate growth is inhibited within fine-grained sediments by a combination of reduced pore water activity in the vicinity of hydrophilic mineral surfaces, and the excess internal energy of small crystals confined in pores. The excess energy can be thought of as a "capillary pressure" in the hydrate crystal, related to the pore size distribution and the state of stress in the sediment framework. The base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature (nearer to the seabed) than would be calculated from bulk thermodynamic equilibrium. Capillary effects or a build up of salt in the system can expand the phase boundary between hydrate and free gas into a divariant field extending over a finite depth range dictated by total methane content and pore-size distribution. Hysteresis between the temperatures of crystallization and dissociation of the clathrate is also predicted. Growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, and lenses in muds; cements in sands) can largely be explained by capillary effects, but kinetics of nucleation and growth are also important. The formation of concentrated gas hydrates in a partially closed system with respect to material transport, or where gas can flush through the system, may lead to water depletion in the host sediment. This "freeze-drying" may be detectable through physical changes to the sediment (low water content and overconsolidation) and/or chemical anomalies in the pore waters and metastable

  6. Using Jupiter's Volatile Inventory to Trace the History Of Ices During Planet Formation

    Science.gov (United States)

    Ciesla, F.

    2014-12-01

    The Galileo probe's measurement of a uniform enrichment of Jupiter's atmosphere in volatiles, including noble gases, relative to a gas of solar composition has proven to be a challenge to models of planet formation. This uniform enrichment requires that Jupiter accreted planetesimals with solar ratios in all elements, except for hydrogen and helium. Given the very low temperatures needed to achieve such compositions if all elements behaved chemically as pure substances, efforts have focused on understanding how extremely volatile elements could be physically incorporated into ices and organics at low temperatures. Two primary methods for incorporation of these volatiles have emerged: formation of clathrate hydrates and trapping of gases during the formation of amorphous ice. These modes for incorporating volatiles make different predictions about the amount of water that would be contained within Jupiter, an issue that will be addressed by the Juno Mission. Either mode for incorporating volatiles will reveal details about the dynamical behavior of ices during planet formation and the environments in which planetary materials were formed. For example, Ciesla (2014) showed that amorphous ice formation, and thus trapping of volatiles in this manner, can occur as water molecules are photodesorbed and freeze-out again on grain surfaces, thus requiring high UV flux environments at the birth of the solar system or significant vertical lofting of grains in the disk by turbulence. I will review the conditions that are required for amorphous trapping and clathrate hydrate formation to have occurred in the solar nebula and discuss the implications for the compositions of the other giant planets and cometary bodies, as well as the relation of these materials to the sources of volatiles on terrestrial planets.

  7. Inhibitory Effects of 6 Macroalgae Extracts on Skeletonema costatum and Isolation of Allelochemicals%六种大型藻浸提液对中肋骨条藻的抑制及活性成分分离

    Institute of Scientific and Technical Information of China (English)

    别聪聪; 李锋民; 李媛媛; 赵雅菡; 王震宇

    2011-01-01

    为比较大型藻抑制赤潮藻的能力,研究了孔石莼、羊栖菜、长浒苔、马尾藻、蜈蚣藻和裙带菜的干粉末海水浸提液对中肋骨条藻的化感抑制作用并从长浒苔中分离出具有强抑制作用的组分.分析6种大型藻浸提液对中肋骨条藻的生长抑制率(Inhibitory rate,IR%)和120 h的半效应浓度(Effect concentration,EC50,120h)发现,孔石莼、羊柄菜、长浒苔、马尾藻和蜈蚣藻的浸提液在浓度达到2.4 g/L时可在实验周期内使中肋骨条藻全部致死,抑制率达到100%,全部致死所需时间分别为96、120、96、144和144 h,当浓度达到4.8 g/L时,6种大型藻均可全部杀死中肋骨条藻,6种大型藻对中肋骨条藻的EC50、120h分别为1.0、1.0、1.1、1.4、1.5和4.7 g/L.从长浒苔浸提液中分离的乙酸乙酯萃取组分具有强抑藻效果,受试条件下,其EC50值为0.08 mg/L.乙酸乙酯相气相色谱-质谱分析表明,组分至少包含14种物质,其中9-十八炔和邻苯二甲酸二异丁酯是含量最大的2种物质,各物质的抑藻活性尚需进一步研究.长浒苔具有很强的抑藻效果,具有应用于赤潮藻控制的潜力,研究结果为分离鉴定抑制中肋骨条藻的化感物质奠定了基础.%For the purpose of finding macroalgae of high allelopathic potency* the allelopathic inhibitory effect of seawater extracts of dry powder of Ulva pertusa, Sargassum fusiforme, Enteromorpha clathrat , Sargassum pathen, Grateloupia filicina and Undaria pinnatifida on the red tide microalgae Skele-tonema costatum were investigated. When the concentration of the macroalgae dry powder reached 2. 4 g/ L, Ulva pertusa, Sargassum fusi forme, Enteromorpha clathrat ^Sargassum pathen and Grateloupia filicina could totally inhibit the growth of Skeletonema costatum, and the lethal time were 96, 120, 96, 144 and 144 h, respectively. And the EC50,120h of these six macroalgae were 1. 0 g/L for Enteromorpha clath-rat and Ulva pertusa, 1. 1

  8. Structure and dynamics of cold water super-Earths: the case of occluded CH4 and its outgassing

    International Nuclear Information System (INIS)

    In this work, we study the transport of methane in the external water envelopes surrounding water-rich super-Earths. We investigate the influence of methane on the thermodynamics and mechanics of the water mantle. We find that including methane in the water matrix introduces a new phase (filled ice), resulting in hotter planetary interiors. This effect renders the super-ionic and reticulating phases accessible to the lower ice mantle of relatively low-mass planets (∼5 ME ) lacking a H/He atmosphere. We model the thermal and structural profile of the planetary crust and discuss five possible crustal regimes which depend on the surface temperature and heat flux. We demonstrate that the planetary crust can be conductive throughout or partly confined to the dissociation curve of methane clathrate hydrate. The formation of methane clathrate in the subsurface is shown to inhibit the formation of a subterranean ocean. This effect results in increased stresses on the lithosphere, making modes of ice plate tectonics possible. The dynamic character of the tectonic plates is analyzed and the ability of this tectonic mode to cool the planet is estimated. The icy tectonic plates are found to be faster than those on a silicate super-Earth. A mid-layer of low viscosity is found to exist between the lithosphere and the lower mantle. Its existence results in a large difference between ice mantle overturn timescales and resurfacing timescales. Resurfacing timescales are found to be 1 Ma for fast plates and 100 Ma for sluggish plates, depending on the viscosity profile and ice mass fraction. Melting beneath spreading centers is required in order to account for the planetary radiogenic heating. The melt fraction is quantified for the various tectonic solutions explored, ranging from a few percent for the fast and thin plates to total melting of the upwelled material for the thick and sluggish plates. Ice mantle dynamics is found to be important for assessing the composition of the

  9. Structure and dynamics of cold water super-Earths: the case of occluded CH{sub 4} and its outgassing

    Energy Technology Data Exchange (ETDEWEB)

    Levi, A.; Podolak, M. [Department of Geophysics and Planetary Science, Tel Aviv University, Tel Aviv 69978 (Israel); Sasselov, D., E-mail: amitlevi.planetphys@gmail.com [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States)

    2014-09-10

    In this work, we study the transport of methane in the external water envelopes surrounding water-rich super-Earths. We investigate the influence of methane on the thermodynamics and mechanics of the water mantle. We find that including methane in the water matrix introduces a new phase (filled ice), resulting in hotter planetary interiors. This effect renders the super-ionic and reticulating phases accessible to the lower ice mantle of relatively low-mass planets (∼5 M{sub E} ) lacking a H/He atmosphere. We model the thermal and structural profile of the planetary crust and discuss five possible crustal regimes which depend on the surface temperature and heat flux. We demonstrate that the planetary crust can be conductive throughout or partly confined to the dissociation curve of methane clathrate hydrate. The formation of methane clathrate in the subsurface is shown to inhibit the formation of a subterranean ocean. This effect results in increased stresses on the lithosphere, making modes of ice plate tectonics possible. The dynamic character of the tectonic plates is analyzed and the ability of this tectonic mode to cool the planet is estimated. The icy tectonic plates are found to be faster than those on a silicate super-Earth. A mid-layer of low viscosity is found to exist between the lithosphere and the lower mantle. Its existence results in a large difference between ice mantle overturn timescales and resurfacing timescales. Resurfacing timescales are found to be 1 Ma for fast plates and 100 Ma for sluggish plates, depending on the viscosity profile and ice mass fraction. Melting beneath spreading centers is required in order to account for the planetary radiogenic heating. The melt fraction is quantified for the various tectonic solutions explored, ranging from a few percent for the fast and thin plates to total melting of the upwelled material for the thick and sluggish plates. Ice mantle dynamics is found to be important for assessing the composition of

  10. Formation of porous gas hydrates: Diffraction experiments and multi-stage model

    Science.gov (United States)

    Staykova, D. K.; Genov, G.; Goreshnik, E.; Salamatin, A. N.; Kuhs, W. F.

    2003-04-01

    Laboratory-grown gas hydrates were examined by cryo scanning electron microscopy and found to have a sub-micron porous structure. This microstructure is undistinguishable from the one observed in natural gas hydrates suggesting similar formation processes. In-situ observations of the formation of synthetic porous methane and carbon dioxide hydrates starting from ice Ih powders with known surfaces areas were made using time-resolved neutron diffraction on the high-flux diffractometer D20 (ILL, Grenoble) at different pressures and temperatures. Some runs were also made going through the ice melting point into liquid water. At similar reduced fugacities, the reaction of carbon dioxide was distinctly faster than that of methane. The transient formation of carbon dioxide hydrate crystal structure II was observed in coexistence with the usual type-I hydrate reaching a maximum of 5% after 5 h of the reaction at 272 K. At lower temperatures a temporary inhibition of formation was observed in the case of carbon dioxide. The rate of methane hydrate growth showed little pressure sensitivity in our experiments at low temperatures ~230 K in contrast to the situation at higher temperatures. A phenomenological model for the kinetics of the gas hydrate formation from ice powders is developed with special account of sample consolidation effects. It describes the initial stage (I) of hydrate film spreading over the ice surface and the two subsequent stages which are limited (II) by the clathration reaction at the ice-hydrate interface and (III) by the gas and water transport (diffusion) through the hydrate shells surrounding the shrinking ice cores. Comparable activation energies of the CH4-hydrate formation are found in deuterated and hydrogenated systems for the reaction-limited process (stage II) to be 8.1 and 9.5 kcal/mol, respectively. In the case of a diffusion-limited clathration (stage III) the activation energy can be estimated as 14.3 kcal/mol. The relevance of our

  11. Megafauna and frozen soil: the drivers of atmospheric CH4 dynamics

    Science.gov (United States)

    Zimov, N.; Zimov, S. A.

    2010-12-01

    During the last deglaciation (LD) a strong increase in atmospheric methane (CH4) concentrations occurred simultaneously with a rise in Greenland temperatures indicating that in the north, during this time period, strong CH4 sources “awakened”, as additionally documented by the appearance of a strong gradient between northern (Greenland) and southern (Antarctica) hemisphere atmospheric CH4 concentrations. This rise could not be caused by wetland expansion. A reconstruction of peatland formation dynamics has indicated that wetlands on Earth were few in LD and only actively expanded 10,000 yr BP, after atmospheric CH4 concentrations began to decline. Destabilization of methane clathrates also could not be the source for atmospheric CH4 increase. Geological CH4 (including methane clathrates) has the highest deuterium content (δD) among all of the known sources of CH4 while atmospheric CH4 δD values determined for the LD were record low. To explain recorded atmospheric CH4 and its isotopic dynamics required a strong northern source, which was active only during the LD and that provided very low δD CH4 values. Such a source is permafrost thawing under anaerobic conditions (or better stated soils of mammoth steppe-tundra ecosystems). Permafrost thawing is the strongest, among known, wetland sources (usually over 100g CH4/m2yr) and has a unique isotopic signature (δD = -400 per mil (-338 to -479 per mil), δ13C = -73 per mil (-58 to -99 per mil)). The main sources of atmospheric CH4 have different isotopic signatures (δ13C, δD). The isotopic content of atmospheric CH4 is a simple function of the weight average for all of the sources. Inclusion of permafrost source into a budget model of the atmospheric methane and its isotopes allowed us to reconstruct the dynamics of methane’s main sources. Model indicated geological source to be negligible as in LGM so and in LD and Holocene. During the glaciation, the largest methane source was megafauna, whose 1

  12. Lanthanide(III) complexation with an amide derived pyridinophane.

    Science.gov (United States)

    Castro, Goretti; Bastida, Rufina; Macías, Alejandro; Pérez-Lourido, Paulo; Platas-Iglesias, Carlos; Valencia, Laura

    2015-02-16

    Herein we report a detailed investigation of the solid state and solution structures of lanthanide(III) complexes with the 18-membered pyridinophane ligand containing acetamide pendant arms TPPTAM (TPPTAM = 2,2',2″-(3,7,11-triaza-1,5,9(2,6)-tripyridinacyclododecaphane-3,7,11-triyl)triacetamide). The ligand crystallizes in the form of a clathrated hydrate, where the clathrated water molecule establishes hydrogen-bonding interactions with the amide NH groups and two N atoms of the macrocycle. The X-ray structures of 13 different Ln(3+) complexes obtained as the nitrate salts (Ln(3+) = La(3+)-Yb(3+), except Pm(3+)) have been determined. Additionally, the X-ray structure of the La(3+) complex obtained as the triflate salt was also obtained. In all cases the ligand provides 9-fold coordination to the Ln(3+) ion, ten coordination being completed by an oxygen atom of a coordinated water molecule or a nitrate or triflate anion. The bond distances of the metal coordination environment show a quadratic change along the lanthanide series, as expected for isostructural series of Ln(3+) complexes. Luminescence lifetime measurements obtained from solutions of the Eu(3+) and Tb(3+) complexes in H2O and D2O point to the presence of a water molecule coordinated to the metal ion in aqueous solutions. The analysis of the Ln(3+)-induced paramagnetic shifts indicates that the complexes are ten-coordinated throughout the lanthanide series from Ce(3+) to Yb(3+), and that the solution structure is very similar to the structures observed in the solid state. The complexes of the light Ln(3+) ions are fluxional due to a fast Δ(λλλλλλ) ↔ Λ(δδδδδδ) interconversion that involves the inversion of the macrocyclic ligand and the rotation of the acetamide pendant arms. The complexes of the small Ln(3+) ions are considerably more rigid, the activation free energy determined from VT (1)H NMR for the Lu(3+) complex being ΔG(⧧)298 = 72.4 ± 5.1 kJ mol(-1).

  13. Experimental Study of Gas Hydrate Dynamics

    Science.gov (United States)

    Fandino, O.; Ruffine, L.

    2011-12-01

    Important quantities of methane and other gases are trapped below the seafloor and in the permafrost by an ice-like solid, called gas hydrates or clathrate hydrates. The latter is formed when water is mixing with different gases at high pressures and low temperatures. Due to a their possible use as a source of energy [1] or the problematic related to flow assurance failure in pipelines [2] the understanding of their processes of formation/destabilisation of these structures becomes a goal for many laboratories research as well as industries. In this work we present an experimental study on the stochastic behaviour of hydrate formation from a bulk phase. The method used here for the experiments was to repeat several time the same hydrate formation procedure and to notice the different from one experiment to another. A variable-volume type high-pressure apparatus with two sapphire windows was used. This device, already presented by Ruffine et al.[3], allows us to perform both kinetics and phase equilibrium measurements. Three initial pressure conditions were considered here, 5.0 MPa, 7.5 MPa and 10.0 MPa. Hydrates have been formed, then allowed to dissociate by stepwise heating. The memory effect has also been investigated after complete dissociation. It turned out that, although the thermodynamics conditions of formation and/or destabilization were reproducible. An attempt to determine the influence of pressure on the nucleation induction time will be discussed. References 1. Sum, A. K.; Koh, C. A.; Sloan, E. D., Clathrate Hydrates: From Laboratory Science to Engineering Practice. Industrial & Engineering Chemistry Research 2009, 48, 7457-7465. 2. Sloan, E. D., A changing hydrate paradigm-from apprehension to avoidance to risk management. Fluid Phase Equilibria 2005, 228, 67-74. 3. Ruffine, L.; Donval, J. P.; Charlou, J. L.; Cremière, A.; Zehnder, B. H., Experimental study of gas hydrate formation and destabilisation using a novel high-pressure apparatus. Marine

  14. Effect of administration of water enriched in O2 by injection or electrolysis on transcutaneous oxygen pressure in anesthetized pigs

    Directory of Open Access Journals (Sweden)

    Charton A

    2014-08-01

    the three groups, but when compared to the control group, the values remained significantly higher in animals that received the water enriched in O2 by electrolysis. Conclusions: In this protocol, water enriched in O2 by electrolysis lessened the decline of peripheral tissue oxygenation. This observation is compatible with the claim that the electrolytic process generates water clathrates which trap O2 and facilitate O2 diffusion along pressure gradients. Potential applications of O2-enriched water include an alternate method of oxygen supply. Keywords: transcutaneous oxygen partial pressure determination, tissue oxygenation, oxygenated water, water clathrate 

  15. CO2 and C2H2 in cold nanodroplets of oxygenated organic molecules and water

    Science.gov (United States)

    Devlin, J. Paul; Balcı, F. Mine; Maşlakcı, Zafer; Uras-Aytemiz, Nevin

    2014-11-01

    Recent demonstrations of subsecond and microsecond timescales for formation of clathrate hydrate nanocrystals hint at future methods of control of environmental and industrial gases such as CO2 and methane. Combined results from cold-chamber and supersonic-nozzle [A. S. Bhabhe, "Experimental study of condensation and freezing in a supersonic nozzle," Ph.D. thesis (Ohio State University, 2012), Chap. 7] experiments indicate extremely rapid encagement of components of all-vapor pre-mixtures. The extreme rates are derived from (a) the all-vapor premixing of the gas-hydrate components and (b) catalytic activity of certain oxygenated organic large-cage guests. Premixing presents no obvious barrier to large-scale conditions of formation. Further, from sequential efforts of the groups of Trout and Buch, a credible defect-based model of the catalysis mechanism exists for guidance. Since the catalyst-generated defects are both mobile and abundant, it is often unnecessary for a high percentage of the cages to be occupied by a molecular catalyst. Droplets represent the liquid phase that bridges the premixed vapor and clathrate hydrate phases but few data exist for the droplets themselves. Here we describe a focused computational and FTIR spectroscopic effort to characterize the aerosol droplets of the all-vapor cold-chamber methodology. Computational data for CO2 and C2H2, hetero-dimerized with each of the organic catalysts and water, closely match spectroscopic redshift patterns in both magnitude and direction. Though vibrational frequency shifts are an order of magnitude greater for the acetylene stretch mode, both CO2 and C2H2 experience redshift values that increase from that for an 80% water-methanol solvent through the solvent series to approximately doubled values for tetrahydrofuran and trimethylene oxide (TMO) droplets. The TMO solvent properties extend to a 50 mol.% solution of CO2, more than an order of magnitude greater than for the water-methanol solvent mixture

  16. Pits formation from volatile outgassing on 67P/Churyumov-Gerasimenko

    CERN Document Server

    Mousis, O; Brugger, B; Jorda, L; Kargel, J S; Bouquet, A; Auger, A -T; Lamy, P; Vernazza, P; Thomas, N; Sierks, H

    2015-01-01

    We investigate the thermal evolution of comet 67P/Churyumov-Gerasimenko's subsurface in the Seth_01 region, where active pits have been observed by the ESA/Rosetta mission. Our simulations show that clathrate destabilization and amorphous ice crystallization can occur at depths corresponding to those of the observed pits in a timescale shorter than 67P/Churyumov-Gerasimenko's lifetime in the comet's activity zone in the inner solar system. Sublimation of crystalline ice down to such depths is possible only in the absence of a dust mantle, which requires the presence of dust grains in the matrix small enough to be dragged out by gas from the pores. Our results are consistent with both pits formation via sinkholes or subsequent to outbursts, the dominant process depending on the status of the subsurface porosity. A sealed dust mantle would favor episodic and disruptive outgassing as a result of an increasing gas pressure in the pores, while a high porosity should allow the formation of large voids in the subsur...

  17. Third international workshop on ice storage for cooling applications

    Energy Technology Data Exchange (ETDEWEB)

    Gorski, A.J. (comp.)

    1986-04-01

    The third international workshop on ice storage for cooling applications which was informal and interactive in nature, was open to persons interested in all ice-growing technologies and in ice storage, both seasonal and diurnal. Presentations were made on some 20 topics, ranging from freezers in Alaska to ice cooling of commercial jet aircraft. Workshop tours included visits to ice-storage systems at Commonwealth Edison's facilities in Bolingbrook and Des Plaines Valley, the A.C. Neilsen builing in Northbrook, and the new State of Illinois Center in Chicago. The first workshop in the present series considered the future of ice storage and predicted applications in the agricultural sector, desalinization, and commercial ice production. Progress has been rapid in the intervening two years, and an important topic at the third workshop was the possible use of ''warm ices'' (clathrate hydrates) for energy storage. This report consists primarily of abstracts of presentations made at the workshop. Persons wishing to obtain further information about particular papers should contact the speakers directly; speakers' addresses and telephone numbers are listed in this report.

  18. Crystal and magnetic structure of Eu4Ga8Ge16

    DEFF Research Database (Denmark)

    Christensen, M.; Bryan, J.D.; Birkedal, H.;

    2003-01-01

    The antiferromagnetic ordering and crystal structure of the clathrate compound Eu4Ga8Ge16 was investigated using multitemperature neutron and synchrotron x-ray powder diffraction. High-resolution low-Q neutron data were measured at long wavelength (lambda=4.2 Angstrom) between 1.5 and 15 K...... for an accurate description of the magnetic structure, whereas high-Q diffraction patterns were collected using neutrons of wavelength 1.9 Angstrom at the same temperatures to determine the nuclear structure precisely. The structure orders antiferromagnetically at about 8 K with ferromagnetic chains parallel...... of 5.99 and 6.98 Angstrom, respectively, leads to an overall antiferromagnetic structure. A fit to a power law of the temperature dependence of the ordered Eu2+ magnetic moment results in a moment of 7.01(7)mu(B) at 0 K in agreement with the 7mu(B) for the free ion value of Eu2+. The temperature...

  19. Influence of the Mixing State of tert- Butyl Alcohol-water Mixtures on the Conformation of Bovine Serum Albumin

    Institute of Scientific and Technical Information of China (English)

    MA,Lin; WANG,Xu; XU,Li; HE,Wei-Ren; WEI,Zhi-Qiang; LIN,Rui-Sen

    2008-01-01

    The hydrodynamic radii of bovine serum albumin (BSA) in TBA-water mixtures were determined by dynamic light scattering measurements and utilized to investigate the conformational change of BSA in TBA-water mixtures, together with the analysis of the fluorescence spectra and UV-vis absorption spectra of BSA. Meanwhile, static light scattering measurements were used to probe the mixing state of the binary mixtures of TBA-water and the ternary mixtures of BSA-TBA-water and its influence on the conformation of the protein. A close relationship between the mixing state of TBA-water mixtures and the conformation of BSA was observed. The mixing state of TBA-water mixture at a low concentration was characterized by the clathrate hydrate of TBA caged by water molecules and it was found that hydrophobic binding of TBA to nonpolar groups of BSA in general destabilized the native structure of the protein, however, addition of a small amount of TBA attenuated the hydrophobic interactions among nonpolar groups of the protein and promoted a more ordered conformation. The results clearly showed that clustering of TBA at a high concentration reduced the effectiveness on destabilization of the compact conformation of proteins.

  20. Martian Atmospheric Methane Plumes from Meteor Shower Infall: A Hypothesis

    Science.gov (United States)

    Fries, M.; Christou, A.; Archer, D.; Conrad, P.; Cooke, W.; Eigenbrode, J.; ten Kate, I. L.; Matney, M.; Niles, P.; Sykes, M.

    2016-01-01

    Methane plumes in the martian atmosphere have been detected using Earth-based spectroscopy, the Planetary Fourier Spectrometer on the ESA Mars Express mission, and the NASA Mars Science Laboratory. The methane's origin remains a mystery, with proposed sources including volcanism, exogenous sources like impacts and interplanetary dust, aqueous alteration of olivine in the presence of carbonaceous material, release from ancient deposits of methane clathrates, and/or biological activity. To date, none of these phenomena have been found to reliably correlate with the detection of methane plumes. An additional source exists, however: meteor showers could generate martian methane via UV pyrolysis of carbon-rich infall material. We find a correlation between the dates of Mars/cometary orbit encounters and detections of methane on Mars. We hypothesize that cometary debris falls onto Mars during these interactions, depositing freshly disaggregated meteor shower material in a regional concentration. The material generates methane via UV photolysis, resulting in a localized "plume" of short-lived methane.

  1. DFT-based inhibitor and promoter selection criteria for pentagonal dodecahedron methane hydrate cage

    Indian Academy of Sciences (India)

    Snehanshu Pal; T K Kundu

    2013-09-01

    Density functional theory (DFT)-based simulations have been performed to provide electronic structure property correlation based reasoning for conceptualizing the effect of encapsulated methane molecule on the formation of methane hydrate cages, the role of methanol and ethylene glycol as inhibitor and the role of tetra-hydro-furan (THF) and cyclopentane as promoter of methane hydrate. Geometry optimization of 512 cage, 51262 cage and 51264 cage with and without encapsulated methane and the cluster of 512 cage with ethylene glycol, methanol, cyclopentane have been performed by density functional theory using B97X-D/6-31++G(d,p) method. Methane hydrate formation inhibition by methanol and ethylene glycol as well as methane hydrate stabilization by cyclopentane and tetrahydrofuran are critically analysed based on the interaction energy, free energy change, dipole moment and infrared frequency calculation. Calculation of free energy change for formation of methane hydrate with/without reagents at various temperature and pressure using optimized structure is reported here. It is observed that hydrogen bond between water molecules of clathrate 512 cages become stronger in the presence of cyclopentane and tetrahydrofuran but weaker/broken in the presence of ethylene glycol and methanol. Simulated results correspond well with experimental findings and can be useful for designing new inhibitor and promoter molecules for gas hydrate formation.

  2. Nuclear data generation for cryogenic moderators and high temperature moderators

    International Nuclear Information System (INIS)

    The commonly used processing codes for nuclear data only allow the generation of cross section data for a limited number of materials and physical conditions.At present, one of the most used computer codes for the generation of neutron cross sections is N J O Y, which is based on a phonon expansion of the scattering function starting from the frequency spectrum.Therefore, the information related to the system's density of states is crucial to produce the required data of interest. In this work the formalism of the Synthetic Model for Molecular Solids (S M M S) was implemented, which is in turn based on the Synthetic Frequency Spectrum (S F S) concept.The synthetic spectrum is central in the present work, and it is built from simple, relevant parameters of the moderator, thus conforming an alternative tool when no information on the actual frequency spectrum of the moderator material is available.S F S 's for several material of interest where produced in this work, for both cryogenic and high temperature moderators.We studied some materials of special interest, like solid methane, ice, methyl clathrate and two which are of special interest in the nuclear industry: graphite and beryllium.The libraries generated in the present work for the materials considered, in spite of their synthetic origin, are able to produce results that are even in better agreement with available information

  3. Hydrogen bonds in methane-water clusters.

    Science.gov (United States)

    Salazar-Cano, Juan-Ramón; Guevara-García, Alfredo; Vargas, Rubicelia; Restrepo, Albeiro; Garza, Jorge

    2016-08-24

    Characterization of hydrogen bonds in CH4-(H2O)12 clusters was carried out by using several quantum chemistry tools. An initial stochastic search provided around 2 500 000 candidate structures, then, using a convex-hull polygon criterion followed by gradient based optimization under the Kohn-Sham scheme, a total of 54 well defined local minima were located in the Potential Energy Surface. These structures were further analyzed through second-order many-body perturbation theory with an extended basis set at the MP2/6-311++G(d,p) level. Our analysis of Gibbs energies at several temperatures clearly suggests a structural preference toward compact water clusters interacting with the external methane molecule, instead of the more commonly known clathrate-like structures. This study shows that CH4-(H2O)12 clusters may be detected at temperatures up to 179 K, this finding provides strong support to a recently postulated hypothesis that suggests that methane-water clusters could be present in Mars at these conditions. Interestingly, we found that water to water hydrogen bonding is strengthened in the mixed clusters when compared to the isolated water dimer, which in turn leads to a weakening of the methane to water hydrogen bonding when compared to the CH4-(H2O) dimer. Finally, our evidence places a stern warning about the abilities of popular geometrical criteria to determine the existence of hydrogen bonds. PMID:27492605

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

    Directory of Open Access Journals (Sweden)

    Thomas M. Vlasic

    2016-08-01

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

  5. Occurrence of organic compound (diploptene) from the East Sea core sediment and its paleoceanographic implications

    International Nuclear Information System (INIS)

    Research focusing on marine sediments has indicated that methane hydrate stored in deep sea sediments and the episodic emission of methane gas into the water column and atmosphere are related to environmental changes over geological time. Marine sediments are known to strongly affect global climatic changes and marine ecosystems. The ideal model of episodic methane hydrate instability due to the intermediate water circulation, is called the clathrate gun hypothesis. It is essential for tracking methane emissions from deep sea sediments through direct and indirect methods. Another approach to tracking methane emissions uses isotopic studies of foraminifera and organic compounds. Diploptene is a common constituent of hydrocarbons reported in marine sediments. The most important source of diploptene in marine sediments is thought to be aerobic methanotrophic bacteria. This study determined the timing of the occurrence of diploptene and related paleoceanographic environmental changes. The results of a preliminary study of two piston cores from the East Sea and their interpretation were also presented. The paper discussed the materials and methods used in the study. It also described vertical variations of diploptene concentration of the two cores and carbon isotopic value of the diploptene. It was concluded that the diploptene was likely derived from bacterial activity. Carbon isotopic values of diploptene from this study showed depleted values, and may indicate the methanogenic bacterial activity. 12 refs., 1 fig

  6. Occurrence of organic compound (diploptene) from the East Sea core sediment and its paleoceanographic implications

    Energy Technology Data Exchange (ETDEWEB)

    Hyun, S.; Yim, U.H.; Shim, W.J. [Korea Ocean Research and Development Inst., Geoje, Kyeongnam (Korea, Republic of); Bahk, J.J.; Nam, S.I.; Lee, Y.J. [Korea Inst. of Geoscience and Mineral Resources (Korea, Republic of); Uchida, M. [National Inst. for Environmental Studies, Onogawa, Tsukuba (Japan)

    2008-07-01

    Research focusing on marine sediments has indicated that methane hydrate stored in deep sea sediments and the episodic emission of methane gas into the water column and atmosphere are related to environmental changes over geological time. Marine sediments are known to strongly affect global climatic changes and marine ecosystems. The ideal model of episodic methane hydrate instability due to the intermediate water circulation, is called the clathrate gun hypothesis. It is essential for tracking methane emissions from deep sea sediments through direct and indirect methods. Another approach to tracking methane emissions uses isotopic studies of foraminifera and organic compounds. Diploptene is a common constituent of hydrocarbons reported in marine sediments. The most important source of diploptene in marine sediments is thought to be aerobic methanotrophic bacteria. This study determined the timing of the occurrence of diploptene and related paleoceanographic environmental changes. The results of a preliminary study of two piston cores from the East Sea and their interpretation were also presented. The paper discussed the materials and methods used in the study. It also described vertical variations of diploptene concentration of the two cores and carbon isotopic value of the diploptene. It was concluded that the diploptene was likely derived from bacterial activity. Carbon isotopic values of diploptene from this study showed depleted values, and may indicate the methanogenic bacterial activity. 12 refs., 1 fig.

  7. Deep-ocean field test of methane hydrate formation from a remotely operated vehicle

    Science.gov (United States)

    Brewer, Peter G.; Orr, Franklin M., Jr.; Friederich, Gernot; Kvenvolden, Keith A.; Orange, Daniel L.; McFarlane, James; Kirkwood, William

    1997-05-01

    We have observed the process of formation of clathrate hydrates of methane in experiments conducted on the remotely operated vehicle (ROV) Ventana in the deep waters of Monterey Bay. A tank of methane gas, acrylic tubes containing seawater, and seawater plus various types of sediment were carried down on Ventana to a depth of 910 m where methane gas was injected at the base of the acrylic tubes by bubble stream. Prior calculations had shown that the local hydrographic conditions gave an upper limit of 525 m for the P-T boundary defining methane hydrate formation or dissociation at this site, and thus our experiment took place well within the stability range for this reaction to occur. Hydrate formation in free seawater occurred within minutes as a buoyant mass of translucent hydrate formed at the gas-water interface. In a coarse sand matrix the filling of the pore spaces with hydrate turned the sand column into a solidified block, which gas pressure soon lifted and ruptured. In a fine-grained black mud the gas flow carved out flow channels, the walls of which became coated and then filled with hydrate in larger discrete masses. Our experiment shows that hydrate formation is rapid in natural seawater, that sediment type strongly influences the patterns of hydrate formation, and that the use of ROV technologies permits the synthesis of large amounts of hydrate material in natural systems under a variety of conditions so that fundamental research on the stability and growth of these substances is possible.

  8. Seasonal and spatial variation in species diversity, abundance, and element accumulation capacities of macroalgae in mangrove forests of Zhanjiang, China

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yubin; LI Yuan; SHI Fei; SUN Xingli; LIN Guanghui

    2014-01-01

    The objective of this study was to investigate whether there was distinctive seasonal and zonal variation in the species diversity, biomass, and element accumulation capacities of macroalgae in two major intertidal mangrove stand types (Avicennia marina assemblage andSonneratia apetala assemblage) in the Zhanjiang region of southern China. Over a year, 31 species in 15 genera were identified in both mangrove assem-blages, of which the dominant species wereCladophoropsis zollingeriand Enteromorpha clathrat.Macroal-gal species were significantly most abundant in spring (p<0.05), followed by summer, winter, and autumn. Variation in the zonal distribution of macroalgal species was conspicuous in both intertidal mangrove as-semblages, with the greatest abundance in the middle zone, and the least in the front zone. Patterns in the seasonal and zonal variation in macroalgal biomass in theS. apetalaassemblage were similar to those of macroalgal species diversity in both mangrove assemblages. The seasonal patterns in tissue concentrations of 15 analyzed elements were not uniform among the macroalgaeC. zollingeri,E. clathrata, andGracilaria salicornia in theA. marina assemblage. All three species exhibited variation in their responses to ambient concentrations of different elements, implying their differential ability to absorb and selectively accumulate certain elements.

  9. Modeling the methane hydrate formation in an aqueous film submitted to steady cooling

    Energy Technology Data Exchange (ETDEWEB)

    Avendano-Gomez, J.R. [ESIQIE, Laboratorio de Ingenieria Quimica Ambiental, Mexico (Mexico). Inst. Politecnico Nacional; Garcia-Sanchez, F. [Laboratorio de Termodinamica, Mexico (Mexico). Inst. Mexicano del Petroleo; Gurrola, D.V. [UPIBI, Laboratorio de Diseno de Plantas, Mexico (Mexico). Inst. Politecnico Nacional

    2008-07-01

    Gas hydrates, or clathrate hydrates, are ice-like compounds that results from the kinetic process of crystallization of an aqueous solution supersaturated with a dissolved gas. This paper presented a model that took into account two factors involved in the hydrate crystallization, notably the stochastic nature of crystallization that causes sub-cooling and the heat resulting from the exothermic enthalpy of hydrate formation. The purpose of this study was to model the thermal evolution inside a hydrate forming system which was submitted to an imposed steady cooling. The study system was a cylindrical thin film of aqueous solution at 19 Mpa. The study involved using methane as the hydrate forming molecule. It was assumed that methane was homogeneously dissolved in the aqueous phase. Ethane hydrate was formed through a kinetic process of nucleation and crystallization. In order to predict the onset time of nucleation, the induction time needed to be considered. This paper discussed the probability of nucleation as well as the estimation of the rate of nucleation. It also presented the mathematical model and boundary conditions. These included assumptions and derivation of the model; boundary conditions; initial conditions; and numerical solution of the model equation. It was concluded that the heat source must be considered when investigating crystallization effects. 34 refs., 2 tabs., 2 figs.

  10. Interstellar and Cometary Dust in Relation to the Origin of Life

    Science.gov (United States)

    Krueger, F. R.; Kissel, J.

    Cometary grains are commonly considered to be the precursors of organic materials in early life on the Earth. It is a persistent mystery, however, how chemical evolution within the earliest protocells was triggered. We discuss the type of organics measured from Comet p/Wild-2, using the Cometary and Intersellar Dust Analyzer (CIDA). This instrument is not sensitive to mineralic cores of dust particles due to their low-impact velocities (6 km/s). The CIDA data allows us to analyze the organic fraction of interstellar dust at ~1 AU from the Sun. Surprisingly, it mainly consists of quinone-type polycyclics, some of them similar to pyrrolo-Cquinoline-Cquinone. Strong redox catalysts are apparently required to trigger the earliest chemical evolutionary steps. Our understanding of the thermochemical evolution of accretion from interstellar clouds containing cosmic grains to comets qualitatively and quantitatively requires a comprehensive understanding of the production of water and CO from the comets. The"dirty snowball" model is rejected as a suitable model for "fresh" comets. Apparently the primordial source of water is twofold: (1) a signicant fraction of cometary clathrates is contained in the mineralic and the organic fractions, producing water by evaporation; (2) rich oxygen containing PAH's in the organic phase produces water by solar radiation-induced chemical processes.

  11. Kinetics of methane hydrate decomposition studied via in situ low temperature X-ray powder diffraction.

    Science.gov (United States)

    Everett, S Michelle; Rawn, Claudia J; Keffer, David J; Mull, Derek L; Payzant, E Andrew; Phelps, Tommy J

    2013-05-01

    Gas hydrate is known to have a slowed decomposition rate at ambient pressure and temperatures below the melting point of ice. As hydrate exothermically decomposes, gas is released and water of the clathrate cages transforms into ice. Based on results from the decomposition of three nominally similar methane hydrate samples, the kinetics of two regions, 180-200 and 230-260 K, within the overall decomposition range 140-260 K, were studied by in situ low temperature X-ray powder diffraction. The kinetic rate constants, k(a), and the reaction mechanisms, n, for ice formation from methane hydrate were determined by the Avrami model within each region, and activation energies, E(a), were determined by the Arrhenius plot. E(a) determined from the data for 180-200 K was 42 kJ/mol and for 230-260 K was 22 kJ/mol. The higher E(a) in the colder temperature range was attributed to a difference in the microstructure of ice between the two regions. PMID:23557375

  12. NEUTRON SCATTERING AND LATTICE DYNAMICAL STUDIES OF THE HIGH-PRESSURE PHASE ICE (II)

    Institute of Scientific and Technical Information of China (English)

    董顺乐; 王燕

    2001-01-01

    Lattice dynamical calculations have been carried out for ice II based on the force field constructed for ice Ih. In order to fully understand ice II inelastic neutron scattering spectra, the decomposed phonon density of states was shown mode by mode. Calculated results have shown that the hydrogen bond force constant between the six-molecule rings is significantly weaker, 75eV/nm2, compared with the force constant, 220eV/nm2, within the rings. Inelastic neutron scattering spectra of clathrate hydrate H2O+He are almost the same as ice II. This means that the absorption of He atoms cannot affect the bond strengths of the ice II host lattice. Based on the force field model for ice II, the van der Waals interactions between water molecules and helium atoms are considered. The results obtained are consistent with experimental data. Lattice dynamical calculations have been carried out for ice II using seven rigid pairwise potentials.It was found that MCY makes the stretching and bending interactions in ice II too weak and makes the O-O bond length too long (~5%), thus its lattice densities are obviously lower than other potential lattices or experimental values.

  13. Observation of Binding and Rotation of Methane and Hydrogen within a Functional Metal–Organic Framework

    Science.gov (United States)

    2016-01-01

    The key requirement for a portable store of natural gas is to maximize the amount of gas within the smallest possible space. The packing of methane (CH4) in a given storage medium at the highest possible density is, therefore, a highly desirable but challenging target. We report a microporous hydroxyl-decorated material, MFM-300(In) (MFM = Manchester Framework Material, replacing the NOTT designation), which displays a high volumetric uptake of 202 v/v at 298 K and 35 bar for CH4 and 488 v/v at 77 K and 20 bar for H2. Direct observation and quantification of the location, binding, and rotational modes of adsorbed CH4 and H2 molecules within this host have been achieved, using neutron diffraction and inelastic neutron scattering experiments, coupled with density functional theory (DFT) modeling. These complementary techniques reveal a very efficient packing of H2 and CH4 molecules within MFM-300(In), reminiscent of the condensed gas in pure component crystalline solids. We also report here, for the first time, the experimental observation of a direct binding interaction between adsorbed CH4 molecules and the hydroxyl groups within the pore of a material. This is different from the arrangement found in CH4/water clathrates, the CH4 store of nature. PMID:27410670

  14. Phononic Structure Engineering: the Realization of Einstein Rattling in Calcium Cobaltate for the Suppression of Thermal Conductivity

    Science.gov (United States)

    Tian, Ruoming; Kearley, Gordon J.; Yu, Dehong; Ling, Chris D.; Pham, Anh; Embs, Jan P.; Shoko, Elvis; Li, Sean

    2016-07-01

    Phonons in condensed matter materials transmit energy through atomic lattices as coherent vibrational waves. Like electronic and photonic properties, an improved understanding of phononic properties is essential for the development of functional materials, including thermoelectric materials. Recently, an Einstein rattling mode was found in thermoelectric material Na0.8CoO2, due to the large displacement of Na between the [CoO2] layers. In this work, we have realized a different type of rattler in another thermoelectric material Ca3Co4O9 by chemical doping, which possesses the same [CoO2] layer as Na0.8CoO2. It remarkably suppressed the thermal conductivity while enhancing its electrical conductivity. This new type of rattler was investigated by inelastic neutron scattering experiments in conjunction with ab-initio molecular dynamics simulations. We found that the large mass of dopant rather than the large displacement is responsible for such rattling in present study, which is fundamentally different from skutterudites, clathrates as well as Na analogue. We have also tentatively studied the phonon band structure of this material by DFT lattice dynamics simulation, showing the relative contribution to phonons in the distinct layers of Ca3Co4O9.

  15. Coupled THCM Modeling of Gas Hydrate Bearing Sediments

    Science.gov (United States)

    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.

  16. Physical properties of gas hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Kliner, J.T.R.; Grozic, J.L.H. [Calgary Univ., AB (Canada)

    2003-07-01

    Gas hydrates are naturally occurring, solid crystalline compounds (clathrates) that encapsulate gas molecules inside the lattices of hydrogen bonded water molecules within a specific temperature-pressure stability zone. Estimates of the total quantity of available methane gas in natural occurring hydrates are based on twice the energy content of known conventional fossil fuels reservoirs. Accurate and reliable in-situ quantification techniques are essential in determining the economic viability of this potential energy yield, which is dependent upon several factors such as sensitivity of the temperature-pressure stability zone, sediment type, porosity, permeability, concentration/abundance of free gas, spatial distribution in pore spaces, specific cage occupancy, and the influence of inhibitors. Various techniques like acoustic P and S waves, time domain reflectometry, and electrical resistance have been used to analyze the quantity and spatial distribution of the gas hydrate samples. These techniques were reviewed and the results obtained in the course of gas hydrate research were presented. 34 refs., 8 figs.

  17. [Experimental study on chemotherapy of acute glanders].

    Science.gov (United States)

    Iliukhin, V I; Rotov, K A; Senina, T V; Snatenkov, E A; Tikhonov, S N; Plekhanova, N G; Kulikova, A S; Shubnikova, E V; Korol', E V; Nekhezina, M O

    2012-01-01

    Glanders is a zoonotic infection inducing acute forms of the disease (pneumonia, sepsis) in humans and animals under certain conditions, which even with the use of modern chemotherapy have unfavourable prognosis. Insufficient of efficacy of antibiotics with in vitro low MIC for planktonic bacterial suspension of Burkholderia mallei in chemotherapy of acute forms of glanders was due to the capacity of the pathogen for intracellular survival and formation of biofilms. Under such conditions the susceptibility of B. mallei to antibiotics lowered by several orders of magnitude. Chemotherapy of the glanders acute forms in animals usually provided only an increase of the lifespan, while among the survivors there was recorded a high relapse rate. More favourable outcomes were observed with the use of in vitro effective antibiotics in the form of clathrate compounds or especially liposomal forms. In the experiments with golden hamsters the survival rate reached 100% in 1000 Dlm infection even with the treatment onset by meropenem liposomal form 48 hours after the infection. Chemotherapeutics in the liposomal form significantly lowered resistance of B. mallei in both the experiments with a suspension of planktonic organisms and the use of bacteria interned in eukaryotic cells (Tetrahymena pyriformis).

  18. Composition and structure of the shallow subsurface of Ceres revealed by crater morphology

    Science.gov (United States)

    Bland, Michael T.; Raymond, Carol A.; Schenk, Paul M.; Fu, Roger R.; Kneissl, Thomas; Pasckert, Jan Hendrik; Hiesinger, Harry; Preusker, Frank; Park, Ryan S.; Marchi, Simone; King, Scott D.; Castillo-Rogez, Julie C.; Russell, Christopher T.

    2016-07-01

    Before NASA’s Dawn mission, the dwarf planet Ceres was widely believed to contain a substantial ice-rich layer below its rocky surface. The existence of such a layer has significant implications for Ceres’s formation, evolution, and astrobiological potential. Ceres is warmer than icy worlds in the outer Solar System and, if its shallow subsurface is ice-rich, large impact craters are expected to be erased by viscous flow on short geologic timescales. Here we use digital terrain models derived from Dawn Framing Camera images to show that most of Ceres’s largest craters are several kilometres deep, and are therefore inconsistent with the existence of an ice-rich subsurface. We further show from numerical simulations that the absence of viscous relaxation over billion-year timescales implies a subsurface viscosity that is at least one thousand times greater than that of pure water ice. We conclude that Ceres’s shallow subsurface is no more than 30% to 40% ice by volume, with a mixture of rock, salts and/or clathrates accounting for the other 60% to 70%. However, several anomalously shallow craters are consistent with limited viscous relaxation and may indicate spatial variations in subsurface ice content.

  19. Proceedings of the 6. international conference on gas hydrates : ICGH 2008

    Energy Technology Data Exchange (ETDEWEB)

    Englezos, P. (ed.) [British Columbia Univ., Vancouver, BC (Canada); Ripmeester, J. (ed.) [National Research Council of Canada, Ottawa, ON (Canada); Dallimore, S.R. [Natural Resources Canada, Ottawa, ON (Canada). Geological Survey of Canada; Servio, P. [McGill Univ., Montreal, PQ (Canada). Dept. of Chemical Engineering; Austvik, T. [Statoil, Trondheim (Norway); Collett, T.S. [United States Geological Survey, Denver, CO (United States); Mehta, A. [Shell E and P Asia Pacific, Sarawak (Malaysia); Paull, C.K. [Monterey Bay Aquarium Research Inst., CA (United States); Sloan, E.D.Jr. [Colorado School of Mines, Golden, CO (United States); Uchida, T. [Hokkaido Univ., Sapporo (Japan)] (comps.)

    2008-07-01

    This international conference provided a forum to highlight gas hydrate research that is underway at academic institutions as well as government and industrial laboratories around the world. The gas or clathrate hydrate research community includes chemical, petroleum and mechanical engineers, geologists, geophysicists, marine biologists, chemists and physicists. The conference was attended by more than 500 delegates who presented their professional knowledge in all areas of the gas hydrates field, emphasizing new aspects. The topics of discussion included resource delineation, reservoir simulation modeling and production technology. Environmental considerations involving natural gas hydrates and global climate change were also highlighted along with carbon dioxide disposal in aquifers and deep oceans. Issues facing oil and gas operations were also discussed, with reference to flow assurance in pipelines, safety issues, permafrost and marine geohazards. Novel technologies involving hydrogen storage, carbon dioxide capture and sequestration were also highlighted along with basic science and engineering aspects of gas hydrate systems. All 417 presentations from the conference have been catalogued separately for inclusion in this database. refs., tabs., figs.

  20. Proceedings of the 6. international conference on gas hydrates : ICGH 2008

    International Nuclear Information System (INIS)

    This international conference provided a forum to highlight gas hydrate research that is underway at academic institutions as well as government and industrial laboratories around the world. The gas or clathrate hydrate research community includes chemical, petroleum and mechanical engineers, geologists, geophysicists, marine biologists, chemists and physicists. The conference was attended by more than 500 delegates who presented their professional knowledge in all areas of the gas hydrates field, emphasizing new aspects. The topics of discussion included resource delineation, reservoir simulation modeling and production technology. Environmental considerations involving natural gas hydrates and global climate change were also highlighted along with carbon dioxide disposal in aquifers and deep oceans. Issues facing oil and gas operations were also discussed, with reference to flow assurance in pipelines, safety issues, permafrost and marine geohazards. Novel technologies involving hydrogen storage, carbon dioxide capture and sequestration were also highlighted along with basic science and engineering aspects of gas hydrate systems. All 417 presentations from the conference have been catalogued separately for inclusion in this database. refs., tabs., figs

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

    Science.gov (United States)

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

    2016-08-01

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

  2. Lattice Boltzmann pore-scale model for multi-component reactive transport

    Science.gov (United States)

    Kang, Qinjun; Lichtner, Peter; Zhang, Dongxiao; Tsimpanogiannis, Ioannis

    2004-11-01

    A better understanding of multi-component flow and reaction in natural and man-made porous media is critical to a wide range of fields, including hydrology (groundwater quality), fossil energy (oil, gas, coalbed methane, clathrates), economic geology (mineral processing and development), geologic carbon sequestration (hydrodynamic and mineral trapping of carbon), and materials manufacturing and degradation (polymer composites, concrete, building materials). This problem is notoriously difficult because it usually involves multiple processes (convection, diffusion, and chemical reaction) and complex geometries and boundaries. In this work, we present a multi-component lattice Boltzmann model for simulating reactive transport in porous media at the pore scale. This model takes into account convection, diffusion, homogeneous reactions among multiple aqueous species, heterogeneous reactions between the aqueous solution and the minerals, as well as the resulting geometrical changes in pore space. Homogeneous reactions are described through local equilibrium mass action relations. Mineral reactions are treated kinetically through boundary conditions at the surface. We have applied this model to a hypothetical two-component system in a synthetically constructed medium, and analyzed the effects of convection, diffusion, reaction rate constants, and chemical compositions on mineral alteration of the porous medium.

  3. Thermoelectric transport in rare-earth compounds

    Energy Technology Data Exchange (ETDEWEB)

    Koehler, Ulrike

    2007-07-01

    This work focuses on the thermoelectric transport in rare-earth compounds. The measurements of the thermal conductivity, thermopower, and Nernst coefficient are supplemented by investigations of other quantities as magnetic susceptibility and specific heat. Chapter 2 provides an introduction to the relevant physical concepts. Section 1 of that chapter summarizes the characteristic properties of rare-earth systems; section 2 gives an overview on thermoelectric transport processes in magnetic fields. The applied experimental techniques as well as the new experimental setup are described in detail in Chapter 3. The experimental results are presented in Chapter 4-6, of which each concentrates on a different subject. In Chapter 4, various Eu clathrates and the skutterudite-like Ce{sub 3}Rh{sub 4}Sn{sub 13} are presented, which have been investigated as potential thermoelectric materials for applications. Chapter 5 focusses on the study of the energy scales in the heavy-fermion series Lu{sub 1-x}Yb{sub x}Rh{sub 2}Si{sub 2} and Ce{sub x}La{sub 1-x}Ni{sub 2}Ge{sub 2} by means of thermopower investigations. Chapter 6 is dedicated to the thermoelectric transport properties of the correlated semimetal CeNiSn with special emphasis on the Nernst coefficient of this compound. (orig.)

  4. Chemical modeling constraints on Martian surface mineralogies formed in an early, warm, wet climate, and speculations on the occurrence of phosphate minerals in the Martian regolith

    Science.gov (United States)

    Plumlee, Geoffrey S.; Ridley, W. Ian; Debraal, Jeffrey D.

    1992-01-01

    This is one in a series of reports summarizing our chemical modeling studies of water-rock-gas interactions at the martian surface through time. The purpose of these studies is to place constraints on possible mineralogies formed at the martian surface and to model the geochemical implications of martian surficial processes proposed by previous researchers. Plumlee and Ridley summarize geochemical processes that may have occurred as a result of inferred volcano- and impact-driven hydrothermal activity on Mars. DeBraal et al. model the geochemical aspects of water-rock interactions and water evaporation near 0 C, as a prelude to future calculations that will model sub-0 C brine-rock-clathrate interactions under the current martian climate. In this report, we discuss reaction path calculations that model chemical processes that may have occurred at the martian surface in a postulated early, warm, wet climate. We assume a temperature of 25 C in all our calculations. Processes we model here include (1) the reaction of rainwater under various ambient CO2 and O2 pressures with basaltic rocks at the martian surface, (2) the formation of acid rain by volcanic gases such as HCl and SO2, (3) the reactions of acid rain with basaltic surficial materials, and (4) evaporation of waters resulting from rainwater-basalt interactions.

  5. RESEARCH ON COUPLED RELATIONSHIP BETWEEN HYDRATION NUMBER WITH RAMAN SPECTRUM

    Institute of Scientific and Technical Information of China (English)

    LEI Huaiyan; LIU Zhihong; FAN Shuanshi; XU Maoquan; GUAN Baocong

    2003-01-01

    As we know, there are three structures-sⅠ, sⅡ, and sH, with hydrocarbonate gas hydrate.Because of those special structures characteristics and potentail large fossil energy resource, gas hydrate play an important role in natural carbonate cycle system. In this paper, CH4, CO2, C3H8, and CH4 +CO2 system have been experimental performed in order to model hydrate formation and discomposition and to obtain hydrate stability conditions of tempreature and pressure. The results from laboratory using Raman spectra show that Raman spectrascopy is a effective tool to identify hydrate structure. Raman spectra of clathrate hydrate guest molecules are presented for two structure (sⅠ and sⅡ) in the following systems: CH4, CO2, C3 H8. Relatively occupancy of CH4 in the large and small cavities of sⅠ were determined by deconvoluting the v1 symmetric bands, resulting in hydration numbers of 6.04±0.03. The freqyuency of the v1 bands for CH4 in structures Ⅰ and Ⅱ differ statistically. The large cavities were measured to be almost fully occupied by CH4 and CO2, whereas only a small fraction of the small cavities are occupied by CH4. No CO2 was found in the small cavities.

  6. Novel hydrogen hydrate structures under pressure.

    Science.gov (United States)

    Qian, Guang-Rui; Lyakhov, Andriy O; Zhu, Qiang; Oganov, Artem R; Dong, Xiao

    2014-01-01

    Gas hydrates are systems of prime importance. In particular, hydrogen hydrates are potential materials of icy satellites and comets, and may be used for hydrogen storage. We explore the H₂O-H₂ system at pressures in the range 0-100 GPa with ab initio variable-composition evolutionary simulations. According to our calculation and previous experiments, the H₂O-H₂ system undergoes a series of transformations with pressure, and adopts the known open-network clathrate structures (sII, C₀), dense "filled ice" structures (C₁, C₂) and two novel hydrate phases. One of these is based on the hexagonal ice framework and has the same H₂O:H₂ ratio (2:1) as the C₀ phase at low pressures and similar enthalpy (we name this phase Ih-C₀). The other newly predicted hydrate phase has a 1:2 H₂O:H₂ ratio and structure based on cubic ice. This phase (which we name C₃) is predicted to be thermodynamically stable above 38 GPa when including van der Waals interactions and zero-point vibrational energy, and explains previously mysterious experimental X-ray diffraction and Raman measurements. This is the hydrogen-richest hydrate and this phase has a remarkable gravimetric density (18 wt.%) of easily extractable hydrogen.

  7. New insights on Saturn's formation from its nitrogen isotopic composition

    CERN Document Server

    Mousis, Olivier; Fletcher, Leigh N; Mandt, Kathleen E; Ali-Dib, Mohamad; Gautier, Daniel; Atreya, Sushil

    2014-01-01

    The recent derivation of a lower limit for the $^{14}$N/$^{15}$N ratio in Saturn's ammonia, which is found to be consistent with the Jovian value, prompted us to revise models of Saturn's formation using as constraints the supersolar abundances of heavy elements measured in its atmosphere. Here we find that it is possible to account for both Saturn's chemical and isotopic compositions if one assumes the formation of its building blocks at $\\sim$45 K in the protosolar nebula, provided that the O abundance was $\\sim$2.6 times protosolar in its feeding zone. To do so, we used a statistical thermodynamic model to investigate the composition of the clathrate phase that formed during the cooling of the protosolar nebula and from which the building blocks of Saturn were agglomerated. We find that Saturn's O/H is at least $\\sim$34.9 times protosolar and that the corresponding mass of heavy elements ($\\sim$43.1 \\Mearth) is within the range predicted by semi-convective interior models.

  8. Large methane releases lead to strong aerosol forcing and reduced cloudiness

    Directory of Open Access Journals (Sweden)

    T. Kurtén

    2011-03-01

    Full Text Available The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller contributions from the associated carbon dioxide or ozone increases. Here, we study the effect of strongly elevated methane (CH4 levels on oxidant and aerosol particle concentrations using a combination of chemistry-transport and general circulation models. A 10-fold increase in methane concentrations is predicted to significantly decrease hydroxyl radical (OH concentrations, while moderately increasing ozone (O3. These changes lead to a 70% increase in the atmospheric lifetime of methane, and an 18% decrease in global mean cloud droplet number concentrations (CDNC. The CDNC change causes a radiative forcing that is comparable in magnitude to the longwave radiative forcing ("enhanced greenhouse effect" of the added methane. Together, the indirect CH4-O3 and CH4-OH-aerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously large temperature changes associated with historic methane releases.

  9. Evidence of fast pebble growth near condensation fronts in the HL Tau protoplanetary disk

    CERN Document Server

    Zhang, Ke; Bergin, Edwin A

    2015-01-01

    Water and simple organic molecular ices dominate the mass of solid materials available for planetesimal and planet formation beyond the water snow line. Here we analyze ALMA long baseline 2.9, 1.3 and 0.87 mm continuum images of the young star HL Tau, and suggest that the emission dips observed are due to rapid pebble growth around the condensation fronts of abundant volatile species. Specifically, we show that the prominent innermost dip at 13 AU is spatially resolved in the 0.87 mm image, and its center radius is coincident with the expected mid-plane condensation front of water ice. In addition, two other prominent dips, at distances of 32 and 63 AU, cover the mid-plane condensation fronts of pure ammonia or ammonia hydrates and clathrate hydrates (especially with CO and N$_2$) formed from amorphous water ice. The spectral index map of HL Tau between 1.3 and 0.87 mm shows that the flux ratios inside the dips are statistically larger than those of nearby regions in the disk. This variation can be explained ...

  10. Fluid Inclusions in the Gold-Bearing Quartz Veins at Um Rus Area, Eastern Desert, Egypt

    Institute of Scientific and Technical Information of China (English)

    MOHAMED EL TOKHI; ABDALLA EL MUSLEM

    2002-01-01

    Fluid inclusions in the gold-bearing quartz veins at the Um Rus area are of three types: H2O, H2O-CO2 and CO2 inclusions. H2O inclusions are the most abundant, they include two phases which exhibit low and high homogenization temperatures ranging from 150 to200℃ and 175 to 250℃, respectively. The salinity of aqueous inclusions, based on ice melting, varies between 6.1 and 8 equiv. wt% NaCl. On the other hand, H2O-CO2 fluid inclusions include three phases. Their total homogenization temperatures range from 270 to 325℃,and their salinity, based on clathrate melting, ranges between 0.8 and 3.8 equiv. wt % NaCl.CO2 fluid inclusions homogenize to a liquid phase and exhibit a low density range from 0.52 to0.66 g/cm3. The partial mixing of H2O-CO2 and salt H2O-NaCl fluid inclusions is the main source of fluids from which the other types of inclusions were derived. The gold-bearing quartz veins are believed to be of medium temperature hydrothermal convective origin.

  11. A HOT GAP AROUND JUPITER'S ORBIT IN THE SOLAR NEBULA

    International Nuclear Information System (INIS)

    The Sun was an order of magnitude more luminous during the first few hundred thousand years of its existence, due in part to the gravitational energy released by material accreting from the solar nebula. If Jupiter was already near its present mass, the planet's tides opened an optically thin gap in the nebula. Using Monte Carlo radiative transfer calculations, we show that sunlight absorbed by the nebula and re-radiated into the gap raised temperatures well above the sublimation threshold for water ice, with potentially drastic consequences for the icy bodies in Jupiter's feeding zone. Bodies up to a meter in size were vaporized within a single orbit if the planet was near its present location during this early epoch. Dust particles lost their ice mantles, and planetesimals were partially to fully devolatilized, depending on their size. Scenarios in which Jupiter formed promptly, such as those involving a gravitational instability of the massive early nebula, must cope with the high temperatures. Enriching Jupiter in the noble gases through delivery trapped in clathrate hydrates will be more difficult, but might be achieved by either forming the planet much farther from the star or capturing planetesimals at later epochs. The hot gap resulting from an early origin for Jupiter also would affect the surface compositions of any primordial Trojan asteroids.

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

    Science.gov (United States)

    Misyura, S. Y.

    2016-07-01

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

  13. NEW INSIGHTS ON SATURN'S FORMATION FROM ITS NITROGEN ISOTOPIC COMPOSITION

    Energy Technology Data Exchange (ETDEWEB)

    Mousis, Olivier; Lunine, Jonathan I. [Center for Radiophysics and Space Research, Space Sciences Building, Cornell University, Ithaca, NY 14853 (United States); Fletcher, Leigh N. [Atmospheric, Oceanic and Planetary Physics, Clarendon Laboratory, Parks Road, Oxford OX1 3PU (United Kingdom); Mandt, Kathleen E. [Southwest Research Institute, San Antonio, TX 78228 (United States); Ali-Dib, Mohamad [Université de Franche-Comté, Institut UTINAM, CNRS/INSU, UMR 6213, Observatoire des Sciences de l' Univers de Besançon (France); Gautier, Daniel [LESIA, Observatoire de Paris, CNRS, UPMC, Univ. Paris-Diderot, F-92195 Meudon Cedex (France); Atreya, Sushil, E-mail: olivier.mousis@obs-besancon.fr [Department of Atmospheric, Oceanic, and Space Sciences, University of Michigan, Ann Arbor, MI 48109-2143 (United States)

    2014-12-01

    The recent derivation of a lower limit for the {sup 14}N/{sup 15}N ratio in Saturn's ammonia, which is found to be consistent with the Jovian value, prompted us to revise models of Saturn's formation using as constraints the supersolar abundances of heavy elements measured in its atmosphere. Here we find that it is possible to account for both Saturn's chemical and isotopic compositions if one assumes the formation of its building blocks at ∼45 K in the protosolar nebula, provided that the O abundance was ∼2.6 times protosolar in its feeding zone. To do so, we used a statistical thermodynamic model to investigate the composition of the clathrate phase that formed during the cooling of the protosolar nebula and from which the building blocks of Saturn were agglomerated. We find that Saturn's O/H is at least ∼34.9 times protosolar and that the corresponding mass of heavy elements (∼43.1 M {sub ⊕}) is within the range predicted by semi-convective interior models.

  14. Large methane releases lead to strong aerosol forcing and reduced cloudiness

    Directory of Open Access Journals (Sweden)

    T. Kurtén

    2011-07-01

    Full Text Available The release of vast quantities of methane into the atmosphere as a result of clathrate destabilization is a potential mechanism for rapid amplification of global warming. Previous studies have calculated the enhanced warming based mainly on the radiative effect of the methane itself, with smaller contributions from the associated carbon dioxide or ozone increases. Here, we study the effect of strongly elevated methane (CH4 levels on oxidant and aerosol particle concentrations using a combination of chemistry-transport and general circulation models. A 10-fold increase in methane concentrations is predicted to significantly decrease hydroxyl radical (OH concentrations, while moderately increasing ozone (O3. These changes lead to a 70 % increase in the atmospheric lifetime of methane, and an 18 % decrease in global mean cloud droplet number concentrations (CDNC. The CDNC change causes a radiative forcing that is comparable in magnitude to the longwave radiative forcing ("enhanced greenhouse effect" of the added methane. Together, the indirect CH4-O3 and CH4-OH-aerosol forcings could more than double the warming effect of large methane increases. Our findings may help explain the anomalously large temperature changes associated with historic methane releases.

  15. Martian zeolites as a source of atmospheric methane

    Science.gov (United States)

    Mousis, Olivier; Simon, Jean-Marc; Bellat, Jean-Pierre; Schmidt, Frédéric; Bouley, Sylvain; Chassefière, Eric; Sautter, Violaine; Quesnel, Yoann; Picaud, Sylvain; Lectez, Sébastien

    2016-11-01

    The origin of the martian methane is still poorly understood. A plausible explanation is that methane could have been produced either by hydrothermal alteration of basaltic crust or by serpentinization of ultramafic rocks producing hydrogen and reducing crustal carbon into methane. Once formed, methane storage on Mars is commonly associated with the presence of hidden clathrate reservoirs. Here, we alternatively suggest that chabazite and clinoptilolite, which belong to the family of zeolites, may form a plausible storage reservoir of methane in the martian subsurface. Because of the existence of many volcanic terrains, zeolites are expected to be widespread on Mars and their Global Equivalent Layer may range up to more than ∼1 km, according to the most optimistic estimates. If the martian methane present in chabazite and clinoptilolite is directly sourced from an abiotic source in the subsurface, the destabilization of a localized layer of a few millimeters per year may be sufficient to explain the current observations. The sporadic release of methane from these zeolites requires that they also remained isolated from the atmosphere during its evolution. The methane release over the ages could be due to several mechanisms such as impacts, seismic activity or erosion. If the methane outgassing from excavated chabazite and/or clinoptilolite prevails on Mars, then the presence of these zeolites around Gale Crater could explain the variation of methane level observed by Mars Science Laboratory.

  16. Structure and Dynamics of Cold Water Super-Earths: The Case of Occluded CH4 and its Outgassing

    CERN Document Server

    Levi, Amit; Podolak, Morris

    2014-01-01

    We study the transport of methane in the external water envelopes surrounding water-rich super-Earths and estimate its outgassing into the atmosphere. We investigate the influence of methane on the thermodynamics and mechanics of the water mantle. We find that including methane in the water matrix introduces a new phase (filled ice) resulting in hotter planetary interiors. This effect renders the super-ionic and reticulating phases accessible to relatively low mass planets lacking a H/He atmosphere. We model the thermal and structural profile of the planetary crust and discuss five possible crustal regimes. The formation of methane clathrate in the subsurface is shown to inhibit the formation of a subterranean ocean. This effect results in increased stresses on the lithosphere making modes of ice plate tectonics possible. The dynamics of the tectonic plates are analysed. We derive overturn and resurfacing time scales as well as the melt fraction underneath spreading centers. Ice mantle dynamics is found to be...

  17. Transient Climate Effects of Large Impacts on Titan

    Science.gov (United States)

    Zahnle, Kevin J.; Korycansky, Donald; Nixon, Conor A.

    2013-01-01

    Titan's thick atmosphere and volatile-rich surface cause it to respond to big impacts in a somewhat Earth-like manner. Here we construct a simple globally-averaged model that tracks the flow of energy through the environment in the weeks, years, and millenia after a big comet strikes Titan. The model Titan is endowed with 1.4 bars of N2 and 0.07 bars of CH4, methane lakes, a water ice crust, and enough methane underground to saturate the regolith to the surface. We find that a nominal Menrva impact is big enough to raise the surface temperature by approx. 80 K and to double the amount of methane in the atmosphere. The extra methane drizzles out of the atmosphere over hundreds of years. An upper-limit Menrva is just big enough to raise the surface to water's melting point. The putative Hotei impact (a possible 800-1200 km diameter basin, Soderblom et al., 2009) is big enough to raise the surface temperature to 350-400 K. Water rain must fall and global meltwaters might range between 50 m to more than a kilometer deep, depending on the details. Global meltwater oceans do not last more than a few decades or centuries at most, but are interesting to consider given Titan's organic wealth. Significant near-surface clathrate formation is possible as Titan cools but faces major kinetic barriers.

  18. Influence of fluorosurfactants on hydrate formation rates

    Energy Technology Data Exchange (ETDEWEB)

    Kim, C.U.; Jeong, K.E.; Chae, H.J.; Jeong, S.Y. [Korea Reasearch Inst. of Chemical Technology, Alternative Chemicals/Fuel Research Center, Yuseong-Gu, Daejon (Korea, Republic of)

    2008-07-01

    Gas hydrates, or clathrates, are ice-like solids that forms when natural gas is in contact with liquid water or ice under high pressure and low temperature. There is significant interest in studying the storage and transportation of gas in the form of hydrates. However, a critical problem impacting the industrial application of gas hydrates for storage and transportation of natural gas is the slow formation rate of natural gas hydrate. Researchers have previously reported on the promotion effect of some additives on gas hydrate formation and hydrate gas content. Fluorosurfactants are significantly superior to nonfluorinated surfactants in wetting action, as well as stability in harsh environments, both thermal and chemical. This paper discussed an experimental investigation into the effects of fluorosurfactants with different ionic types on the formation of methane hydrate. The surfactants used were FSN-100 of DuPont Zonyl as non-ionic surfactant and FC-143 of DuPont as anionic surfactant. The paper discussed the experimental apparatus for methane hydrate formation. It also discussed hydrate formation kinetics and the series of hydrate formation experiments that were conducted in the presence of fluorosurfactants. Last, the paper explored the results of the study. It was concluded that anionic fluorosurfactant of FC-143 had a better promoting effect on methane hydrate formation compared with nonionic surfactant of FSN-100. 8 refs., 2 tabs., 2 figs.

  19. A protosolar nebula origin for the ices agglomerated by Comet 67P/Churyumov-Gerasimenko

    CERN Document Server

    Mousis, O; Luspay-Kuti, A; Guillot, T; Marty, B; Ali-Dib, M; Wurz, P; Altwegg, K; Bieler, A; Hässig, M; Rubin, M; Vernazza, P; Waite, J H

    2016-01-01

    The nature of the icy material accreted by comets during their formation in the outer regions of the protosolar nebula is a major open question in planetary science. Some scenarios of comet formation predict that these bodies agglomerated from crystalline ices condensed in the protosolar nebula. Concurrently, alternative scenarios suggest that comets accreted amorphous ice originating from the interstellar cloud or from the very distant regions of the protosolar nebula. On the basis of existing laboratory and modeling data, we find that the N$_2$/CO and Ar/CO ratios measured in the coma of the Jupiter family comet 67P/Churyumov-Gerasimenko by the ROSINA instrument aboard the European Space Agency's Rosetta spacecraft match those predicted for gases trapped in clathrates. If these measurements are representative of the bulk N$_2$/CO and Ar/CO ratios in 67P/Churyumov-Gerasimenko, it implies that the ices accreted by the comet formed in the nebula and do not originate from the interstellar medium, supporting the...

  20. Subsurface characterization of 67P/Churyumov-Gerasimenko's Abydos site

    CERN Document Server

    Brugger, B; Morse, A; Marboeuf, U; Jorda, L; Guilbert-Lepoutre, A; Andrews, D; Barber, S; Lamy, P; Luspay-Kuti, A; Mandt, K; Morgan, G; Sheridan, S; Vernazza, P; Wright, I P

    2016-01-01

    On November 12, 2014, the ESA/Rosetta descent module Philae landed on the Abydos site of comet 67P/Churyumov-Gerasimenko. Aboard this module, the Ptolemy mass spectrometer measured a CO/CO2 ratio of 0.07 +/- 0.04 which differs substantially from the value obtained in the coma by the Rosetta/ROSINA instrument, suggesting a heterogeneity in the comet nucleus. To understand this difference, we investigated the physico-chemical properties of the Abydos subsurface leading to CO/CO2 ratios close to that observed by Ptolemy at the surface of this region. We used a comet nucleus model that takes into account different water ice phase changes (amorphous ice, crystalline ice and clathrates), as well as diffusion of molecules throughout the pores of the matrix. The input parameters of the model were optimized for the Abydos site and the ROSINA CO/CO2 measured ratio is assumed to correspond to the bulk value in the nucleus. We find that all considered structures of water ice are able to reproduce the Ptolemy observation ...

  1. Soft x-ray spectroscopy of Ba24Ge100: electronic phase transition and Ba-atom rattling.

    Science.gov (United States)

    Rachi, Takeshi; Kitajima, Masaki; Kobayashi, Kensuke; Guo, FangZhun; Nakano, Takehito; Ikemoto, Yuka; Kobayashi, Keisuke; Tanigaki, Katsumi

    2005-08-15

    The electronic states of Ba24Ge100 are studied by soft x-ray photoelectron spectroscopy (XPS) at a high-energy photon factory. A large reduction in the density of states (DOS) at the Fermi level is clearly shown before and after the electronic phase transition at 200 K. The changes in the spectrum widths and the fine structures of the core-level Ba 4d spectra give a very reasonable indication of the Ba-atom rattlings in the clathrate polyhedra. On-resonance experiments using the excitation from Ba 3d to 4f levels display that the wave functions of Ba 5d and 6s orbitals give only a small contribution to make a Fermi surface through the hybridization with the Ge20 cluster orbitals. Importantly, reliable values of the DOS at the Fermi level NEF are successfully deduced, using two data sets of DOS obtained from high-resolution XPS and the total magnetic susceptibilities by a superconducting quantum interference device, to be 0.149 and 0.0427 states eV(-1) (Ge atom)(-1) for a high-temperature and for a low-temperature phase.

  2. Survey of solar thermal energy storage subsystems for thermal/electric applications

    Energy Technology Data Exchange (ETDEWEB)

    Segaser, C. L.

    1978-08-01

    A survey of the current technology and estimated costs of subsystems for storing the thermal energy produced by solar collectors is presented. The systems considered were capable of producing both electricity and space conditioning for three types of loads: a single-family detached residence, an apartment complex of 100 units, and a city of 30,000 residents, containing both single-family residences and apartments. Collector temperatures will be in four ranges: (1) 100 to 250/sup 0/F (used for space heating and single-cycle air conditioners and organic Rankine low-temperature turbines); (2) 300 to 400/sup 0/F (used for dual-cycle air conditioners and low-temperature turbines); (3) 400 to 600/sup 0/F (using fluids from parabolic trough collectors to run Rankine turbines); (4) 800 to 1000/sup 0/F (using fluids from heliostats to run closed-cycle gas turbines and steam Rankine turbines). The solar thermal energy subsystems will require from 60 to 36 x 10/sup 5/ kWhr (2.05 x 10/sup 5/ to 1.23 x 10/sup 10/ Btu) of thermal storage capacity. In addition to sensible heat and latent heat storage materials, several other media were investigated as potential thermal energy storage materials, including the clathrate and semiclathrate hydrates, various metal hydrides, and heat storage based on inorganic chemical reactions.

  3. Observation of Binding and Rotation of Methane and Hydrogen within a Functional Metal–Organic Framework

    KAUST Repository

    Savage, Mathew

    2016-07-27

    The key requirement for a portable store of natural gas is to maximize the amount of gas within the smallest possible space. The packing of methane (CH4) in a given storage medium at the highest possible density is, therefore, a highly desirable but challenging target. We report a microporous hydroxyl-decorated material, MFM-300(In) (MFM = Manchester Framework Material, replacing the NOTT designation), which displays a high volumetric uptake of 202 v/v at 298 K and 35 bar for CH4 and 488 v/v at 77 K and 20 bar for H2. Direct observation and quantification of the location, binding, and rotational modes of adsorbed CH4 and H2 molecules within this host have been achieved, using neutron diffraction and inelastic neutron scattering experiments, coupled with density functional theory (DFT) modeling. These complementary techniques reveal a very efficient packing of H2 and CH4 molecules within MFM-300(In), reminiscent of the condensed gas in pure component crystalline solids. We also report here, for the first time, the experimental observation of a direct binding interaction between adsorbed CH4 molecules and the hydroxyl groups within the pore of a material. This is different from the arrangement found in CH4/water clathrates, the CH4 store of nature.

  4. Soft functional polynuclear coordination compounds containing pyrimidine bridges

    Science.gov (United States)

    Navarro, Jorge A. R.; Barea, Elisa; Galindo, Miguel A.; Salas, Juan M.; Romero, M. Angustias; Quirós, Miguel; Masciocchi, Norberto; Galli, Simona; Sironi, Angelo; Lippert, Bernhard

    2005-08-01

    In this account, we describe the use of simple pyrimidine derivatives in combination with metal ions to build highly structured molecular architectures containing functional nanoenvironments, cavities and surfaces that can interact with additional species. The supramolecular structure of these systems can be rationally controlled by metal fragment geometry, reaction conditions and presence of templating agents. Thus, the use of transition metals with low coordination numbers or blocked bonding positions in combination with pyrimidines (e.g. 2-hydroxypyrimidine, 4-hydroxypyrimidine, 2,4-dihydroxypyrimidine, 2-aminopyrimidine) leads to the formation of either discrete assemblies, 1D polymers or helixes. When metal ions with higher coordination possibilities are applied instead, 2D and 3D networks are generated. Some of the assemblies built in this way possess functional cavities, pores and surfaces that can interact with additional species by means of hydrophobic, electrostatic, H-bonding interactions and coordinative bonds to give rise to recognition processes. The latter range from molecular recognition in homogeneous phase as well as clathrate formation, to heterogeneous solid-gas and solid-liquid adsorption phenomena. It should be noted that these materials are not rigid but able to undergo guest-induced reorganisation processes even in the solid state. Finally, some of these materials also combine additional interesting magneto-optical properties. Thus, dual systems can be envisaged in which two or more of these properties are present in the same material.

  5. Phononic Structure Engineering: the Realization of Einstein Rattling in Calcium Cobaltate for the Suppression of Thermal Conductivity.

    Science.gov (United States)

    Tian, Ruoming; Kearley, Gordon J; Yu, Dehong; Ling, Chris D; Pham, Anh; Embs, Jan P; Shoko, Elvis; Li, Sean

    2016-01-01

    Phonons in condensed matter materials transmit energy through atomic lattices as coherent vibrational waves. Like electronic and photonic properties, an improved understanding of phononic properties is essential for the development of functional materials, including thermoelectric materials. Recently, an Einstein rattling mode was found in thermoelectric material Na0.8CoO2, due to the large displacement of Na between the [CoO2] layers. In this work, we have realized a different type of rattler in another thermoelectric material Ca3Co4O9 by chemical doping, which possesses the same [CoO2] layer as Na0.8CoO2. It remarkably suppressed the thermal conductivity while enhancing its electrical conductivity. This new type of rattler was investigated by inelastic neutron scattering experiments in conjunction with ab-initio molecular dynamics simulations. We found that the large mass of dopant rather than the large displacement is responsible for such rattling in present study, which is fundamentally different from skutterudites, clathrates as well as Na analogue. We have also tentatively studied the phonon band structure of this material by DFT lattice dynamics simulation, showing the relative contribution to phonons in the distinct layers of Ca3Co4O9.

  6. A review of the hydrate based gas separation (HBGS) process for carbon dioxide pre-combustion capture

    International Nuclear Information System (INIS)

    In this work, a systematic review of the literature work done so far on the use of hydrate crystallization as a basis to develop data for the hydrate based gas separation (HBGS) process for the capture of CO2 from fuel gas mixtures is presented. Such a gas mixture may arise in integrated gasification combined cycle (IGCC) power plants. A thorough assessment of the thermodynamic, kinetic factors and economic aspects of the HBGS process and critical comments are presented. Compared with competing technologies, high CO2 capacity and the use of water as a solvent are key advantages for the HBGS process for CO2 capture. Furthermore, in this review, a snapshot of the current state-of-the-art is presented and further research and development opportunities and pathways for commercializing the HBGS process for pre-combustion capture of CO2 from IGCC power plants are discussed. - Highlights: • A review on a novel process to capture CO2 using water via clathrates is presented. • Hydrate based gas separation process (HBGS) for pre-combustion capture has much promise. • Current state-of-the-art on HBGS process and future directions are presented. • HBGS process is the most environmentally benign approach as water is used as a solvent

  7. Composition and structure of the shallow subsurface of Ceres revealed by crater morphology

    Science.gov (United States)

    Bland, Michael; Carol A. Raymond,; Paul Schenk,; Roger R. Fu,; Thomas Kneisl,; Jan Hendrick Pasckert,; Harold Hiesinger,; Frank Preusker,; Ryan S. Park,; Simone Marchi,; Scott King,; Julie C. Castillo-Rogez,; Christopher T. Russell,

    2016-01-01

    Before NASA’s Dawn mission, the dwarf planet Ceres was widely believed to contain a substantial ice-rich layer below its rocky surface. The existence of such a layer has significant implications for Ceres’s formation, evolution, and astrobiological potential. Ceres is warmer than icy worlds in the outer Solar System and, if its shallow subsurface is ice-rich, large impact craters are expected to be erased by viscous flow on short geologic timescales. Here we use digital terrain models derived from Dawn Framing Camera images to show that most of Ceres’s largest craters are several kilometres deep, and are therefore inconsistent with the existence of an ice-rich subsurface. We further show from numerical simulations that the absence of viscous relaxation over billion-year timescales implies a subsurface viscosity that is at least one thousand times greater than that of pure water ice. We conclude that Ceres’s shallow subsurface is no more than 30% to 40% ice by volume, with a mixture of rock, salts and/or clathrates accounting for the other 60% to 70%. However, several anomalously shallow craters are consistent with limited viscous relaxation and may indicate spatial variations in subsurface ice content.

  8. Hydration of amino acids: FTIR spectra and molecular dynamics studies.

    Science.gov (United States)

    Panuszko, Aneta; Adamczak, Beata; Czub, Jacek; Gojło, Emilia; Stangret, Janusz

    2015-11-01

    The hydration of selected amino acids, alanine, glycine, proline, valine, isoleucine and phenylalanine, has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure and the chemometric method have been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To support interpretation of obtained spectral results, molecular dynamics simulations of amino acids were performed. The structural-energetic characteristic of these solute-affected water molecules shows that, on average, water affected by amino acids forms stronger and shorter H-bonds than those in pure water. Differences in the influence of amino acids on water structure have been noticed. The effect of the hydrophobic side chain of an amino acid on the solvent interactions seems to be enhanced because of the specific cooperative coupling of water strong H-bond chain, connecting the carboxyl and amino groups, with the clathrate-like H-bond network surrounding the hydrocarbon side chain. The parameter derived from the spectral data, which corresponds to the contributions of the population of weak hydrogen bonds of water molecules which have been substituted by the stronger ones in the hydration sphere of amino acids, correlated well with the amino acid hydrophobicity indexes.

  9. NASA Tech Briefs, December 2003

    Science.gov (United States)

    2003-01-01

    Topics covered include: Organic/Inorganic Hybrid Polymer/Clay Nanocomposites; Less-Toxic Coatings for Inhibiting Corrosion of Aluminum; Liquid Coatings for Reducing Corrosion of Steel in Concrete; Processable Polyimides Containing APB and Reactive End Caps; Rod/Coil Block Copolyimides for Ion-Conducting Membranes; Techniques for Characterizing Microwave Printed Antennas; Cylindrical Antenna With Partly Adaptive Phased-Array Feed; Command Interface ASIC - Analog Interface ASIC Chip Set; Predicting Accumulations of Ice on Aerodynamic Surfaces; Analyzing Aeroelasticity in Turbomachines; Software for Allocating Resources in the Deep Space Network; Expert Seeker; High-Speed Recording of Test Data on Hard Disks; Functionally Graded Nanophase Beryllium/Carbon Composites; Thin Thermal-Insulation Blankets for Very High Temperatures; Aerostructures Test Wing; Flight-Test Evaluation of Flutter-Prediction Methods; Piezoelectrically Actuated Microvalve for Liquid Effluents; Larger-Stroke Piezoelectrically Actuated Microvalve; Innovative, High-Pressure, Cryogenic Control Valve: Short Face-to-Face, Reduced Cost; Safer Roadside Crash Walls Would Limit Deceleration; Improved Interactive Medical-Imaging System; Scanning Microscopes Using X Rays and Microchannels; Slotting Fins of Heat Exchangers to Provide Thermal Breaks; Methane Clathrate Hydrate Prospecting; Automated Monitoring with a BSP Fault-Detection Test; Automated Monitoring with a BCP Fault-Decision Test; Vector-Ordering Filter Procedure for Data Reduction; Remote Sensing and Information Technology for Large Farms; Developments at the Advanced Design Technologies Testbed; Spore-Forming Bacteria that Resist Sterilization; and Acoustical Applications of the HHT Method.

  10. Thermoelectric transport in rare-earth compounds

    International Nuclear Information System (INIS)

    This work focuses on the thermoelectric transport in rare-earth compounds. The measurements of the thermal conductivity, thermopower, and Nernst coefficient are supplemented by investigations of other quantities as magnetic susceptibility and specific heat. Chapter 2 provides an introduction to the relevant physical concepts. Section 1 of that chapter summarizes the characteristic properties of rare-earth systems; section 2 gives an overview on thermoelectric transport processes in magnetic fields. The applied experimental techniques as well as the new experimental setup are described in detail in Chapter 3. The experimental results are presented in Chapter 4-6, of which each concentrates on a different subject. In Chapter 4, various Eu clathrates and the skutterudite-like Ce3Rh4Sn13 are presented, which have been investigated as potential thermoelectric materials for applications. Chapter 5 focusses on the study of the energy scales in the heavy-fermion series Lu1-xYbxRh2Si2 and CexLa1-xNi2Ge2 by means of thermopower investigations. Chapter 6 is dedicated to the thermoelectric transport properties of the correlated semimetal CeNiSn with special emphasis on the Nernst coefficient of this compound. (orig.)

  11. Synthesis, X-Ray Structure, and Characterization of a Complex Containing the Hexakis(ureacobalt(II Cation and Lattice Urea Molecules

    Directory of Open Access Journals (Sweden)

    Labrini Drakopoulou

    2007-01-01

    Full Text Available The 12: 1 reaction of urea (U with CoI2 in EtOH yielded the “clathrate-coordination” compound [CoU6]I2·4U (1. The complex crystallizes in the monoclinic space group P21/c. The lattice constants are a = 9.844(4, b = 7.268(3, c = 24.12(1 Å, and β=98.12(1∘. The crystal structure determination demonstrates the existence of octahedral [CoU6]2+ cations, I- counterions, and two different types (two U1 and two U2 of hydrogen-bonded, lattice urea molecules. The [CoU6]2+ cations and the U1 lattice molecules form two-dimensional hydrogen-bonded layers which are parallel to the ab plane. The I- anions are placed above and below each layer, and are hydrogen bonded both to U1 molecules and [CoU6]2+ cations. Each U2 molecule is connected to a [CoU6]2+ cation through an N–H⋯O hydrogen bond resulting in a three-dimensional network. Room temperature magnetic susceptibility and spectroscopic (solid-state UV/Vis, IR, Raman data of 1 are discussed in terms of the nature of bonding and the known structure.

  12. A consistent and verifiable macroscopic model for the dissolution of liquid CO2 in water under hydrate forming conditions

    International Nuclear Information System (INIS)

    Direct injection of liquid CO2 into the ocean has been proposed as one method to reduce the emission levels of CO2 into the atmosphere. When liquid CO2 is injected (normally as droplets) at ocean depths >500 m, a solid interfacial region between the CO2 and the water is observed to form. This region consists of hydrate clathrates and hinders the rate of dissolution of CO2. It is, therefore, expected to have a significant impact on the injection of liquid CO2 into the ocean. Up until now, no consistent and predictive model for the shrinking of droplets of CO2 under hydrate forming conditions has been proposed. This is because all models proposed to date have had too many unknowns. By computing rates of the physical and chemical processes in hydrates via molecular dynamics simulations, we have been able to determine independently some of these unknowns. We then propose the most reasonable model and use it to make independent predictions of the rates of mass transfer and thickness of the hydrate region. These predictions are compared to measurements, and implications to the rates of shrinkage of CO2 droplets under varying flow conditions are discussed. (author)

  13. Trend for Thermoelectric Materials and Their Earth Abundance

    Science.gov (United States)

    Amatya, R.; Ram, R. J.

    2012-06-01

    The low crustal abundance of materials such as tellurium (Te) (0.001 ppm by weight), antimony (Sb) (0.2 ppm), and germanium (Ge) (1.4 ppm) contributes to their price volatility as applications (competing with thermoelectrics) continue to grow, for example, cadmium telluride photovoltaics, antimony-lead alloy for batteries, and Ge for fiber optics and infrared optical technologies. Previous consideration of material scarcity has focused on Te-based thermoelectrics. Here, we broaden the analysis to include recent high-figure-of-merit ( ZT) materials such as skutterudites, Zintl phase compounds, and clathrates that employ Sb, ytterbium (2.8 ppm), and Ge. The maximum demonstrated ZT for each particular alloy exhibits an empirical dependence on the crustal abundance, A, such that ZT = A - b , where b is in the range from 0.05 to 0.10. This analysis shows that no material with crustal abundance of 30 ppm (~4 × 1018 metric tons) has ZT greater than 0.8.

  14. Dynamical delivery of volatiles to the outer main belt

    Science.gov (United States)

    Grazier, Kevin R.; Castillo-Rogez, Julie C.; Sharp, Philip W.

    2014-04-01

    We quantify the relative contribution of volatiles supplied from outer Solar System planetesimal reservoirs to large wet asteroids during the first few My after the beginning of the Solar System. To that end, we simulate the fate of planetesimals originating within different regions of the Solar System - and thus characterized by different chemical inventories - using a highly accurate integrator tuned to handle close planet/planetesimal encounters. The fraction of icy planetesimals crossing the Asteroid Belt was relatively significant, and our simulations show that planetesimals originating from the Jupiter/Saturn region were orders of magnitude more abundant than those stemming from the Uranus and Neptune regions when the planets were just embryos. As the planets reached their full masses the Jupiter/Saturn and Saturn/Uranus regions contributed similar fractions of planetesimals for any material remaining in these reservoirs late in the stage of planetary formation, This implies that large asteroids like Ceres accreted very little material enriched in low-eutectic volatiles (e.g., methanol, nitrogen and methane ices, etc.) and clathrate hydrates expected to condense at the very low temperatures predicted for beyond Saturn’s orbit in current early solar nebula models. Further, a large fraction of the content in organics of Ceres and neighboring ice-rich objects originates from the outer Solar System.

  15. Compositions of Oceans on Icy Solar System Bodies (Invited)

    Science.gov (United States)

    Zolotov, M. Y.

    2010-12-01

    Interior oceans may exist on at least several solar system bodies: Europa, Enceladus, Ganymede, Titan and Triton. Compositions of the oceans could reflect bulk chemistries on the bodies, degree and timing of differendentition, current temperature and pressure conditions, and chemical exchanges between icy shells, liquid layers, and suboceanic solids (rocks, sediments, ices and clathrates). Observational signs are sparse and modeling is the major approach to evaluate oceanic compositions. On Europa, a presence of S(VI) species and CO2 at endogenic surface features [1] suggests sulfates and C species (organic and/or inorganic) in the ocean. The detection of NaCl and Na2CO3/NaHCO3-bearing grains emitted from Enceladus [2] implies the dominance of Na, Cl and carbonate/bicarbonate ions in the past and/or present alkaline fluids in the interior. These observations are consistent with independent models for water-rock interaction [3]. Evaluated low contents of other elements (Mg, Fe, Ca, K, S, P, etc.) in initial oceanic waters [3] are accounted for by low solubilities of minerals deposited from water solutions (serpentine, saponite, magnetite, carbonates, sulfides and phosphates). Oceanic redox states are affected by the composition of accreted ices and rocks, hydrogen production through oxidation of solids (mainly Fe-Ni metal) by water and an efficiency of H2 escape. Formation of a sulfate-bearing ocean (as on Europa) through oxidation of sulfides could have been driven by radiolytically-formed oxidants (H2O2, O2), high-temperature (>500 K) hydrothermal activity and H2 escape. Formation of sulfate facilitates leaching of Mg from minerals leading to the Mg-SO4-Na-Cl ocean. Although some of these factors could have played roles on the Galilean satellites, formation of sulfate-bearing oceans beyond Jupiter is unlikely. Accretion of cometary-type ices on moons allows an existence of water-methanol-ammonia liquids at ~153 K, although ammonia could have been sequestered in

  16. Inferred gas hydrate and permafrost stability history models linked to climate change in the Beaufort-Mackenzie Basin, Arctic Canada

    Directory of Open Access Journals (Sweden)

    J. Majorowicz

    2012-03-01

    Full Text Available Atmospheric methane from episodic gas hydrate (GH destabilization, the "clathrate gun" hypothesis, is proposed to affect past climates, possibly since the Phanerozoic began or earlier. In the terrestrial Beaufort-Mackenzie Basin (BMB, GHs occur commonly below thick ice-bearing permafrost (IBP, but they are rare within it. Two end-member GH models, where gas is either trapped conventionally (Case 1 or where it is trapped dynamically by GH formation (Case 2, were simulated using profile (1-D models and a 14 Myr ground surface temperature (GST history based on marine isotopic data, adjusted to the study setting, constrained by deep heat flow, sedimentary succession conductivity, and observed IBP and Type I GH contacts in Mallik wells. Models consider latent heat effects throughout the IBP and GH intervals. Case 1 GHs formed at ~0.9 km depth only ~1 Myr ago by in situ transformation of conventionally trapped natural gas. Case 2 GHs begin to form at ~290–300 m ~6 Myr ago in the absence of lithological migration barriers. During glacial intervals Case 2 GH layers expand both downward and upward as the permafrost grows downward through and intercalated with GHs. The distinctive model results suggest that most BMB GHs resemble Case 1 models, based on the observed distinct and separate occurrences of GHs and IBP and the lack of observed GH intercalations in IBP. Case 2 GHs formed >255 m, below a persistent ice-filled permafrost layer that is as effective a seal to upward methane migration as are Case 1 lithological seals. All models respond to GST variations, but in a delayed and muted manner such that GH layers continue to grow even as the GST begins to increase. The models show that the GH stability zone history is buffered strongly by IBP during the interglacials. Thick IBP and GHs could have persisted since ~1.0 Myr ago and ~4.0 Myr ago for Cases 1 and 2, respectively. Offshore BMB IBP and GHs formed terrestrially during Pleistocene sea level low

  17. Carbon dioxide on the satellites of Saturn: Results from the Cassini VIMS investigation and revisions to the VIMS wavelength scale

    Science.gov (United States)

    Cruikshank, D.P.; Meyer, A.W.; Brown, R.H.; Clark, R.N.; Jaumann, R.; Stephan, K.; Hibbitts, C.A.; Sandford, S.A.; Mastrapa, R.M.E.; Filacchione, G.; Ore, C.M.D.; Nicholson, P.D.; Buratti, B.J.; McCord, T.B.; Nelson, R.M.; Dalton, J.B.; Baines, K.H.; Matson, D.L.

    2010-01-01

    Several of the icy satellites of Saturn show the spectroscopic signature of the asymmetric stretching mode of C-O in carbon dioxide (CO2) at or near the nominal solid-phase laboratory wavelength of 4.2675 ??m (2343.3 cm-1), discovered with the Visible-Infrared Mapping Spectrometer (VIMS) on the Cassini spacecraft. We report here on an analysis of the variation in wavelength and width of the CO2 absorption band in the spectra of Phoebe, Iapetus, Hyperion, and Dione. Comparisons are made to laboratory spectra of pure CO2, CO2 clathrates, ternary mixtures of CO2 with other volatiles, implanted and adsorbed CO2 in non-volatile materials, and ab initio theoretical calculations of CO2 * nH2O. At the wavelength resolution of VIMS, the CO2 on Phoebe is indistinguishable from pure CO2 ice (each molecule's nearby neighbors are also CO2) or type II clathrate of CO2 in H2O. In contrast, the CO2 band on Iapetus, Hyperion, and Dione is shifted to shorter wavelengths (typically ???4.255 ??m (???2350.2 cm-1)) and broadened. These wavelengths are characteristic of complexes of CO2 with different near-neighbor molecules that are encountered in other volatile mixtures such as with H2O and CH3OH, and non-volatile host materials like silicates, some clays, and zeolites. We suggest that Phoebe's CO2 is native to the body as part of the initial inventory of condensates and now exposed on the surface, while CO2 on the other three satellites results at least in part from particle or UV irradiation of native H2O plus a source of C, implantation or accretion from external sources, or redistribution of native CO2 from the interior. The analysis presented here depends on an accurate VIMS wavelength scale. In preparation for this work, the baseline wavelength calibration for the Cassini VIMS was found to be distorted around 4.3 ??m, apparently as a consequence of telluric CO2 gas absorption in the pre-launch calibration. The effect can be reproduced by convolving a sequence of model detector

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

    Science.gov (United States)

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

    2004-01-01

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

  19. Big Impacts and Transient Oceans on Titan

    Science.gov (United States)

    Zahnle, K. J.; Korycansky, D. G.; Nixon, C. A.

    2014-01-01

    We have studied the thermal consequences of very big impacts on Titan [1]. Titan's thick atmosphere and volatile-rich surface cause it to respond to big impacts in a somewhat Earth-like manner. Here we construct a simple globally-averaged model that tracks the flow of energy through the environment in the weeks, years, and millenia after a big comet strikes Titan. The model Titan is endowed with 1.4 bars of N2 and 0.07 bars of CH4, methane lakes, a water ice crust, and enough methane underground to saturate the regolith to the surface. We assume that half of the impact energy is immediately available to the atmosphere and surface while the other half is buried at the site of the crater and is unavailable on time scales of interest. The atmosphere and surface are treated as isothermal. We make the simplifying assumptions that the crust is everywhere as methane saturated as it was at the Huygens landing site, that the concentration of methane in the regolith is the same as it is at the surface, and that the crust is made of water ice. Heat flow into and out of the crust is approximated by step-functions. If the impact is great enough, ice melts. The meltwater oceans cool to the atmosphere conductively through an ice lid while at the base melting their way into the interior, driven down in part through Rayleigh-Taylor instabilities between the dense water and the warm ice. Topography, CO2, and hydrocarbons other than methane are ignored. Methane and ethane clathrate hydrates are discussed quantitatively but not fully incorporated into the model.

  20. Eocene climate and Arctic paleobathymetry: A tectonic sensitivity study using GISS ModelE-R

    Science.gov (United States)

    Roberts, C. D.; Legrande, A. N.; Tripati, A. K.

    2009-12-01

    The early Paleogene (65-45 million years ago, Ma) was a ‘greenhouse’ interval with global temperatures warmer than any other time in the last 65 Ma. This period was characterized by high levels of CO2, warm high-latitudes, warm surface-and-deep oceans, and an intensified hydrological cycle. Sediments from the Arctic suggest that the Eocene surface Arctic Ocean was warm, brackish, and episodically enabled the freshwater fern Azolla to bloom. The precise mechanisms responsible for the development of these conditions remain uncertain. We present equilibrium climate conditions derived from a fully-coupled, water-isotope enabled, general circulation model (GISS ModelE-R) configured for the early Eocene. We also present model-data comparison plots for key climatic variables (SST and δ18O) and analyses of the leading modes of variability in the tropical Pacific and North Atlantic regions. Our tectonic sensitivity study indicates that Northern Hemisphere climate would have been very sensitive to the degree of oceanic exchange through the seaways connecting the Arctic to the Atlantic and Tethys. By restricting these seaways, we simulate freshening of the surface Arctic Ocean to ~6 psu and warming of sea-surface temperatures by 2°C in the North Atlantic and 5-10°C in the Labrador Sea. Our results may help explain the occurrence of low-salinity tolerant taxa in the Arctic Ocean during the Eocene and provide a mechanism for enhanced warmth in the north western Atlantic. We also suggest that the formation of a volcanic land-bridge between Greenland and Europe could have caused increased ocean convection and warming of intermediate waters in the Atlantic. If true, this result is consistent with the theory that bathymetry changes may have caused thermal destabilisation of methane clathrates in the Atlantic.

  1. Climate sensitivity to Arctic seaway restriction during the early Paleogene

    Science.gov (United States)

    Roberts, Christopher D.; LeGrande, Allegra N.; Tripati, Aradhna K.

    2009-09-01

    The opening and closing of ocean gateways affects the global distribution of heat, salt, and moisture, potentially driving climatic change on regional to global scales. Between 65 and 45 million years ago (Ma), during the early Paleogene, exchange between the Arctic and global oceans occurred through two narrow and shallow seaways, the Greenland-Norway seaway and the Turgai Strait. Sediments from the Arctic Ocean suggest that, during this interval, the surface ocean was warm, brackish, and episodically enabled the freshwater fern Azolla to bloom. The precise mechanisms responsible for the development of these conditions in the Paleogene Arctic remain uncertain. Here we show results from an isotope-enabled, atmosphere-ocean general circulation model, which indicate that Northern Hemisphere climate would have been very sensitive to the degree of oceanic exchange through the Arctic seaways. We also present modelled estimates of seawater and calcite δ18O for the Paleogene. By restricting these seaways, we simulate freshening of the surface Arctic Ocean to ~ 6 psu and warming of sea-surface temperatures by 2 °C in the North Atlantic and 5-10 °C in the Labrador Sea. Our results may help explain the occurrence of low-salinity tolerant taxa in the Arctic Ocean during the Eocene and provide a mechanism for enhanced warmth in the north western Atlantic. We propose that the formation of a volcanic land-bridge between Greenland and Europe could have caused increased ocean convection and warming of intermediate waters in the Atlantic. If true, this result is consistent with the theory that bathymetry changes may have caused thermal destabilisation of methane clathrates and supports a tectonic trigger hypothesis for the Paleocene Eocene Thermal Maximum (PETM).

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

    Science.gov (United States)

    Brown, Erika P; Koh, Carolyn A

    2016-01-01

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

  3. Diffuse neutron scattering studies of proton ordering in ice Ih at different pressures

    International Nuclear Information System (INIS)

    Complete text of publication follows. A series of diffuse neutron scattering measurements from D2O single crystal ice Ih at different pressures were made on Prisma using the standard He pressuriser at ISIS. The measurements show that there is no clear change to the diffuse scattering pattern for pressures up to 2.8 kbar at 230 K. The pressure of 2.8 kbar is also well above the necessary pressure required for the formation of ice II at this temperature (which is 2.2 kbar). Hence the structure of the crystal appears to be stabilised by the presence of He gas which may occupy the centre cavities of the ice structure. However, when the pressure increases to 3.1 kbar at 120 K, the structure of ice Ih starts to deform, firstly the d-spacing of Bragg reflections in the direction of (hh0) increases, for instance, the (220) peak increases from 2.245 to 2.256 A (instead of a decrease under such high pressure) and the transition is completed at temperature of 180 K (i.e. the 2.245 A component completely disappears). More interestingly, all Bragg peaks were disappeared when the temperature increases to 200 K although the background remained the same, after searching for Bragg reflections without success and from examination of the sample, we believe that the sample transformed to a clathrate structure. The lack of diffraction rings indicates the sample to be single crystalline but in a considerably different orientation. (author)

  4. Dynamics of H2 adsorbed in porous materials as revealed by computational analysis of inelastic neutron scattering spectra.

    Science.gov (United States)

    Pham, Tony; Forrest, Katherine A; Space, Brian; Eckert, Juergen

    2016-06-29

    The inelastic scattering of neutrons from adsorbed H2 is an effective and highly sensitive method for obtaining molecular level information on the type and nature of H2 binding sites in porous materials. While these inelastic neutron scattering (INS) spectra of the hindered rotational and translational excitations on the adsorbed H2 contain a significant amount of information, much of this can only be reliably extracted by means of a detailed analysis of the spectra through the utilization of models and theoretical calculations. For instance, the rotational tunneling transitions observed in the INS spectra can be related to a value for the barrier to rotation for the adsorbed H2 with the use of a simple phenomenological model. Since such an analysis is dependent on the model, it is far more desirable to use theoretical methods to compute a potential energy surface (PES), from which the rotational barriers for H2 adsorbed at a particular site can be determined. Rotational energy levels and transitions for the hindered rotor can be obtained by quantum dynamics calculations and compared directly with experiment with an accuracy subject only to the quality of the theoretical PES. In this paper, we review some of the quantum and classical mechanical calculations that have been performed on H2 adsorbed in various porous materials, such as clathrate hydrates, zeolites, and metal-organic frameworks (MOFs). The principal aims of these calculations have been the interpretation of the INS spectra for adsorbed H2 along with the extraction of atomic level details of its interaction with the host. We describe calculations of the PES used for two-dimensional quantum rotation as well as rigorous five-dimensional quantum coupled translation-rotation dynamics, and demonstrate that the combination of INS measurements and computational modeling can provide important and detailed insights into the molecular mechanism of H2 adsorption in porous materials. PMID:27160665

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

    Science.gov (United States)

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

    2004-01-01

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

  6. Thermodynamic stability and crystallization behavior of molecular complexes with TEP host

    Science.gov (United States)

    Fijiwara, Atsushi; Kitamura, Mitsutaka

    2013-06-01

    In the crystallization of molecular complex (co-crystal, clathrate complex), polymorphism in regard to the host structure frequently appears. Previously, we studied the release process of the biocide, CMI (5-chloro-2-methyl-4-isothiazolin-3-one) from the molecular complex with TEP (1,1,2,2-tetrakis(4-hydroxyphenyl)ethane) (TEP·2CMI) in methanol-water mixed solvents. It was clear that the release process of the biocide (CMI) is composed of the transformation from the TEP·2CMI crystal to a more stable molecular complex crystal with solvent. In this work, the crystallization was performed in the methanol solutions including TEP and CMI at constant temperature (298 K and 308 K). It appeared that two kinds of TEP molecular complexes (TEP·2CMI and TEP·2MeOH) crystallize competitively. The crystallization zone of each molecular complex was shown in the map using the coordinates of initial concentrations of TEP and CMI. In the boundary zone both molecular complexes appeared and the transformation from TEP·2CMI to TEP·2MeOH was observed, indicating that the stable form is TEP·2MeOH. Without the boundary zone the corresponding stable form crystallized in each zone. The value of the initial concentration ratio of CMI/TEP for the selective crystallization of TEP·2CMI was higher at 298 K (1.54) than that (1.36) at 308 K. The equilibrium concentrations of TEP and CMI in the presence of two molecular complexes were expressed using the dissociation constants of the molecular complexes and it was indicated that the dissociation of TEP·2CMI highly increases with temperature

  7. Integrative taxonomy and molecular phylogeny of genus Aplysina (Demospongiae: Verongida from Mexican Pacific.

    Directory of Open Access Journals (Sweden)

    José Antonio Cruz-Barraza

    Full Text Available Integrative taxonomy provides a major approximation to species delimitation based on integration of different perspectives (e.g. morphology, biochemistry and DNA sequences. The aim of this study was to assess the relationships and boundaries among Eastern Pacific Aplysina species using morphological, biochemical and molecular data. For this, a collection of sponges of the genus Aplysina from the Mexican Pacific was studied on the basis of their morphological, chemical (chitin composition, and molecular markers (mitochondrial COI and nuclear ribosomal rDNA: ITS1-5.8-ITS2. Three morphological species were identified, two of which are new to science. A. clathrata sp. nov. is a yellow to yellow-reddish or -brownish sponge, characterized by external clathrate-like morphology; A. revillagigedi sp. nov. is a lemon yellow to green, cushion-shaped sometimes lobate sponge, characterized by conspicuous oscules, which are slightly elevated and usually linearly distributed on rims; and A. gerardogreeni a known species distributed along the Mexican Pacific coast. Chitin was identified as the main structural component within skeletons of the three species using FTIR, confirming that it is shared among Verongida sponges. Morphological differences were confirmed by DNA sequences from nuclear ITS1-5.8-ITS2. Mitochondrial COI sequences showed extremely low but diagnostic variability for Aplysina revillagigedi sp. nov., thus our results corroborate that COI has limited power for DNA-barcoding of sponges and should be complemented with other markers (e.g. rDNA. Phylogenetic analyses of Aplysina sequences from the Eastern Pacific and Caribbean, resolved two allopatric and reciprocally monophyletic groups for each region. Eastern Pacific species were grouped in general accordance with the taxonomic hypothesis based on morphological characters. An identification key of Eastern Pacific Aplysina species is presented. Our results constitute one of the first approximations

  8. Europa's Crust and Ocean: Origin, Composition, and the Prospects for Life

    Science.gov (United States)

    Kargel, J.S.; Kaye, J.Z.; Head, J. W.; Marion, G.M.; Sassen, R.; Crowley, J.K.; Ballesteros, O.P.; Grant, S.A.; Hogenboom, D.L.

    2000-01-01

    We have considered a wide array of scenarios for Europa's chemical evolution in an attempt to explain the presence of ice and hydrated materials on its surface and to understand the physical and chemical nature of any ocean that may lie below. We postulate that, following formation of the jovian system, the europan evolutionary sequence has as its major links: (a) initial carbonaceous chondrite rock, (b) global primordial aqueous differentiation and formation of an impure primordial hydrous crust, (c) brine evolution and intracrustal differentiation, (d) degassing of Europa's mantle and gas venting, (e) hydrothermal processes, and (f) chemical surface alteration. Our models were developed in the context of constraints provided by Galileo imaging, near infrared reflectance spectroscopy, and gravity and magnetometer data. Low-temperature aqueous differentiation from a carbonaceous CI or CM chondrite precursor, without further chemical processing, would result in a crust/ocean enriched in magnesium sulfate and sodium sulfate, consistent with Galileo spectroscopy. Within the bounds of this simple model, a wide range of possible layered structures may result; the final state depends on the details of intracrustal differentiation. Devolatilization of the rocky mantle and hydrothermal brine reactions could have produced very different ocean/crust compositions, e.g., an ocean/crust of sodium carbonate or sulfuric acid, or a crust containing abundant clathrate hydrates. Realistic chemical-physical evolution scenarios differ greatly in detailed predictions, but they generally call for a highly impure and chemically layered crust. Some of these models could lead also to lateral chemical heterogeneities by diapiric upwellings and/or cryovolcanism. We describe some plausible geological consequences of the physical-chemical structures predicted from these scenarios. These predicted consequences and observed aspects of Europa's geology may serve as a basis for further analys is

  9. Methane and nitrous oxide in the ice core record.

    Science.gov (United States)

    Wolff, Eric; Spahni, Renato

    2007-07-15

    Polar ice cores contain, in trapped air bubbles, an archive of the concentrations of stable atmospheric gases. Of the major non-CO2 greenhouse gases, methane is measured quite routinely, while nitrous oxide is more challenging, with some artefacts occurring in the ice and so far limited interpretation. In the recent past, the ice cores provide the only direct measure of the changes that have occurred during the industrial period; they show that the current concentration of methane in the atmosphere is far outside the range experienced in the last 650,000 years; nitrous oxide is also elevated above its natural levels. There is controversy about whether changes in the pre-industrial Holocene are natural or anthropogenic in origin. Changes in wetland emissions are generally cited as the main cause of the large glacial-interglacial change in methane. However, changing sinks must also be considered, and the impact of possible newly described sources evaluated. Recent isotopic data appear to finally rule out any major impact of clathrate releases on methane at these time-scales. Any explanation must take into account that, at the rapid Dansgaard-Oeschger warmings of the last glacial period, methane rose by around half its glacial-interglacial range in only a few decades. The recent EPICA Dome C (Antarctica) record shows that methane tracked climate over the last 650,000 years, with lower methane concentrations in glacials than interglacials, and lower concentrations in cooler interglacials than in warmer ones. Nitrous oxide also shows Dansgaard-Oeschger and glacial-interglacial periodicity, but the pattern is less clear.

  10. Macroscopic investigation of hydrate film growth at the hydrocarbon/water interface

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, C.J.; Miller, K.T.; Koh, C.A.; Sloan, E.D. [Colorado School of Mines, Golden, CO (United States). Dept. of Chemical Engineering

    2008-07-01

    Clathrate hydrates are ice-like crystalline compounds that form as thin porous crystalline films at the interface between the water phase and the hydrocarbon guest molecule phase. The growth characteristics of these hydrate films are important in seafloor carbon dioxide sequestration, gas hydrate transport, and flow assurance in oil and gas pipelines. This paper presented a study that employed digital video microscopy to investigate the hydrate film thickness as a function of time, as well as the propagation rate for methane and cyclopentane hydrate. The purpose of the study was to enhance past measurements of hydrate film growth by incorporating gas consumption measurements simultaneously with film thickness measurements to determine which phase supplied the hydrate former during hydrate formation. The study also advanced the physical knowledge of hydrate formation by relating film formation with the water droplet to hydrate shell conversion. The paper included a schematic of the hydrate film growth apparatus and image acquisition and analysis as well as an illustration of the nucleation of a water droplet immersed in cyclopentane. The results were presented for cyclopentane hydrate film growth; methane hydrate film growth; film growth in an oil/methane/ water system; film growth/development into water phase; and gas consumption for hydrate film growth. The paper also discussed the source of methane for hydrate formation; solubility of methane in water; growth rates; proposed mechanism of hydrate film growth at the hydrocarbon/water interface; and, transferability between hydrate formation for a pool of liquid versus a water droplet. It was concluded that gas consumption data during hydrate formation presented evidence of an aqueous phase supply of hydrate former to the initial hydrate growth, followed by a vapor phase supply of hydrate former in the thickening stage of hydrate film formation. 25 refs., 18 figs.,.

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

    Science.gov (United States)

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

    2014-12-01

    Interfacial interactions between liquid-solid and solid-solid phases/surfaces are of fundamental importance to the formation of hydrate deposits in oil and gas pipelines. This work establishes the effect of five categories of physical and chemical modification to steel on clathrate hydrate adhesive force: oleamide, graphite, citric acid ester, nonanedithiol, and Rain-X anti-wetting agent. Hydrate adhesive forces were measured using a micromechanical force apparatus, under both dry and water-wet surface conditions. The results show that the graphite coating reduced hydrate-steel adhesion force by 79%, due to an increase in the water wetting angle from 42 ± 8° to 154 ± 7°. Two chemical surface coatings (nonanedithiol and the citric acid ester) induced rapid hydrate growth in the hydrate particles; nonanedithiol increased hydrate adhesive force by 49% from the baseline, while the citric acid ester coating reduced hydrate adhesion force by 98%. This result suggests that crystal growth may enable a strong adhesive pathway between hydrate and other crystalline structures, however this effect may be negated in cases where water-hydrocarbon interfacial tension is minimised. When a liquid water droplet was placed on the modified steel surfaces, the graphite and citric acid ester became less effective at reducing adhesive force. In pipelines containing a free water phase wetting the steel surface, chemical or physical surface modifications alone may be insufficient to eliminate hydrate deposition risk. In further tests, the citric acid ester reduced hydrate cohesive forces by 50%, suggesting mild activity as a hybrid anti-agglomerant suppressing both hydrate deposition and particle agglomeration. These results demonstrate a new capability to develop polyfunctional surfactants, which simultaneously limit the capability for hydrate particles to aggregate and deposit on the pipeline wall. PMID:25332072

  12. RECENT ADVANCES IN HYDRATE-BASED TECHNOLOGIES FOR NATURAL GAS STORAGE--A REVIEW

    Institute of Scientific and Technical Information of China (English)

    Yasuhiko H. Mori

    2003-01-01

    Interest in the possibility of storing and transporting natural gas in the form of clathrate hydrates has been increasing in recent years, particularly in some gas-importing and exporting countries.The technologies necessary for realizing this possibility may be classified into those relevant to the four serial processes (a) the formation of a hydrate, (b) the processing (dewatering, pelletizing, etc. ) of the formed hydrate, (c) the storage and transportation of the processed hydrate, and (d) the regasification (dissociation) of the hydrate. The technological development of any of these processes is still at an early stage. For hydrate formation, for example, various rival operations have been proposed. However,many of them have never been subjected to actual tests for practical use. More efforts are required for examining the different hydrate-formation technologies and for rating them by comparison. The general design of the processing of the formed hydrate inevitably depends on both the hydrate-formation process and the storage/transportation process, hence it has a wide variability. The major uncertainty in the storage-process design lies in the as-yet unclarified utility of the "self-preservation" effect of the naturalgas hydrates. The process design as well as the relevant cost evaluation should strongly depend on whether the hydrates are well preserved at atmospheric pressure in large-scale storage facilities. The regasification process has been studied less extensively than the former processes. The state of the art of the technological development in each of the serial processes is reviewed, placing emphasis on the hydrate formation process.

  13. NMR investigations of surfaces and interfaces using spin-polarized xenon

    International Nuclear Information System (INIS)

    129Xe NMR is potentially useful for the investigation of material surfaces, but has been limited to high surface area samples in which sufficient xenon can be loaded to achieve acceptable signal to noise ratios. In Chapter 2 conventional 129Xe NMR is used to study a high surface area polymer, a catalyst, and a confined liquid crystal to determine the topology of these systems. Further information about the spatial proximity of different sites of the catalyst and liquid crystal systems is determined through two dimensional exchange NMR in Chapter 3. Lower surface area systems may be investigated with spin-polarized xenon, which may be achieved through optical pumping and spin exchange. Optically polarized xenon can be up to 105 times more sensitive than thermally polarized xenon. In Chapter 4 highly polarized xenon is used to examine the surface of poly(acrylonitrile) and the formation of xenon clathrate hydrates. An attractive use of polarized xenon is as a magnetization source in cross polarization experiments. Cross polarization from adsorbed polarized xenon may allow detection of surface nuclei with drastic enhancements. A non-selective low field thermal mixing technique is used to enhance the 13C signal of CO2 of xenon occluded in solid CO2 by a factor of 200. High-field cross polarization from xenon to proton on the surface of high surface area polymers has enabled signal enhancements of ∼1,000. These studies, together with investigations of the efficiency of the cross polarization process from polarized xenon, are discussed in Chapter 5. Another use of polarized xenon is as an imaging contrast agent in systems that are not compatible with traditional contrast agents. The resolution attainable with this method is determined through images of structured phantoms in Chapter 6

  14. Role of megafauna and frozen soil in the atmospheric CH4 dynamics.

    Directory of Open Access Journals (Sweden)

    Sergey Zimov

    Full Text Available Modern wetlands are the world's strongest methane source. But what was the role of this source in the past? An analysis of global 14C data for basal peat combined with modelling of wetland succession allowed us to reconstruct the dynamics of global wetland methane emission through time. These data show that the rise of atmospheric methane concentrations during the Pleistocene-Holocene transition was not connected with wetland expansion, but rather started substantially later, only 9 thousand years ago. Additionally, wetland expansion took place against the background of a decline in atmospheric methane concentration. The isotopic composition of methane varies according to source. Owing to ice sheet drilling programs past dynamics of atmospheric methane isotopic composition is now known. For example over the course of Pleistocene-Holocene transition atmospheric methane became depleted in the deuterium isotope, which indicated that the rise in methane concentrations was not connected with activation of the deuterium-rich gas clathrates. Modelling of the budget of the atmospheric methane and its isotopic composition allowed us to reconstruct the dynamics of all main methane sources. For the late Pleistocene, the largest methane source was megaherbivores, whose total biomass is estimated to have exceeded that of present-day humans and domestic animals. This corresponds with our independent estimates of herbivore density on the pastures of the late Pleistocene based on herbivore skeleton density in the permafrost. During deglaciation, the largest methane emissions originated from degrading frozen soils of the mammoth steppe biome. Methane from this source is unique, as it is depleted of all isotopes. We estimated that over the entire course of deglaciation (15,000 to 6,000 year before present, soils of the mammoth steppe released 300-550 Pg (10(15 g of methane. From current study we conclude that the Late Quaternary Extinction significantly affected

  15. Evidence for Global Biogeochemical Changes During the Toarcian Oceanic Anoxic Event

    Science.gov (United States)

    Them, T. R., II; Gill, B. C.; Gröcke, D. R.; Selby, D. S.; Martindale, R. C.; Caruthers, A. H.; Tulsky, E. T. T.

    2015-12-01

    The global versus regional nature of the Toarcian Oceanic Anoxic Event (T-OAE; ~183 million years ago) has been heavily debated over the course of the last decade. Several lines of geochemical evidence support a significant perturbation to the carbon cycle and redox-sensitive elemental cycles across this interval. It is thought that these represent feedbacks to the emplacement of the Karoo-Ferrar large igneous province. These include: elevated atmospheric pCO2, an enhanced greenhouse effect and hydrologic cycle leading to increased weathering rates, dissociation of biogenic methane clathrates, and widespread ocean anoxia. Despite evidence for these global phenomena, the overwhelming majority of stratigraphic successions studied are located in Europe. The global magnitude of these biogeochemical perturbations has been challenged, with some considering that this event was regional to Europe, and others suggesting that the carbon isotope excursion (CIE) itself is not a reliable stratigraphic marker. In order to test these competing hypotheses, we have generated a geochemical dataset to reconstruct paleoceanographic and paleoclimatological changes across the T-OAE from western North America. The Toarcian strata in western Alberta consist primarily of organic-rich calcareous siltstones and shales. These deposits represent ideal sedimentary facies to reconstruct environmental changes through the use of geochemical proxy data, especially those that use redox-sensitive transition metals. Ammonite biostratigraphy suggests a nearly continuous sequence from the late Pliensbachian to middle Toarcian. The organic carbon isotopes show the prominent negative CIE interpreted to relate to the release of isotopically depleted carbon at the onset of the T-OAE. Pyrite sulfur weight percentages increase across the CIE and remain elevated, and iron speciation data suggest the development of anoxic conditions. Initial osmium isotope compositions become more radiogenic during the CIE

  16. Basins and the South Polar Terrain of Enceladus: Hotspots vs. Coldspots, and More Evidence for Crustal Spreading and Convergence

    Science.gov (United States)

    McKinnon, William B.; Schenk, P. M.

    2009-09-01

    Stereo-derived topographic mapping of 50% of Enceladus reveals at least 6 large-scale, ovoid depressions (basins) 90-175 km across and 800-to-1500 m deep and uncorrelated with geologic boundaries (Schenk and McKinnon, GRL, in press). Their shape and scale are inconsistent with impact, geoid deflection, or with dynamically supported topography. Isostatic thinning of Enceladus’ ice shell associated with upwellings (and tidally-driven ice melting) can plausibly account for the basins. Thinning implies upwarping of the base of the shell of 10-20 km beneath the depressions, depending on total shell thickness; loss of near-surface porosity due to enhanced heat flow may also contribute to basin lows. Alternatively, the basins may overly cold, inactive, and hence denser ice, but thermal isostasy alone requires thermal expansion more consistent with clathrate hydrate than water ice. In contrast to the basins, the south polar depression (SPD) is larger ( 350 wide) and shallower ( 0.4-to-0.8 km deep) and correlates with the area of tectonic deformation and active resurfacing. The SPD also differs in that the floor is relatively flat (i.e., conforms roughly to the global triaxial shape, or geoid) with broad, gently sloping flanks. The relative flatness across the SPD suggests that it is in or near isostatic equilibrium, and underlain by denser material, supporting the polar sea hypothesis of Collins and Goodman [2007]. Near flatness is also predicted by a crustal spreading origin for the "tiger stripes” [e.g., Barr, 2008]; the extraordinary, high CIRS heat flows imply half-spreading rates in excess of 10 cm/yr, a very young surface age ( 250,000 yr), and a rather thin lithosphere (hence modest thermal topography). Topographic rises in places along the outer margin of the SPD correlate with parallel ridges and deformation along the edge of the resurfaced terrain, consistent with a compressional, imbricate thrust origin for these ridges, driven by the spreading.

  17. Encapsulated discrete octameric water cluster, 1D water tape, and 3D water aggregate network in diverse MOFs based on bisimidazolium ligands

    Science.gov (United States)

    Shi, Ruo-Bing; Pi, Min; Jiang, Shuang-Shuang; Wang, Yuan-Yuan; Jin, Chuan-Ming

    2014-08-01

    Four new metal-organic frameworks, [Zn(2-mBIM)2(SO3CF3)2·(H2O)4] (1), [Zn(BMIE)(1,4-BDC)]·(H2O)3 (2), [Cd(BIM)2(OH)(H2O)2(PF6)]·(H2O)4 (3), and [Cd(PA-BIM)2 (ClO4)2]·11.33H2O (4) (2-mBIM = bis(2-methylimidazol-1-yl)methane, BMIE = 1,2-bis[1-(2-methylimidazole)-diethoxy]ethane, BIM = bis(imidazol-1-yl)methane, and PA-BIM = 1,1-bis [(2-phenylazo)imidazol-1-yl]methane) have been prepared and structurally characterized. Complex 1 exhibits an infinite 1D cationic beaded-chain structure, which encapsulated discrete octameric water clusters that are comprised of a chair-like hexameric water cluster with two extra water molecules dangling on two diagonal vertices of the chair. Complex 2 forms a 1D infinite zigzag metal-organic chain structure with a 1D T4(0)A(4) water tape. Complexes 3 show a 2D grid-like sheet structure with the 1D water tape T4(0)A(0)2(0) motif. Complex 4 is a porous 3D MOF with tetrahedron-coordinated Cd(II) centers and trans-conformation PA-BIM ligands. These holes are occupied by a fascinating three-dimensional water clathrate network, which consists of cage-shaped structural tetradecameric water cluster (H2O)14 units and six independent bridged water molecules. The results suggest that the bisimidazolium ligands and anions play crucial roles in the formation of the different host structures and different guest water aggregations. Additionally, the thermal stabilities and photoluminescence spectra of the complexes have been discussed.

  18. Fluid inclusion and phase equilibrium studies at the Cannivan Gulch molybdenum deposit, Montana, USA: Effect of CO 2 on molybdenite-powellite stability

    Science.gov (United States)

    Darling, Robert S.

    1994-01-01

    The molybdenum deposit at Cannivan Gulch is characterized by both stockwork- and skarn type mineralization. The vein mineral assemblages, however, differ considerably between the various host rocks. In the Cannivan stock, molybdenite occurs in typical quartz + K-feldspar or quartz + muscovite veins. In the country rocks, molybdenite occurs in chlorite + pyrite + magnetite veins containing variable amounts of quartz, calcite, and epidote. Primary fluid inclusions in quartz and fluorite contain aqueous liquid, CO 2 liquid, and CO 2 vapor (average XCO2 = 0.05). Microthermometric and Laser Raman microspectrographic analyses indicate CO 2 is the principal volatile phase. First melting temperatures in the aqueous portion indicate the dissolved salt is principally NaCl. Final CO 2-clathrate melting temperatures indicate NaCl contents ranging from 2 to 7 wt% relative to H 2O. Homogenization temperatures range from 196 to 272°C. Four chlorite temperatures from two samples range from 296 to 319°C. In P- T space, the four chlorite univariants intersect four fluid inclusion isochores (from the same samples) at temperatures of 300 ± 20° C and 1500 ± 300 bars, which are the inferred P and T of molybdenite formation. Mineral equilibria in vein assemblages from country rocks at Cannivan Gulch indicate fO2 and fS2 conditions of molybdenite formation between the pyrite-pyrrhotite-magnetite and pyrite-magnetite-hematite buffers. Formation of a calcite-molybdenite assemblage over powellite suggests that even small amounts of CO 2 ( XCO2 = 0.05) in an ore fluid greatly extend the stability field of molybdenite to higher oxygen fugacities.

  19. 超声法制备苯甲酸钠微胶囊的工艺研究%Research on Processing Technology of Sodium Benzoate Microcapsules by Ultrasound

    Institute of Scientific and Technical Information of China (English)

    章斌; 刘志聪; 侯小桢; 赖宣; 许淼鑫; 王士超

    2014-01-01

    以β-环糊精为壁材,以包埋率为指标,采用单因素试验和Box-Behnken 中心组合设计试验对超声法制备苯甲酸钠微胶囊的工艺进行优化。试验结果表明:超声法制备苯甲酸钠包合物的最佳工艺条件为芯/壁材比1∶7.17,超声包埋时间29.9 min,超声包埋功率180 W,此条件下的实际包埋率为80.5%,与模型预测值之间具有较好的拟合性。%Takeβ-cyclodextrin as wall material and embedding rate of sodium benzoate as main index, the single factor experiment and Box-Behnken response surface methodology for optimization of sodi-um benzoate microcapsules by ultrasound method is explored.The results show that the optimum process conditions for preparation of sodium benzoate clathrate by ultrasound method are as follows:the core/wall material ratio of 1∶7.17,the ultrasonic embedding time of 29.9 min,the ultrasonic embedding power of 180 W,the embedding rate can reach 80.5%,and the regression model is con-sistent with the predicted results.

  20. NMR investigations of surfaces and interfaces using spin-polarized xenon

    Energy Technology Data Exchange (ETDEWEB)

    Gaede, H C [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    1995-07-01

    {sup 129}Xe NMR is potentially useful for the investigation of material surfaces, but has been limited to high surface area samples in which sufficient xenon can be loaded to achieve acceptable signal to noise ratios. In Chapter 2 conventional {sup 129}Xe NMR is used to study a high surface area polymer, a catalyst, and a confined liquid crystal to determine the topology of these systems. Further information about the spatial proximity of different sites of the catalyst and liquid crystal systems is determined through two dimensional exchange NMR in Chapter 3. Lower surface area systems may be investigated with spin-polarized xenon, which may be achieved through optical pumping and spin exchange. Optically polarized xenon can be up to 10{sup 5} times more sensitive than thermally polarized xenon. In Chapter 4 highly polarized xenon is used to examine the surface of poly(acrylonitrile) and the formation of xenon clathrate hydrates. An attractive use of polarized xenon is as a magnetization source in cross polarization experiments. Cross polarization from adsorbed polarized xenon may allow detection of surface nuclei with drastic enhancements. A non-selective low field thermal mixing technique is used to enhance the {sup 13}C signal of CO{sub 2} of xenon occluded in solid CO{sub 2} by a factor of 200. High-field cross polarization from xenon to proton on the surface of high surface area polymers has enabled signal enhancements of {approximately}1,000. These studies, together with investigations of the efficiency of the cross polarization process from polarized xenon, are discussed in Chapter 5. Another use of polarized xenon is as an imaging contrast agent in systems that are not compatible with traditional contrast agents. The resolution attainable with this method is determined through images of structured phantoms in Chapter 6.

  1. To other worlds via the laboratory (Invited)

    Science.gov (United States)

    Lorenz, R. D.

    2009-12-01

    Planetary science is fun, largely by virtue of the wide range of disciplines and techniques it embraces. Progress relies not only on spacecraft observation and models, but also on laboratory work to provide reference data with which to interpret observations and to provide quantitative constraints on model parameters. An important distinction should be drawn between two classes of investigation. The most familiar, pursued by those who make laboratory studies the focus of their careers, is the construction of well-controlled experiments, typically to determine the functional dependence of some desired physical property upon one or two controlled parameters such as temperature, pressure or concentration. Another class of experiment is more exploratory - to 'see what happens'. This exercise often reveals that models may be based on entirely false assumptions. In some cases laboratory results also have value as persuasive tools in providing graphic support for unfamiliar properties or processes - the iconic image of 'flaming ice' makes the exotic notion of methane clathrate immediately accessible. This talk will review the role of laboratory work in planetary science and especially the outer solar system. A few of the author's personal forays into laboratory measurements will be discussed in the talk; These include the physical properties of dessicated icy loess in the US Army Permafrost tunnel in Alaska (as a Mars analog), the use of a domestic microwave oven to measure radar absorptivity (in particular of ammonia-rich water ice) and the generation of waves - and ice - on the surface of a liquid by wind with fluid and air parameters appropriate to Mars and Titan rather than Earth using the MARSWIT wind tunnel at NASA Ames.

  2. Measurements of 14C in ancient ice from Taylor Glacier, Antarctica constrain in situ cosmogenic 14CH4 and 14CO production rates

    Science.gov (United States)

    Petrenko, Vasilii V.; Severinghaus, Jeffrey P.; Schaefer, Hinrich; Smith, Andrew M.; Kuhl, Tanner; Baggenstos, Daniel; Hua, Quan; Brook, Edward J.; Rose, Paul; Kulin, Robb; Bauska, Thomas; Harth, Christina; Buizert, Christo; Orsi, Anais; Emanuele, Guy; Lee, James E.; Brailsford, Gordon; Keeling, Ralph; Weiss, Ray F.

    2016-03-01

    Carbon-14 (14C) is incorporated into glacial ice by trapping of atmospheric gases as well as direct near-surface in situ cosmogenic production. 14C of trapped methane (14CH4) is a powerful tracer for past CH4 emissions from "old" carbon sources such as permafrost and marine CH4 clathrates. 14C in trapped carbon dioxide (14CO2) can be used for absolute dating of ice cores. In situ produced cosmogenic 14C in carbon monoxide (14CO) can potentially be used to reconstruct the past cosmic ray flux and past solar activity. Unfortunately, the trapped atmospheric and in situ cosmogenic components of 14C in glacial ice are difficult to disentangle and a thorough understanding of the in situ cosmogenic component is needed in order to extract useful information from ice core 14C. We analyzed very large (≈1000 kg) ice samples in the 2.26-19.53 m depth range from the ablation zone of Taylor Glacier, Antarctica, to study in situ cosmogenic production of 14CH4 and 14CO. All sampled ice is >50 ka in age, allowing for the assumption that most of the measured 14C originates from recent in situ cosmogenic production as ancient ice is brought to the surface via ablation. Our results place the first constraints on cosmogenic 14CH4 production rates and improve on prior estimates of 14CO production rates in ice. We find a constant 14CH4/14CO production ratio (0.0076 ± 0.0003) for samples deeper than 3 m, which allows the use of 14CO for correcting the 14CH4 signals for the in situ cosmogenic component. Our results also provide the first unambiguous confirmation of 14C production by fast muons in a natural setting (ice or rock) and suggest that the 14C production rates in ice commonly used in the literature may be too high.

  3. Ice particle crystallization in the presence of ethanol: an in situ study by Raman and X-ray diffraction.

    Science.gov (United States)

    Facq, Sébastien; Danède, Florence; Chazallon, Bertrand

    2013-06-13

    Two distinct ethanol aqueous solution droplets ((X(EtOH))L = 8.7 wt % and 46.5 wt %) are investigated by in situ Raman spectroscopy and X-ray diffraction between 253 and 88 K. Structural changes are identified by modifications in the O-H and C-H stretching modes (2800-3800 cm(-1) spectral region) during freezing and annealing events. They are attributed to the formation of ice and/or different hydrate structures in the EtOH-water system. At high initial ethanol concentration, the particle is found to be composed of a modified clathrate I (cubic structure) at 211 K on cooling and transformed into an ethanol hydrate II (monoclinic structure) on annealing between ∼143 and 173 K. This latter decomposes at ∼200 K and leaves an aqueous solution and ice Ih which further dissociates above ∼230 K. At low initial concentration, ice first forms on cooling and the particle consists of a crystalline ice core embedded in a liquid layer of high ethanol content at ~200 K (or an amorphous layer at lower T). A new hydrate (IV) of distinct structure (orthorhombic) is observed on annealing (from 100 K) between ∼123 K and ∼142 K (depending on initial composition), which transforms into the ethanol hydrate II at ∼160 K. The hydrate II decomposes at ∼200 K, and ice Ih remains (and dissociate above ∼220 K) in coexistence with the liquid layer of high ethanol content. It is proposed that the complex crystalline ice particles formed may have the potential to impact several atmospherical processes differently in comparison to the pure ice case. PMID:23682626

  4. 沉积盆地中的流体包裹体:理论基础、图解与分析方法%Fluid inclusions in sedimentary basins:Theoretical basis, diagrams, analytical techniques

    Institute of Scientific and Technical Information of China (English)

    Jean DUBESSY

    2004-01-01

    This paper is focused on the methods to study fluid inclusions in order to get the relevant information. First, the H2 Osalts systems are described and special attention is made upon the determination of the composition from microthermometric data and using new analytical techniques. Application to the study of fluid mixing is exemplified. The different diagrams of H2O-( gas)-salts systems with special attention of the CO2-CH4 system are presented. The complexity of the H2 O-( gas)-salts systems at low temperature, due to the presence of clathrates, is described. The use of micro-Raman spectrometry is specially focused for methanebearing aqueous fluids. The identification of the immiscibility process based on phase diagrams analysis is detailed.%本文主要介绍如何利用流体包裹体来获得合理的数据.首先对H2O-体系进行总结,着重介绍利用显微测温法和其他新的分析技术来确定流体的组成,并举例说明流体混合在流体包裹体研究中的应用.介绍了H2O-(气)-盐体系特别是CO2-CH4体系的图解,探讨了在低温下由于笼合物的形成H2O-(气)-盐体系的复杂相变.重点介绍显微激光拉曼光谱仪在含甲烷水溶液流体中的应用,并根据相图详细讨论了如何确定流体的不混溶.

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

    Science.gov (United States)

    Brown, Erika P; Koh, Carolyn A

    2016-01-01

    Investigating the effect of surfactants on clathrate hydrate growth and morphology, especially particle shell strength and cohesion force, is critical to advancing new strategies to mitigate hydrate plug formation. In this study, dodecylbenzenesulfonic acid and polysorbate 80 surfactants were included during the growth of cyclopentane hydrates at several concentrations above and below the critical micelle concentration. A novel micromechanical method was applied to determine the force required to puncture the hydrate shell using a glass cantilever (with and without surfactants), with annealing times ranging from immediately after the hydrate nucleated to 90 minutes after formation. It was shown that the puncture force was decreased by the addition of both surfactants up to a maximum of 79%. Over the entire range of annealing times (0-90 minutes), the thickness of the hydrate shell was also measured. However, there was no clear change in shell thickness with the addition of surfactants. The growth rate of the hydrate shell was found to vary less than 15% with the addition of surfactants. The cohesive force between two hydrate particles was measured for each surfactant and found to be reduced by 28% to 78%. Interfacial tension measurements were also performed. Based on these results, microscopic changes to the hydrate shell morphology (due to the presence of surfactants) were proposed to cause the decrease in the force required to break the hydrate shell, since no macroscopic morphology changes were observed. Understanding the hydrate shell strength can be critical to reducing the capillary bridge interaction between hydrate particles or controlling the release of unconverted water from the interior of the hydrate particle, which can cause rapid hydrate conversion. PMID:26618773

  6. Un fusible de méthane pour l'explosion cambrienne : les cycles du carbone et dérive des pôles

    Science.gov (United States)

    Kirschvink, Joseph L.; Raub, Timothy D.

    2003-01-01

    The dramatic diversification of animal groups known as the Cambrian Explosion (evolution's 'Big Bang') remains an unsolved puzzle in Earth Science. The Vendian-Cambrian interval is characterized by anomalously high rates of apparent plate motion, interpreted as True Polar Wander (TPW), and by more than a dozen large, high-frequency perturbations in carbon isotopes that dwarf all others observed through the past 65 million years. We suggest that these biological, tectonic, and geochemical events are intimately related in the following fashion. First, tropical continental margins and shelf-slopes which formed during fragmentation of the supercontinent Rodinia accumulated massive quantities of isotopically-light organic carbon during Late Neoproterozoic time, as indicated by strikingly heavy isotope ratios in inorganic carbon during interglacial intervals. Second, an initial phase of Vendian TPW moved these organic-rich deposits to high latitude, where conditions favored trapping biogenic methane in layers of gas hydrate and perhaps permafrost. Continued sedimentation during Late Vendian time added additional hydrate/gas storage volume and stabilized underlying units until the geothermal gradient moved them out of the clathrate stability field, building up deep reservoirs of highly pressurized methane. Finally, a burst of TPW brought these deposits back to the Tropics, where they gradually warmed and were subjected to regional-scale thermohaline eddy variation and related sedimentation regime changes. Responding to the stochastic character of such changes, each reservoir reached a critical failure point independently at times throughout the Cambrian. By analogy with the Late Paleocene Thermal Maximum event, these methane deposits yield transient, greenhouse-induced pulses of global warming when they erupt. Temperature correlates powerfully with biodiversity; the biochemical kinetics of metabolism at higher temperature decrease generation time and maintain relatively

  7. Deep-ocean field test of methane hydrate formation from a remotely operated vehicle

    Science.gov (United States)

    Brewer, P.G.; Orr, F.M.; Friederich, G.; Kvenvolden, K.A.; Orange, D.L.; McFarlane, J.; Kirkwood, W.

    1997-01-01

    We have observed the process of formation of clathrate hydrates of methane in experiments conducted on the remotely operated vehicle (ROY) Ventana in the deep waters of Monterey Bay. A tank of methane gas, acrylic tubes containing seawater, and seawater plus various types of sediment were carried down on Ventana to a depth of 910 m where methane gas was injected at the base of the acrylic tubes by bubble stream. Prior calculations had shown that the local hydrographic conditions gave an upper limit of 525 m for the P-T boundary defining methane hydrate formation or dissociation at this site, and thus our experiment took place well within the stability range for this reaction to occur. Hydrate formation in free sea-water occurred within minutes as a buoyant mass of translucent hydrate formed at the gas-water interface. In a coarse sand matrix the Filling of the pore spaces with hydrate turned the sand column into a solidified block, which gas pressure soon lifted and ruptured. In a fine-grained black mud the gas flow carved out flow channels, the walls of which became coated and then filled with hydrate in larger discrete masses. Our experiment shows that hydrate formation is rapid in natural seawater, that sediment type strongly influences the patterns of hydrate formation, and that the use of ROV technologies permits the synthesis of large amounts of hydrate material in natural systems under a variety of conditions so that fundamental research on the stability and growth of these substances is possible.

  8. Fluid Evolution During Mineralization of Atashkuh Fluorite-Barite (±Sulfide Deposit, South of Delijan

    Directory of Open Access Journals (Sweden)

    Seyed Javad Moghaddasi

    2016-07-01

    the Atashkuh deposit. Fluid inclusions are of several types: (1 two-phase, liquid-vapor (LV, two- phase aqueous with hydrohalite (LVHH, multiphase (SH, H2O-CO2 with clathrate (C1 and without clathrate (C2 were recognized and analyzed. The first ice melting temperature (Te of fluorite, barite and quartz two-phase aqueous (LV inclusions varies between -22°C and -25°C, representing a H2O ± NaCl ± KCl multiphase solution (Van den Kerkhof and Hein, 2001. The last ice melting temperatures of three samples (Tmice vary between -4.9°C to -9.7°C, -3.2°C to -7.2°C and -2°C to -4.8°C which indicate salinities of 7.7-13.6, 5.2-10.7 and 3.2-7.5 wt% NaCl equivalent for fluorite, barite and quartz. The final homogenization temperatures (Thtotal of these inclusions vary between 90 and 205 °C for fluorite, 130 to 270 °C for barite and 110 to 193 °C for quartz. The CO2 melting temperatures (TmCO2 of fluorite and quartz C1 inclusions show ranges of -57.1 to -58.5 °C which suggest the presence of CH4 and/or N2 impurities (Burruss, 1981. The clathrate melting temperature (Tmclath varies between 4.8 and 8.5 °C representing a salinity of 5.3 to 9.2 and 3 to 6.7 wt% NaCl equivalent for fluorite and quartz. The CO2 homogenization temperature (ThCO2 in these inclusions is 7.4 to 18.8 °C for fluorite and 13.4 to 27.5 °C for quartz. The homogenization temperature (Thtotal for these inclusions is 170-210 °C for fluorite and 195-280 °C for quartz. References Burruss, R.C., 1981. Analysis of phase equilibria in C–O–H–S fluid inclusions. Mineralogical Association of Canada Short Course, 6(3: 39-74. Ghorbani, M., 2013. The economic geology of Iran, mineral deposits and natural resources. Springer Netherlands, 569 pp. Thiele, O., Alavi, M., Assefi, R., Hushmand-zadeh, A., Seyed-Emami, K. and Zahedi, M., 1968. Explanatory text of the Golpaygan quadrangle map, scale 1:250,000. Geological Survey of Iran. Geological quadrangle E7, 24 pp. Van den Kerkhof, A.M. and Hein, U.F., 2001

  9. 盐湖丰产元素与Zintl化合物(续完)%The Correlation of Abundant Elements and Zintl Phases

    Institute of Scientific and Technical Information of China (English)

    贾永忠; 景燕; 马军; 岳都元; Claude Belin; Monique Tillard

    2011-01-01

    Zintl化合物是以Edward Zintl命名的化合物,是一类由电正性的碱金属或碱土金属与电负性的13族或14族元素形成的特殊金属间化合物.其价键模式可以是离子键、金属键和共价键共存,其中的准金属可以共价键的形式形成各种形式的离子簇,因而其结构复杂多样.这类化合物的部分阴离子簇不仅具有稳定的笼状、层状和链状结构,并且具有特殊的光、电、磁等性能,使得在半导体、催化、电极材料等方面都有应用的前景和发展潜力.介绍了几个特殊Zintl化合物体系,盐湖丰产元素在Zinfi化合物中的作用,指出了含有盐湖丰产元素的Zintl化合物的应用前景和方向.%The term Zintl phase has been coined in honour of Edward Zintl,a German chemist. Zintl phases are formed by combinations of moderately electronegative post-transition elements, such as main group 13 and 14 elements with electropositive alkaline or alkaline-earth metals. In these combinations, owing to electron transfers ( total or partial) from the electropositive to the electronegative elements, anionic frameworks are formed in solid state that range from isolated anionic clusters, rings. cages and 1,2 or 3-D extended structures of which clathrates are among the most remarkable.The authors discuss the correlation of salt lake resources and Zintl phases. The potential applications of Zintl phases in salt lake resources are briefly discussed. This strategy for the synthesis of solid state compounds, which comprised light elements of salt lake resources, main group 13 and 14 elements and transition metal, have unique magnetic, electronic, thermoelectric, colossal magnetoresistance and ferromagnetic properties.

  10. An atmosphere-ocean GCM modelling study of the climate response to changing Arctic seaways in the early Cenozoic.

    Science.gov (United States)

    Roberts, C. D.; Legrande, A. N.; Tripati, A. K.

    2008-12-01

    previous findings on the potential influence of Arctic gateways on ocean overturning and also suggests that Northern Hemisphere climate, particularly in the North Atlantic, was very sensitive to changes in Arctic seaways. This result is of particular significance when considered in the context of the Paleocene Eocene Thermal Maximum (PETM). Volcanic activity prior to the PETM may have been responsible for the formation of a sub-aerial barrier in the North Atlantic, and consequently may have driven warming of intermediate waters sufficient to destabilize methane clathrates. Evidence for freshening of Arctic ocean waters prior to the PETM would support this hypothesis.

  11. New constraints on the deep oxygen abundance in Uranus and Neptune

    Science.gov (United States)

    Cavalié, Thibault; Venot, Olivia; Selsis, Franck; Hersant, Franck; Hartogh, Paul

    2016-10-01

    One of the great mysteries in the Solar System is how Giant Planets formed. Two main formation scenarios coexist: disk gravitational instability and core accretion. These scenarios differ not only in the time required to form planets, but also in the final composition of the planets' interiors. In this sense, heavy element abundances are key constraints and they depend on how the ices of the planetesimal that formed the cores of these planets condensed (e.g., amorphous or crystalline).Measuring the deep oxygen abundance can help differentiating the condensation processes of the planetesimal ices. Indeed, clathration needs a larger amount of water than the amorphous ice scenario. While Galileo probably failed to measure the Jovian deep oxygen abundance, Juno should shed light on this long lasting question. Measuring Saturn's deep oxygen is a goal of the entry probe that will be proposed to ESA (Mousis et al. 2016). Regarding the Ice Giants, there is no such mission planned in the near future to measure their deep oxygen abundance and it is very challenging to probe remotely below the water cloud in these planets with microwaves. Another way to constrain the deep oxygen abundance consists in using thermochemical modeling to link upper tropospheric disequilibrium species to the deep oxygen.In this paper, we apply a thermochemical and diffusion model to the ice giant tropospheres to constrain their deep oxygen abundance from CO observations. Because the results depend on the thermal structure, on the strength of tropospheric mixing, and to a lesser extent on the deep carbon abundance, we have explored a 4D parameter space (temperature, tropospheric mixing, deep oxygen and carbon abundance) for each planet to fit their upper tropospheric composition. For instance, we have computed a series of classical thermal profiles based on dry/wet adiabats and new profiles that account for the mean molecular weight gradient at the water condensation layer (following the

  12. Organic synthesis in the outer Solar System: Recent laboratory simulations for Titan, the Jovian planets, Triton and comets

    Science.gov (United States)

    Sagan, C.; Thompson, W. R.; Khare, B. N.; Chyba, C. F.

    1991-01-01

    We tabulate the most abundant gases and their radiation yields, for two experimental pressures: 0.24 mb, more relevant to upper atmosphere excitation, and 17 mb, more relevant to tropospheric, cosmic ray excitation. The yields computed in the 0.24 mb experiment combined with measured electronic fluxes and a simple, eddy diffusion model of Titan's atmosphere predict abundances of detected molecules in agreement with those found by Voyager and for heavier products, in somewhat better agreement with observation than photochemical absolute reaction rate kinetics models. All Voyager organics are accounted for and no detectable products are found that Voyager did not detect. A striking increase of products with multiple bonds is found with decreasing pressure. Hydrocarbon abundances decline slowly with increasing carbon number. Additionally, we list preliminary estimates for the yield of the heteropolymer, which seems to be produced in a quantity comparable (in moles of C+N consumed) to the total amount of gaseous product. The production rate required to sustain Titan's haze against sedimentation also indicates yields of this order. As can be seen from the table, over 10(exp 9) years substantial amounts of these products can accumulate on the surface -- ranging from cm thickness for the (C+N equals 4) species to a meter or more for HCN and C2H2; we also expect a meter or more of tholins. Similar analyses have been or are being done for the Jovian planets and Triton. Charged particle irradiation of hydrocarbon clathrates or mixed hydrocarbon/water ices produces a range of organic products, reddening and darkening of the ices and characteristic infrared spectra. From such spectra, the predicted emission by fine particles in cometary comae well-matches the observed 3.4 micron emission spectra of Comet Halley and other recent comets. Heliocentric evolution of organic emission features in comets is predicted. Organic products of such ice irradiation may account for colors and

  13. Permeability Reduction in Passively Degassing Seawater-dominated Volcanic-hydrothermal systems: Processes and Perils on Raoul Island, Kermadecs (NZ)

    Science.gov (United States)

    Christenson, B. W.; Reyes, A. G.

    2014-12-01

    The 2006 eruption from Raoul Island occurred apparently in response to local tectonic swarm activity, but without any precursory indication of volcanic unrest within the hydrothermal system on the island. The eruption released some 200 T of SO2, implicating the involvement of a deep magmatic vapor input into the system during/prior to the event. In the absence of any recognized juvenile material in the eruption products, previous explanations for this eruptive event focused on this vapor being a driving force for the eruption. In 2004, at least 80 T/d of CO2 was escaping from the hydrothermal system, but mainly through areas that did not correspond to the 2006 eruption vents. The lack of a pre-eruptive hydrothermal system response related to the seismic event in 2006 can be explained by the presence of a hydrothermal mineralogic seal in the vent area of the volcano. Evidence for the existence of such a seal was found in eruption deposits in the form of massive fracture fillings of aragonite, calcite and anhydrite. Fluid inclusion homogenization temperatures in these phases range from ca. 140 °C to 220 °C which, for pure water indicate boiling point depths of between 40 and 230 m assuming a cold hydrostatic pressure constraint. Elevated pressures behind this seal are consistent with the occurrence of CO2 clathrates in some inclusion fluids, indicating CO2 concentrations approaching 1 molal in the parent fluids. Reactive transport modeling of magmatic volatile inputs into what is effectively a seawater-dominated hydrothermal system provide valuable insights into seal formation. Carbonate mineral phases ultimately come to saturation along this flow path, but we suggest that focused deposition of the observed massive carbonate seal is facilitated by near-surface boiling of these CO2-enriched altered seawaters, leading to large degrees of supersaturation which are required for the formation of aragonite. As the seal grew and permeability declined, pore pressures

  14. Guest Molecule Exchange Kinetics for the 2012 Ignik Sikumi Gas Hydrate Field Trial

    Energy Technology Data Exchange (ETDEWEB)

    White, Mark D.; Lee, Won Suk

    2014-05-14

    A commercially viable technology for producing methane from natural gas hydrate reservoirs remains elusive. Short-term depressurization field tests have demonstrated the potential for producing natural gas via dissociation of the clathrate structure, but the long-term performance of the depressurization technology ultimately requires a heat source to sustain the dissociation. A decade of laboratory experiments and theoretical studies have demonstrated the exchange of pure CO2 and N2-CO2 mixtures with CH4 in sI gas hydrates, yielding critical information about molecular mechanisms, recoveries, and exchange kinetics. Findings indicated the potential for producing natural gas with little to no production of water and rapid exchange kinetics, generating sufficient interest in the guest-molecule exchange technology for a field test. In 2012 the U.S. DOE/NETL, ConocoPhillips Company, and Japan Oil, Gas and Metals National Corporation jointly sponsored the first field trial of injecting a mixture of N2-CO2 into a CH4-hydrate bearing formation beneath the permafrost on the Alaska North Slope. Known as the Ignik Sikumi #1 Gas Hydrate Field Trial, this experiment involved three stages: 1) the injection of a N2-CO2 mixture into a targeted hydrate-bearing layer, 2) a 4-day pressurized soaking period, and 3) a sustained depressurization and fluid production period. Data collected during the three stages of the field trial were made available after an extensive quality check. These data included continuous temperature and pressure logs, injected and recovered fluid compositions and volumes. The Ignik Sikumi #1 data set is extensive, but contains no direct evidence of the guest-molecule exchange process. This investigation is directed at using numerical simulation to provide an interpretation of the collected data. A numerical simulator, STOMP-HYDT-KE, was recently completed that solves conservation equations for energy, water, mobile fluid guest molecules, and hydrate guest

  15. Gas hydrates: past and future geohazard?

    Science.gov (United States)

    Maslin, Mark; Owen, Matthew; Betts, Richard; Day, Simon; Dunkley Jones, Tom; Ridgwell, Andrew

    2010-05-28

    Gas hydrates are ice-like deposits containing a mixture of water and gas; the most common gas is methane. Gas hydrates are stable under high pressures and relatively low temperatures and are found underneath the oceans and in permafrost regions. Estimates range from 500 to 10,000 giga tonnes of carbon (best current estimate 1600-2000 GtC) stored in ocean sediments and 400 GtC in Arctic permafrost. Gas hydrates may pose a serious geohazard in the near future owing to the adverse effects of global warming on the stability of gas hydrate deposits both in ocean sediments and in permafrost. It is still unknown whether future ocean warming could lead to significant methane release, as thermal penetration of marine sediments to the clathrate-gas interface could be slow enough to allow a new equilibrium to occur without any gas escaping. Even if methane gas does escape, it is still unclear how much of this could be oxidized in the overlying ocean. Models of the global inventory of hydrates and trapped methane bubbles suggest that a global 3( degrees )C warming could release between 35 and 940 GtC, which could add up to an additional 0.5( degrees )C to global warming. The destabilization of gas hydrate reserves in permafrost areas is more certain as climate models predict that high-latitude regions will be disproportionately affected by global warming with temperature increases of over 12( degrees )C predicted for much of North America and Northern Asia. Our current estimates of gas hydrate storage in the Arctic region are, however, extremely poor and non-existent for Antarctica. The shrinking of both the Greenland and Antarctic ice sheets in response to regional warming may also lead to destabilization of gas hydrates. As ice sheets shrink, the weight removed allows the coastal region and adjacent continental slope to rise through isostacy. This removal of hydrostatic pressure could destabilize gas hydrates, leading to massive slope failure, and may increase the risk of

  16. Scientific Advancements and Technological Developments of High P-T Neutron Diffraction at LANSCE, Los Alamos

    Science.gov (United States)

    Zhao, Y.; Daemen, L. L.; Zhang, J.

    2003-12-01

    In-situ high P-T neutron diffraction experiments provide unique opportunities to study the crystal structure, hydrogen bonding, magnetism, and thermal parameters of light elements (eg. H, Li, B) and heavy elements (eg. Ta, U, Pu,), that are virtually impossible to determine with x-ray diffraction techniques. For example, thermoelasticity and Debye-Waller factor as function of pressure and temperature can be derived using in-situ high P-T neutron diffraction techniques. These applications can also be extended to a much broader spectrum of scientific problems. For instance, puzzles in Earth science such as the carbon cycle and the role of hydrous minerals for water exchange between lithosphere and biosphere can be directly addressed. Moreover, by introducing in-situ shear, texture of metals and minerals accompanied with phase transitions at high P-T conditions can also be studied by high P-T neutron diffraction. We have successfully conducted high P-T neutron diffraction experiments at LANSCE and achieved simultaneous high pressures and temperatures of 10 GPa and 1500 K. With an average 3-6 hours of data collection, the diffraction data are of sufficiently high quality for the determination of structural parameters and thermal vibrations. We have studied hydrous mineral (MgOD), perovskite (K.15,Na.85)MgF3, clathrate hydrates (CH4-, CO2-, and H2-), metals (Mo, Al, Zr), and amorphous materials (carbon black, BMG). The aim of our research is to accurately map bond lengths, bond angles, neighboring atomic environments, and phase stability in P-T-X space. Studies based on high-pressure neutron diffraction are important for multi-disciplinary science and we welcome researchers from all fields to use this advanced technique. We have developed a 500-ton toroidal press, TAP-98, to conduct simultaneous high P-T neutron diffraction experiments inside of HIPPO (High-Pressure and Preferred-Orientation diffractometer). We have also developed a large gem-crystal anvil cell, ZAP-01

  17. Water interactions with hydrophobic groups: Assessment and recalibration of semiempirical molecular orbital methods

    International Nuclear Information System (INIS)

    In this work, we present a study of the ability of different semiempirical methods to describe intermolecular interactions in water solution. In particular, we focus on methods based on the Neglect of Diatomic Differential Overlap approximation. Significant improvements of these methods have been reported in the literature in the past years regarding the description of non-covalent interactions. In particular, a broad range of methodologies has been developed to deal with the properties of hydrogen-bonded systems, with varying degrees of success. In contrast, the interactions between water and a molecule containing hydrophobic groups have been little analyzed. Indeed, by considering the potential energy surfaces obtained using different semiempirical Hamiltonians for the intermolecular interactions of model systems, we found that none of the available methods provides an entirely satisfactory description of both hydrophobic and hydrophilic interactions in water. In addition, a vibrational analysis carried out in a model system for these interactions, a methane clathrate cluster, showed that some recent methods cannot be used to carry out studies of vibrational properties. Following a procedure established in our group [M. I. Bernal-Uruchurtu, M. T. C. Martins-Costa, C. Millot, and M. F. Ruiz-López, J. Comput. Chem. 21, 572 (2000); W. Harb, M. I. Bernal-Uruchurtu, and M. F. Ruiz-López, Theor. Chem. Acc. 112, 204 (2004)], we developed new parameters for the core-core interaction terms based on fitting potential energy curves obtained at the MP2 level for our model system. We investigated the transferability of the new parameters to describe a system, having both hydrophilic and hydrophobic groups, interacting with water. We found that only by introducing two different sets of parameters for hydrophilic and hydrophobic hydrogen atom types we are able to match the features of the ab initio calculated properties. Once this assumption is made, a good agreement with the

  18. Modelling the carbon cycle though Neoproterozoic Earth system changes

    Science.gov (United States)

    Bjerrum, C. J.; Canfield, D. E.

    2011-12-01

    The Neoproterozoic-Cambrian records major changes in geochemical proxies as a result of a profound reorganization of the Earth system. Extensive glaciations and the first oxygenation of the deep ocean with a shift from sulfidic/ferruginous conditions to more oxic conditions was accompanied by the radiation of the first animals. The reorganization was also recorded in enigmatic large-amplitude fluctuations in the isotopic composition of marine carbonate carbon (δ13CIC ), were only some are associated with major known glaciations. The carbon isotope events seem to grow in amplitude through the Neoproterozoic culminating in the Shuram anomaly - the largest in Earth history. The δ13CIC events are also accompanied by changes in the isotope composition of marine organic carbon (δ13COC), where the co-variation of δ13CIC and δ13COC seems to evolve from markedly positive relationship over a subdued δ13COC variation and an almost inverse pattern. There is limited understanding as to why or how the structure of these isotope events evolved over time and how these events may tie to the reorganization of the Earth system. We use our published quantitative model of the Shuram anomaly to explore carbon cycle dynamics during the Neoproterozoic. By changing in pre-event atmosphere-ocean chemistry we explore which factors contribute to the observed patterns of the large Neoproterozoic carbon isotope events. In particular, decreasing atmospheric CO2 and a slight increase of oxygen together with an increasing CO source from rising DOC concentrations results in progressively larger event amplitudes with changing co-variation between δ13CIC and δ13COC , culminating with the structure observed for the Shurum-Wonaka anomaly in the Ediacaran. In our model, the carbon isotope excursions were driven by methane from sediment-hosted clathrate hydrate deposits. Being a powerful greenhouse gas, methane increased temperature and melted icecaps. These combined to produce a negative 18O

  19. Constraining the cause of the end-Guadalupian extinction with coupled records of carbon and calcium isotopes

    Science.gov (United States)

    Jost, A. B.; Mundil, R.; He, B.; Brown, S. T.; Altiner, D.; Sun, Y.; DePaolo, D. J.; Payne, J.

    2013-12-01

    A negative δ13C excursion in carbonate sediments from Guadalupian (Middle Permian) and Lopingian (Late Permian) stratigraphic sections has been interpreted to result from a large carbon cycle disturbance during end-Guadalupian extinction event (ca. 260 Ma). However, the carbon isotope data alone are insufficient to uniquely determine the type and magnitude of perturbations to the global carbon cycle. The carbon and calcium cycles are coupled via CaCO3 burial, so changes in calcium isotopes can be used to constrain the cause of a carbon isotope excursion. In this study, we present coupled carbon and calcium isotope records from three Guadalupian-Lopingian (G/L) sections in China and Turkey. Isotope records among our studied sections are inconsistent in both their δ13C and δ44/40Ca records. Similar inconsistencies in δ13C among sections occur across previously published datasets. Sections with large (>3‰) changes in δ13C either show evidence for diagenetic alteration or do not show δ13C and δ44/40Ca changes consistent with severe volcanic degassing from Emeishan or methane clathrate destabilization. We conclude that the large isotopic changes are more likely the result of local burial conditions or diagenetic effects, rather than a large carbon cycle disturbance. Perturbations to the global carbon and calcium cycles appear to have been much smaller across the G/L transition than across the subsequent Permian-Triassic boundary. This finding is consistent with recent paleobiological data showing that the end-Guadalupian extinction was much less severe than previously believed, and was indistinguishable in magnitude from background intervals. However, selective extinction of marine animals with passive respiratory physiology indicates that the G/L extinction cannot simply be due to background extinction or sampling failure, and that it was triggered by some environmental event. Therefore, any environmental event must have been small enough to not generate large

  20. H{sub 2} storage in microporous materials: a comparison between zeolites and Mos

    Energy Technology Data Exchange (ETDEWEB)

    Ricchiardi, G.; Regli, L.; Vitillo, J. G.; Cocina, D.; Bordiga, S.; Lamberti, C.; Spoto, G.; Zecchina, A.; Bjorgen, M.; Lillerud, K. P.

    2005-07-01

    One of the main concerns about a hydrogen-based energy economy is the efficient storage and transport of this highly flammable gas. Many strategies have been followed or suggested in recent years to solve this problem. The most important ones are: 1) storage in metals and alloys; 2) storage in complex hydrides (alanates, borides); 3) storage by trapping in clathrates (ice and others); 4) storage in microporous materials (carbons, zeolitic materials, metal-organic frameworks, polymers). [1, 2] In this work we have focused our attention on microporous materials, where the crucial point is the strength of the interaction between the molecular hydrogen and the internal surfaces of micropores and/ or of cages of entrapping materials. It is known from fundamental studies that H2 strongly interacts with ions in the gas but that the presence of counterions decreases the interaction energy substantially. The most prominent class of microporous materials, which contains isolated and exposed cations, are zeolites and zeotypes: ideal systems to investigate the interaction of H2 with both dispersive and electrostatic forces [3]. So, even if they are not sufficiently light to represent the final solution to H2 storage, the availability of a large variety of frameworks and chemical compositions combined with low cost and superior mechanical and thermal stabilities increases the interest in these materials. In this work we have studied in detail, by means of volumetric and spectroscopic measurements, zeolites with CHA topology (as they are characterized by a strong acidity and by a big surface area). H-SSZ-13 zeolite, characterized by a low Al content (Si/Al = 11), has shown the best properties in hydrogen storage in respect to all the other zeolites and zeotypes with different compositions and topologies [4]. The results have been compared with those obtained for MOF-5 [5], a well known Metal-Organic Framework, indicated as a very good material for molecular hydrogen storage [6

  1. Hydrogeologic Controls on the Deep Terrestrial Biosphere - Chemolithotrophic Energy for Subsurface Life on Earth and Mars

    Science.gov (United States)

    Sherwood Lollar, B.; Moran, J.; Tille, S.; Voglesonger, K.; Lacrampe-Couloume, G.; Onstott, T.; Pratt, L.; Slater, G.

    2009-05-01

    potential clathrates will affect the porosity and permeability, and net flux of gases from the Martian crust, the underlying principles of fracture-controlled energy sequestration and episodic release remain. Furthermore understanding the origin and distribution of biogenic and geologic sources of CH4 at these analog Earth sites will inform models and strategies for deciphering the origin of CH4 recently reported in the Martian atmosphere.

  2. Pcw/phemos for Arctic Weather, Climate and Air Quality: a Quasi-Geostationary View of the Arctic and Environs

    Science.gov (United States)

    McConnell, J. C.; O'Neill, N. T.; McElroy, C. T.; Solheim, B.; Buijs, H.; Rahnama, P.; Walker, K. A.; Martin, R. V.; Sioris, C.; Garand, L.; Trichtchenko, A.; Nassar, R.

    2011-12-01

    abundance data on methane and possibly CO2 to assess perturbations due to their increasing release from the permafrost and from shallowly buried clathrates. We will outline the scientific objectives and the status of the current instrument design and challenges.

  3. Hydrates in the California Borderlands: 2D CSEM inversion results from towed and seafloor arrays

    Science.gov (United States)

    Kannberg, P. K.; Constable, S.; Key, K.

    2013-12-01

    Methane hydrate, an ice-like solid clathrate of methane and water, forms in shallow continental slope sediments, and is both a potential energy source and geologic hazard. Traditionally, methane hydrate presence is inferred from a seismically detected bathymetry tracking velocity inversion, known as the bottom-simulating reflector (BSR). However the BSR is an indicator of free gas at the base of the hydrate stability zone, and not an indicator of hydrate. As such, seismic methods are limited in their capacity to identify and quantify hydrate presence and concentration. Controlled source electromagnetic (CSEM) methods are sensitive to, and are able to directly detect, the presence of electrically resistive methane hydrate and free gas. Additionally, because shallow resistors can mimic deeper resistors in seafloor instruments, understanding the shallow sediment structure can inform deeper crustal modeling. We conducted two CSEM surveys in the San Nicolas Basin, located 150km west of San Diego where a BSR was identified from legacy seismics. Both surveys were conducted using a deep-towed EM transmitter followed by 4 towed 3-axis electric field receivers spaced every 200 m from 400-1000 m behind the transmitter. Either a half-hertz or quarter-hertz modified square wave was transmitted on a 200 ampere, 100 m dipole that was flown between 50 and 100m above the seafloor. The short transmitter-receiver offset allows resolution of shallow structure (less than 1km below seafloor), while the longer transmitter-seafloor receiver resolves deeper structure. Between the two surveys, 27 seafloor receivers were deployed and ~150km of lines were towed, including 5 transects of the basin coincident with legacy seismic lines, and a short-offset repeatability study. Initial 1D modeling showed the presence of a resistor coincident with the BSR. Further 2D inversions using the MARE2DEM inversion program were run for the towed array. These inversions show a 4 ohm-m resistor in the central

  4. Hydrates in the California Borderlands Revisited: Results from a Controlled-Source Electromagnetic Survey of the Santa Cruz Basin.

    Science.gov (United States)

    Kannberg, P. K.; Constable, S.

    2014-12-01

    Methane hydrate, an ice-like clathrate of water and methane, forms in shallow continental slope sediments, and is both a potential energy source and geologic hazard. Hydrates presence is traditionally inferred from the presence of the bottom simulating reflector (BSR), a seismic velocity inversion resulting from free gas pooling at the base of the hydrate stability field. The BSR is not a measure of hydrate, but rather a proxy for free gas presence. Whereas seismic methods are sensitive to velocity anomalies, controlled-source electromagnetic (CSEM) methods are sensitive to conductivity anomalies. The electrically resistive methane hydrate makes a favorable target for CSEM surveys, which are capable of detecting and potentially quantifying the presence of methane hydrate directly. Building on previous work 100km to the south in the San Nicolas Basin, we present initial results from a 6-day June 2014 survey in the Santa Cruz Basin, located 100km west of Los Angeles. CSEM surveys are performed by deep-towing an EM source that is transmitting a known signal; this signal is detected by towed and seafloor receivers. The initial EM source signal is altered by the electrical properties of the surrounding environment. Conductors such as brine and seawater are attenuating mediums, while resistors such as methane hydrate, gas, and oil are preservative of the original signal. Twenty-one seafloor receivers, as well as a 4 receiver towed array were deployed to image the resistivity structure of the Santa Cruz Basin. Using 30-year-old 2D seismic profiles as a guide, potential hydrate targets were identified, and the transmitter and array were towed over 150 km on 6 lines with 5 seafloor receivers each. The 6 towed lines were coincident with legacy seismic lines. The towed array is sensitive to sediment depths less than 1km, allowing for high data density through the hydrate stability field. The larger transmitter-receiver offsets of the seafloor receivers allow sensitivity to at

  5. Nuclear Quantum Effects in Ice Phases and Water from First Principles Calculations

    Science.gov (United States)

    Pamuk, Betul

    Despite the simplicity of the molecule, condensed phases of water show many physical anomalies, some of which are still unexplained to date. This thesis focuses on one striking anomaly that has been largely neglected and never explained. When hydrogen (1H) is replaced by deuterium (2 D), zero point fluctuations of the heavy isotope causes ice to expand, whereas in normal isotope effect, heavy isotope causes volume contraction. Furthermore, in a normal isotope effect, the shift in volume should decrease with increasing temperature, while, in ice, the volume shift increases with increasing temperature and persists up to the melting temperature and also exists in liquid water. In this dissertation, nuclear quantum effects on structural and cohesive properties of different ice polymorphs are investigated. We show that the anomalous isotope effect is well described by first principles density functional theory with van der Waals (vdW-DF) functionals within the quasi-harmonic approximation. Our theoretical modeling explains how the competition between the intra- and inter-molecular bonding of ice leads to an anomalous isotope effect in the volume and bulk modulus of ice. In addition, we predict a normal isotope effect when 16O is replaced by 18O, which is experimentally confirmed. Furthermore, the transition from proton disordered hexagonal phase, ice Ih to proton ordered hexagonal phase, ice XI occurs with a temperature difference between 1H and 2D of 6K, in good agreement with experimental value of 4K. We explain, for first time for that this temperature difference is entirely due to the zero point energy. In the second half of this thesis, we expand our study to the other ice phases: ice Ic, ice IX, ice II, ice VIII, clathrate hydrates, and low and high density amorphous ices. We employ the methodology that we have developed to investigate the isotope effect in structures with different configurations. We show that there is a transition from anomalous isotope effect

  6. The late Precambrian greening of the Earth.

    Science.gov (United States)

    Knauth, L Paul; Kennedy, Martin J

    2009-08-01

    Many aspects of the carbon cycle can be assessed from temporal changes in the (13)C/(12)C ratio of oceanic bicarbonate. (13)C/(12)C can temporarily rise when large amounts of (13)C-depleted photosynthetic organic matter are buried at enhanced rates, and can decrease if phytomass is rapidly oxidized or if low (13)C is rapidly released from methane clathrates. Assuming that variations of the marine (13)C/(12)C ratio are directly recorded in carbonate rocks, thousands of carbon isotope analyses of late Precambrian examples have been published to correlate these otherwise undatable strata and to document perturbations to the carbon cycle just before the great expansion of metazoan life. Low (13)C/(12)C in some Neoproterozoic carbonates is considered evidence of carbon cycle perturbations unique to the Precambrian. These include complete oxidation of all organic matter in the ocean and complete productivity collapse such that low-(13)C/(12)C hydrothermal CO(2) becomes the main input of carbon. Here we compile all published oxygen and carbon isotope data for Neoproterozoic marine carbonates, and consider them in terms of processes known to alter the isotopic composition during transformation of the initial precipitate into limestone/dolostone. We show that the combined oxygen and carbon isotope systematics are identical to those of well-understood Phanerozoic examples that lithified in coastal pore fluids, receiving a large groundwater influx of photosynthetic carbon from terrestrial phytomass. Rather than being perturbations to the carbon cycle, widely reported decreases in (13)C/(12)C in Neoproterozoic carbonates are more easily interpreted in the same way as is done for Phanerozoic examples. This influx of terrestrial carbon is not apparent in carbonates older than approximately 850 Myr, so we infer an explosion of photosynthesizing communities on late Precambrian land surfaces. As a result, biotically enhanced weathering generated carbon-bearing soils on a large

  7. Martian Polar Caps: Folding, Faulting, Flowing Glaciers of Multiple Interbedded Ices

    Science.gov (United States)

    Kargel, J. S.

    2001-12-01

    The Martian south polar cap (permanent CO2 cap and polar layered deposits), exhibit abundant, varied, and widespread deformational phenomena. Folding and boudinage are very common. Strike-slip or normal faults are rarer. Common in the vicinity of major troughs and scarps are signs of convergent flow tectonics manifested as wrinkle-ridge-like surface folds, thrust faults, and viscous forebulges with thin-skinned extensional crevasses and wrinkle-ridge folds. Such flow convergence is predicted by theory. Boudinage and folding at the 300-m wavelength scale, indicating rheologically contrasting materials, is widely exposed at deep levels along erosional scarps. Independent morphologic evidence indicates south polar materials of contrasting volatility. Hence, the south polar cap appears to be a multiphase structure of interbedded ices. The north polar cap locally also exhibits flow indicators, though they are neither as common nor as varied as in the south. The large-scale quasi-spiral structure of the polar caps could be a manifestation of large-scale boudinage. According to this scenario, deep-level boudinage continuously originates under the glacial divide (the polar cap summit). Rod-like boudin structures are oriented transverse to flow and migrate outward with the large-scale flow field. Troughs develop over areas between major boudins. A dynamic competition, and possibly a rough balance, develops between the local flow field in the vicinity of a trough (which tends to close the trough by lateral closure and upwelling flow) and sublimation erosion (which tends to widen and deepen them). Over time, the troughs flow to the margins of the polar cap where they, along with other polar structures, are destroyed by sublimation. Major ice types contributing to rheological and volatility layering may include, in order of highest to lowest mechanical strength, CO2 clathrate hydrate, water ice containing inert/insoluble dust, pure water ice, water ice containing traces of

  8. 河豚鱼肝油中EPA、DHA的纯化与含量测定%Purification and Content Determination of EPA and DHA in Puffer Fish Liver Oil

    Institute of Scientific and Technical Information of China (English)

    郭斌; 孟磊; 彭宏伟; 李智

    2011-01-01

    OBJECTIVE: To study purification method of EPA and DHA in the puffer fish liver oil and to establish the methods for the content determination of EPA and DHA. METHODS: Unsaturated fatty acid was purified by refinement, salt fractionation,hypothermy-sylvite method and urea clathration method. After activated by methyl ester, the content of EPA and DHA were detected by GC chromatography. RESULTS: Highly purified unsaturated fatty acids were purified from puffer fish liver oil and the content of EPA and DHA was 0.261 9 g· g-1 and 0.452 7 g· g-1, respectively. The calibration curves were linear in the ranges of 0.05-0.25 mg· mL-1 for EPA methyl ester and DHA methyl ester. CONCLUSION: It is a feasible method for purification of EPA and DHA in puffer fish liver oil. The method is simple, accurate and reproducible for the content determination.%目的:研究河豚鱼肝油中二十碳五烯酸(EPA)和二十二碳六烯酸(DHA)的纯化方法,并建立EPA和DHA的含量测定方法.方法:河豚鱼肝油经精炼、盐析、低温-钾盐乙醇法和尿素包合法相结合纯化得不饱和脂肪酸;不饱和脂肪酸经甲脂化后,采用气相色谱法测定EPA和DHA的含量.结果:河豚鱼肝油经纯化可获得高纯度的不饱和脂肪酸;EPA和DHA的含量分别为0.261 9g·g-1和0.4527 g·g-1.EPA甲酯和DHA甲酯标准品浓度均在0.05~0.25mg·mL-1范围内同其与内标的峰面积比值呈良好的线性关系(r分别为0.999 7、0.999 8).结论:河豚鱼肝油中EPA和DHA的纯化方法可行;检测方法操作简单、结果准确、重复性良好,是一种可行的含量测定方法.

  9. Constraining the cause of the end-Guadalupian extinction with coupled records of carbon and calcium isotopes

    Science.gov (United States)

    Jost, Adam B.; Mundil, Roland; He, Bin; Brown, Shaun T.; Altiner, Demir; Sun, Yadong; DePaolo, Donald J.; Payne, Jonathan L.

    2014-06-01

    A negative δC13 excursion in carbonate sediments near the Guadalupian/Lopingian (Middle/Late Permian) boundary has been interpreted to have resulted from a large carbon cycle disturbance during the end-Guadalupian extinction event (ca. 260 Ma). However, the carbon isotope data alone are insufficient to uniquely determine the type and magnitude of perturbation to the global carbon cycle. Calcium isotopes can be used to further constrain the cause of a carbon isotope excursion because the carbon and calcium cycles are coupled via CaCO3 burial. In this study, we present coupled carbon and calcium isotope records from three Guadalupian-Lopingian (G/L) sections in China (Penglaitan and Chaotian) and Turkey (Köserelik Tepe). The δC13 and δCa44/40 records differ among our studied sections and do not co-vary in the same manner. No section shows δC13 and δCa44/40 changes consistent with massive, rapid volcanic CO2 emissions or methane clathrate destabilization. Additionally, many sections with large (>3‰) changes in δC13 exhibit δO18 evidence for diagenetic alteration. Only one section exhibits a large excursion in the δCa44/40 of limestone but the absence of a similar excursion in the δCa44/40 of conodont apatite suggests that the limestone excursion reflects a mineralogical control rather than a perturbation to the global calcium cycle. Hence, we interpret the large isotopic changes observed in some sections to have resulted from local burial conditions or diagenetic effects, rather than from a large carbon and calcium cycle disturbance. Perturbations to the global carbon and calcium cycles across the G/L transition were much less intense than the disturbances that occurred across the subsequent Permian-Triassic boundary. This finding is consistent with the much smaller magnitude of the end-Guadalupian extinction relative to the end-Permian.

  10. Origin and character of gaseous hydrocarbons in the hydrate and non-hydrate charged sediments on the Norway - Svalbard margins

    Energy Technology Data Exchange (ETDEWEB)

    Vaular, Espen Nesheim

    2011-05-15

    Gas incubated in clathrate water-structures, stabilizes the hydrogen bonded substance termed gas hydrate. In the marine environment vast amount of carbon is stored as gas hydrates within the temperature and pressure zone these ice-like structures are stable. Natural gas hydrate mapping and characterization is important basic research that brings about critical knowledge concerning various topics. Natural gas hydrates is a vital part of the carbon cycle, it is a potential energy resource (and thereby a potential climate agent) and it is a potential geo-hazard. One of the goals the GANS initiative aimed at exploring, was the hydrate bearing sediment of the Norway -Svalbard margins, to investigate the character and expansion of natural gas hydrates. Part of the investigation was to define how the gas in the hydrated sediment was produced and where it came from. As a result this thesis addresses the matter of light hydrocarbon characterization and origin in two Norwegian hydrate deposits. On cruises to Vestnesa on the Svalbard margin and to Nyegga in the mid-Norwegian margin, samples of hydrate charged and non-hydrate charged sediments were obtained and analyzed. Through compositional and isotopic analyses the origin of the hydrate bound gas in the fluid escape feature G11 at Nyegga was determined. The hydrate incubated methane is microbial produced as well as parts of the hydrate bound ethane. The compositional analysis in both the Nyegga area and at the Vestnesa Ridge points at thermogenic contributions in the sediment interstitials and pore water. The two hydrate bearing margins show large differences in hydrocarbon content and microbial activity in the pockmarks investigated. The gravity cores from the penetrated pockmark at Vestnesa showed low hydrocarbon content and thus suggest ceased or periodic venting. The fluid flow escape features at Nyegga show large variety of flux rates based on ROV monitoring and headspace analysis of the sediment and pore water. The

  11. Study on gas hydrate as a new energy resource in the 21th century

    Energy Technology Data Exchange (ETDEWEB)

    Ryu, Byeong-Jae; Kwak Young-Hoon; Kim, Won-Sik [Korea Institute of Geology Mining and Materials, Taejon (KR)] (and others)

    1999-12-01

    Natural gas hydrate, a special type of clathrate hydrates, is a metastable solid compound which mainly consists of methane and water, and generally called as gas hydrate. It is stable in the specific low-temperature/high-pressure conditions. Gas hydrates play an important role as major reservoir of methane on the earth. On the other hand, the formation and dissociation of gas hydrates could cause the plugging in pipeline, gas kick during production, atmospheric pollution and geohazard. To understand the formation and dissociation of the gas hydrate, the experimental equilibrium conditions of methane hydrate were measured in pure water, 3 wt.% NaCl and MgCl{sub 2} solutions. The equilibrium conditions of propane hydrates were also measured in pure water. The relationship between methane hydrate formation time and overpressure was also analyzed through the laboratory work. The geophysical surveys using air-gun system and multibeam echo sounder were implemented to develop exploration techniques and to evaluate the gas hydrate potential in the East Sea, Korea. General indicators of submarine gas hydrates on seismic data is commonly inferred from the BSR developed parallel to the see floor, amplitude blanking at the upper part of the BSR, and phase reversal and decrease of the interval velocity at BSR. The field data were processed using Geobit 2.9.5 developed by KIGAM to detect the gas hydrate indicators. The accurate velocity analysis was performed by XVA (X-window based Velocity Analysis). Processing results show that the strong reflector occurred parallel to the sea floor were shown at about 1800 ms two way travel time. The interval velocity decrease at this strong reflector and at the reflection phase reversal corresponding to the reflection at the sea floor. Gas hydrate stability field in the study area was determined using the data of measured hydrate equilibrium condition, hydrothermal gradient and geothermal gradient. The depth of BSR detected in the seismic

  12. Effects of 3 Kinds of Hydrophilic Polymers on Ketoprofen/Cyclodextrin Complex Solubilization%3种亲水性聚合物对酮洛芬/环糊精包合物增溶作用的影响

    Institute of Scientific and Technical Information of China (English)

    许伟

    2012-01-01

    OBJECTIVE: To investigate the effect of hydrophilic polymers on the solubility of drug in ketoprofen/cyclodextrin complex. METHODS: Different kinds of polymers including 0.1% PVP K30, 0.1% HPMC, 0.1% PEG 6000, were added into the ketoprofen/cyclodextrin system respectively or not, and phase solubility method was adapted to calculate the dissolution and the apparent stability constants (Ka) under 25 ℃. RESULTS: In 4 kinds of system, PEG 6000 increased the solubility of ketoprofen significantly, which was from 172.9 mmol·L-1 to 308.9 mmol·L-1, and the Ka increased from 0.042 to 0.940. CONCLUSION: Hydrophilic polymer PEG 6000 is shown to increase the clathration effect of cyclodextrin on drugs.%目的:研究聚合物对酮洛芬/环糊精包合物中药物溶解度的影响.方法:在酮洛芬/羟丙-β-环糊精体系中不加聚合物以及分别添加浓度均为0.1%的聚乙烯吡咯烷酮(K30)、羟丙基甲基纤维素(HPMC)、聚乙二醇(6000)3种高分子水溶性聚合物的情况下,于25℃下采用相溶解度法,考察药物在4种体系中的溶解度和表观稳定常数(Ks).结果:4种体系中,以加入聚乙二醇(6000)后酮洛芬的溶解度增加最明显,从172.9 mmol·L-1增加到308.9mmol·L-1,Ks从0.042增大到0.940.结论:亲水性聚合物聚乙二醇(6000)能够增强药物与环糊精的包合作用.

  13. Magnetofossils as tracers of oxygenation change: a case study from the stratified Pettaquamscutt River Estuary

    Science.gov (United States)

    Chen, A. P.; Berounsky, V. M.; Chan, M. K.; Moskowitz, B. M.; Andrade Lima, E.; Kopp, R. E.; Cady, C.; Weiss, B. P.; Hesse, P. P.

    2013-12-01

    Magnetotactic bacteria (MB) are motile organisms commonly found around the oxic-anoxic-interface (OAI) in sediments and stratified water columns. Magnetite and greigite crystals synthesized by MB intracellularly, termed magnetosomes, can be preserved in sediments as magnetofossils. Changes in OAI thickness (due to changes in temperature, clathrate dissociation & methane oxidation, organic carbon supply/oxidation, or sedimentation rate) would produce proportional changes in MB population and sedimentary magnetofossil concentration. While potentially useful as an oxygenation proxy, magnetofossil quantification techniques and variables controlling their preservation in sediments need to be better understood. Most prior work focused on cultured magnetite-MB and sediment mixtures while studies of greigite-MB (found just below the OAI in the sulfidic hypolimnion) is lacking because axenic cultures do not exist. To address these issues, we study wild magnetite- and greigite-MB from the seasonally stratified Pettaquamscutt River Estuary Upper Basin (RI, USA) as a function of water depth, d. Transmission electron microscope imaging of 21 MB (377 magnetosomes) revealed a complexity in wild MB not found in cultures. From d=3.9 m-7.0 m, live-cell assays confirmed the presence of multiple MB morphotypes, both north- (majority) and south-seeking (minority), and a few magnetic protists. Based on a previous microscopy study just 1.4 km south of Upper Basin (Bazylinski et al., 1995), magnetite-MB are expected for dgreigite-MB for 5.0 mgreigite-MB for d>6.0 m. Coercivity distributions for all depths are characterized by a small variance, reflecting uniformity in magnetosome size. Interestingly, despite changing from dominant magnetite to greigite-MB with increasing depth, the median coercivity remained largely unchanged. Median coercivity is therefore not diagnostic of magnetosome mineralogy. We also report ferromagnetic resonance spectroscopy (FMR) results. The first derivative of

  14. Pressure laboratories for parameter controlled experimentation of deep sea environments

    Science.gov (United States)

    Steffen, H.; Holscher, B.; Gust, G.; Thomsen, L.

    2003-04-01

    the measurement of pressure effects on bacterial respiration rates and the trapping and observation of deep sea zooplankton. Gas hydrate related experiments address the decomposition of core sampled natural clathrates as well as growth and dissolution of artificial, homogenous gas hydrates under varying environmental parameters such as pressure, temperature and boundary layer stress (see Drews et al.). Drews, M. et al.: Simulating the dissolution of gas hydrates at the deep sea floor in the pressure chamber under controlled P/T and shear stress conditions, this volume.

  15. Air fractionation in plate-like inclusions within the EPICA-DML deep ice core

    Science.gov (United States)

    Nedelcu, A.; Faria, S. H.; Kipfstuhl, S.; Schmidt, B.; Kuhs, W. F.

    2009-04-01

    than this, they suggest that the diffusion of chemical traces in the ice matrix may not be negligible, at least locally, on a timescale of few years. These results could be important for the interpretation of ice-core paleoclimate records. Muguruma, J., S. Mae and A. Higashi, 1966. Void formation by non-basal glide in ice single crystals, Philos. Mag., 13(123), 625-629. Mae, S., 1968. Void formation during non-basal glide in ice single crystals under tension, Philos. Mag., 18(151), 101-114. Gow, A. J., 1971. Relaxation of ice in deep drill cores from Antarctica, J. Glaciol., 76(11), 2533-2541. Nedelcu, A. F., S. H. Faria and W. F. Kuhs, in press. Raman spectra of plate-like inclusions in the EPICA-DML ice core. J. Glaciol., 55(189) Nakahara, J., Y. Shigesato, A. Higashi, T. Hondoh and C.C. Langway, 1988. Raman spectra of natural clathrates in deep ice cores, Philos. Mag. B, 57(3), 421-430. Ikeda, T., H. Fukazawa, S. Mae, L. Pepin, P. Duval, B. Champagnon, V. Y. Lipenkov and T. Hondoh, 1999. Extreme fractionation of gases caused by formation of clathrate hydrates in Vostok Antarctic ice, Geophys. Res. Lett., 26(1), 91-94. Ikeda-Fukazawa, T., T. Hondoh, T. Fukumura, H. Fukazawa and S. Mae, 2001. Variation in N2/O2 ratio of occluded air in Dome Fuji antarctic ice, J. Geophys. Res., 106(D16), 17799-17810. Ikeda-Fukazawa, T., K. Fukumizu, K. Kawamura, S. Aoki, T. Nakazawa and T. Hondoh, 2005. Effects of molecular diffusion on trapped gas composition in polar ice cores, Earth Planet.Sci.Lett.,229(3-4),183-192. Severinghaus, J. P., and M. O. Battle, 2006. Fractionation of gases in polar ice during bubble close-off: new constraints from firn air, Ne, Kr and Xe observations, Earth Planet. Sci. Lett., 244(1-2), 474-500.

  16. Enceladus' Interior: A Liquid Circulation Model

    Science.gov (United States)

    Matson, Dennis L.; Johnson, Torrence; Lunine, Jonathan; Castillo-Rogez, Julie

    We are studying a model for Enceladus' interior in which the water, gas, dust and heat are supplied to the plumes by a relatively deeply circulating brine solution. Data indicates such a source for the erupting material. On the basis of ammonia in the plume gas Waite et al. [1] suggested that the jets might originate from a liquid water region under Enceladus' icy surface. Postberg et al. [2] noted that the presence of ". . . grains that are rich in sodium salts (0.5-2 percent by mass). . . can arise only if the plumes originate from liquid water." Waite et al. [1] also regard the some of the plume chemicals as evidence for interactions with an ice layer presumably overlying the liquid water reservoir. They suggest that this could be in the form of dissociation of clathrate hydrates [3]. Additionally, there is a large heat flow of more than 15 GW [4, 5] coming out of Enceladus' south polar region. We consider a model that brings heat and chemical species up to the surface from a reservoir or "ocean" located below the ice crust that may be many tens of kilometers thick. Water transits to the surface via vertical conduits. The Cassini INMS data suggest that the water has a relatively large gas content of order a few percent. As the water travels upward and the pressure is released, exolving gases form bubbles. Since the bubbly liquid is less dense than the ice, it moves upward. (This part of the model is a variant of the "Perrier Ocean" Europa model of Crawford and Stevenson [6]. A similar model was studied for Ganymede by Murchie and Head [7].) Postberg et al. [2] model the plume eruptions that result from the water, gases, salts, and other chemicals that our circulation model provides. In the near-surface reservoir feeding the plumes, bubbles reaching the surface of the water pop and throw a very fine spray. Some of these very small droplets of brine exit with the plume gas and provide the observed salt-rich dust particles [2]. Much of the water-borne heat is

  17. Global Assessment of Methane Gas Hydrates: Outreach for the public and policy makers

    Science.gov (United States)

    Beaudoin, Yannick

    2010-05-01

    The United Nations Environment Programme (UNEP), via its official collaborating center in Norway, GRID-Arendal, is in the process of implementing a Global Assessment of Methane Gas Hydrates. Global reservoirs of methane gas have long been the topic of scientific discussion both in the realm of environmental issues such as natural forces of climate change and as a potential energy resource for economic development. Of particular interest are the volumes of methane locked away in frozen molecules known as clathrates or hydrates. Our rapidly evolving scientific knowledge and technological development related to methane hydrates makes these formations increasingly prospective to economic development. In addition, global demand for energy continues, and will continue to outpace supply for the foreseeable future, resulting in pressure to expand development activities, with associated concerns about environmental and social impacts. Understanding the intricate links between methane hydrates and 1) natural and anthropogenic contributions to climate change, 2) their role in the carbon cycle (e.g. ocean chemistry) and 3) the environmental and socio-economic impacts of extraction, are key factors in making good decisions that promote sustainable development. As policy makers, environmental organizations and private sector interests seek to forward their respective agendas which tend to be weighted towards applied research, there is a clear and imminent need for a an authoritative source of accessible information on various topics related to methane gas hydrates. The 2008 United Nations Environment Programme Annual Report highlighted methane from the Arctic as an emerging challenge with respect to climate change and other environmental issues. Building upon this foundation, UNEP/GRID-Arendal, in conjunction with experts from national hydrates research groups from Canada, the US, Japan, Germany, Norway, India and Korea, aims to provide a multi-thematic overview of the key

  18. The European Research Infrastructure IAGOS - From dedicated field studies to routine observations of the atmosphere by instrumented passenger aircraft

    Science.gov (United States)

    Petzold, Andreas; Volz-Thomas, Andreas; Gerbig, Christoph; Thouret, Valerie; Cammas, Jean-Pierre; Brenninkmeijer, Carl A. M.; Iagos Team

    2013-04-01

    The global distribution of trace species is controlled by a complex interplay between natural and anthropogenic sources and sinks, atmospheric short- to long-range transport, and in future by diverse, largely not yet quantified feedback mechanisms such as enhanced evaporation of water vapour in a warming climate or possibly the release of methane from melting marine clathrates. Improving global trace gas budgets and reducing the uncertainty of climate predictions crucially requires representative data from routine long-term observations as independent constraint for the evaluation and improvement of model parameterizations. IAGOS (In-service Aircraft for a Global Observing System; www.iagos.org) is a new European Research Infrastructure which operates a unique global observing system by deploying autonomous instruments aboard a fleet of passenger aircraft. IAGOS consists of two complementary building blocks: IAGOS-CORE deploys newly developed high-tech instrumentation for regular in-situ measurements of atmospheric chemical species (O3, CO, CO2, NOx, NOy, H2O, CH4), aerosols and cloud particles. Involved airlines ensure global operation of the network. In IAGOS-CARIBIC a cargo container is operated as a flying laboratory aboard one passenger aircraft. IAGOS aims at the provision of long-term, frequent, regular, accurate, and spatially resolved in-situ observations of the atmospheric chemical composition in the UTLS and the extra tropical troposphere and on vertical profiles of greenhouse gases, reactive trace gases and aerosols throughout the troposphere. It builds on almost 20 years of scientific and technological expertise gained in the research projects MOZAIC (Measurement of Ozone and Water Vapour on Airbus In-service Aircraft) and CARIBIC (Civil Aircraft for the Regular Investigation of the Atmosphere Based on an Instrument Container). The European consortium includes research centres, universities, national weather services, airline operators and aviation

  19. 天然气水合物形成与生长影响因素综述%Review of influence factors of natural gas hydrate formation and growth

    Institute of Scientific and Technical Information of China (English)

    丁麟; 史博会; 吕晓方; 柳扬; 宫敬

    2016-01-01

    Natural gas hydrate is a kind of complex clathrate crystal formed by water and natural gas molecules,which has an important significance for research and utilization in industries of oil/gas pipeline transportation,natural gas storage and refrigeration. While the formation and growth of natural gas hydrate is a complex process involving multi-components and multistages,and the influence of different factors on hydrate formation and growth still needs to be understood. This paper introduces the physical process of natural gas formation and three hypotheses of natural gas nucleation. Then,the influences of substrate amphipathy,additives,porous media environment and impurities,liquid composition,temperature,pressure and flow conditions on hydrate formation and growth are discussed. At last,this paper points out that quantification of inhibition of hydrate caused by different crude oil compositions,influence of wax on mass transfer and heat transfer during hydrate growth,and a microscopic mechanism of kinetic hydrate inhibition should be further studied in the future.%天然气水合物(NGH)是水分子和天然气分子形成的一种复杂的笼型晶体,其在油气管道输送、天然气储存和制冷等行业中都具有重要的研究意义和利用价值,但天然气水合物的形成是一个多组分、多阶段的复杂过程,不同因素对于天然气水合物形成和生长的影响尚有待明确。本文介绍了天然气水合物形成的物理过程以及水合物成核的3种机理假说;详细梳理了基质两亲性、添加剂、多孔介质环境和杂质、液体组成、温度压力以及流动条件等因素对于天然气水合物形成和生长的影响,并对其作了简要分析。同时指出,原油组成对于水合物抑制效果的定量化、蜡晶结构对于水合物形成过程中传质和传热的影响以及微观化的动力学抑制剂抑制机理等都是水合物相关研究中需要进一步深入探究和明确的问题。

  20. Apparent Km of mitochondria for oxygen computed from Vmax measured in permeabilized muscle fibers is lower in water enriched in oxygen by electrolysis than injection

    Directory of Open Access Journals (Sweden)

    Zoll J

    2015-07-01

    Full Text Available Joffrey Zoll,1 Jamal Bouitbir,1 Pascal Sirvent,2 Alexis Klein,3 Antoine Charton,1,4 Liliana Jimenez,3 François R Péronnet,5 Bernard Geny,1 Ruddy Richard61Physiology Department, Faculty of Medicine and EA3072, Université de Strasbourg, Strasbourg, 2Clermont Université, Université Blaise Pascal, EA 3533, Laboratoire des Adaptations Métaboliques à l’Exercice en Conditions Physiologiques et Pathologiques, Clermont-Ferrand, 3Danone Research, Centre Daniel Carasso, Palaiseau, 4Department of Anesthesia and Critical Care and EA3072, Hôpital de Hautepierre, Université de Strasbourg, France; 5Kinesiology Department, Université de Montréal, Montréal, QC, Canada; 6Department of Sport Medicine and Functional Explorations and INRA UMR 1019, Faculty of Medicine, Université d’Auvergne, Clermont-Ferrand, FranceBackground: It has been suggested that oxygen (O2 diffusion could be favored in water enriched in O2 by a new electrolytic process because of O2 trapping in water superstructures (clathrates, which could reduce the local pressure/content relationships for O2 and facilitate O2 diffusion along PO2 gradients.Materials and methods: Mitochondrial respiration was compared in situ in saponin-skinned fibers isolated from the soleus muscles of Wistar rats, in solution enriched in O2 by injection or the electrolytic process 1 at an O2 concentration decreasing from 240 µmol/L to 10 µmol/L (132 mmHg to 5 mmHg, with glutamate–malate or N, N, N', N'-tetramethyl-p-phenylenediamine dihydrochloride (TMPD–ascorbate (with antimycin A as substrates; and 2 at increasing adenosine diphosphate (ADP concentration with glutamate–malate as substrate.Results: As expected, maximal respiration decreased with O2 concentration and, when compared to glutamate–malate, the apparent Km O2 of mitochondria for O2 was significantly lower with TMPD–ascorbate with both waters. However, when compared to the water enriched in O2 by injection, the Km O2 was

  1. Natural Gas Hydrates as CH4 Source and CO2 Sink - What do SO2 Impurities do?

    Science.gov (United States)

    Beeskow-Strauch, B.; Schicks, J. M.; Spangenberg, E.; Erzinger, J.

    2009-04-01

    The large amounts of gas hydrates stored in natural reservoirs are thought to be a promising future energy source. The recently discussed idea of methane extraction from these formations, together with the subsequent storage of CO2 in form of gas hydrates is an elegant approach to bring forward. A number of experiments have been performed on lab scale showing the replacement of CH4 by CO2 and vice versa. For instance, Graue and Kvamme (2006) demonstrated with Magnetic Resonance Images of core plug experiments the possibility of CH4 extraction by using liquid CO2. Laser Raman investigations of Schicks et al. (2007) showed, on the other hand, the ineffectiveness and slowness of the CH4 exchange reaction with gaseous CO2. After 120 hours, only 20% CH4 were exchanged for CO2. Natural methane hydrates which include often higher hydrocarbons tend to be even more stable than pure methane hydrates (Schicks et al., 2006). Contrary to lab conditions, industrial emitted CO2 contains - despite much effort to clean it - traces of impurities. For instance, CO2 emitted from the state-of-the-art Vattenfall Oxyfuel pilot plant in Schwarze Pumpe should reach a quality of >99.7% CO2 but still contains small amounts of N2, Ar, O2, SOx and NOx (pers. comm. Dr. Rolland). Here we present a microscopic and laser Raman study in a p-T range of 1 to 4 MPa and 271 to 280K focussing on CO2 hydrate formation and CH4-exchange reaction in the presence of 1% SO2. The experiments have been performed in a small-scale cryocell. The Raman spectra show that CO2 and SO2 occupy both large and small cages of the hydrate lattice. SO2 occurs strongly enriched in the hydrate clathrate, compared to its concentration in the feed gas which causes a strong acidification of the liquid phase after hydrate dissociation. Our study reveals that the hydrate formation rate from impure CO2 is similar to that of pure CO2 hydrate but that the stability of the CO2-SO2-hydrate exceeds that of pure CO2 hydrate. The improved

  2. Study on the stability of anthocyanin in purple sweet potato beverage%紫甘薯饮料中花青素的稳定性研究

    Institute of Scientific and Technical Information of China (English)

    孙鹏尧; 周芳宁; 李喜层; 曹燕华; 袁素辉; 牟德华

    2014-01-01

    The spectrum characteristics of anthocyanins in purple sweet potato beverage with different pH was analyzed, besides, the effect of pH, temperature, Vc, sugar, and light on the stability of anthocyanin from purple sweet potato beverage were studied. The results showed that the anthocyanins had better stability at the pH of 2.2, 3.0, 4.0. The stability gradually decreased along with the pH increased. High temperature had obvious effect on the stability of purple sweet potato antho-cyanins and the higher the temperature was, the lower retention of anthocyanin had. Vc could accelerate the degradation of anthocyanins. Glucose and lactose had no effect on the stability of anthocyanins. Clathrate which formed of Fe3+and antho-cyan might reduce the stability of anthocyanins, however, other metal ions had no influence almost. The stability of antho-cyanins decreased under the light. Natural light had no obvious impact in a short period of time. Incandescent light and ul-traviolet lamp could speed up decomposition of anthocyanin.%研究了不同pH值紫甘薯饮料中花青素的色泽光谱特性以及pH值、温度、抗坏血酸、糖、光照等因素对紫甘薯饮料中花青素稳定性的影响。结果表明, pH值为2.2、3.0、4.0时花青素较稳定,随着pH值的升高,稳定性逐渐降低;高温处理对紫甘薯花青素的稳定性的影响较显著,温度越高,花青素的保留率越低;抗坏血酸的加入会加速花色苷的降解;葡萄糖和乳糖的加入对花色苷的稳定性无影响; Fe3+与花青素类物质形成络合物,降低了花青素的稳定性,其他的金属离子对花色苷的稳定性影响不大;光照使花青素稳定性降低,自然光在短时间内影响较小,花色苷在白炽灯和紫外灯照射下降解速度加快。

  3. Oceanic ecosystem dynamics during gigantic volcanic episodes: the Ontong Java and Manihiki Plateaus recorded by calcareous nannoplankton. (Invited)

    Science.gov (United States)

    Erba, E.

    2010-12-01

    Earth's volcanic activity introduces environmental stress that biota are forced to survive. There is a general consensus on the role of volcanogenic carbon dioxide increases, and implicit tectonic-igneous events, triggering major climate changes and profound variations in chemical, physical and trophic characteristics of the oceans through the Phanerozoic. Cretaceous geological records indicate conditions of excess atmCO2 (up to 2000-3000 ppm) derived from construction of Large Igneous Provinces (LIPs). In such “high CO2 world” and greenhouse conditions, the deep ocean became depleted of oxygen promoting the accumulation and burial of massive amounts of organic matter; such episodes are recognized as Oceanic Anoxic Events (OAEs) and their geological records merit careful examination of how the Earth system, and Life in particular, can overcome extreme experiments of global change. The Early Aptian (˜ 120 million years ago) OAE1a is a complex example of volcanicCO2-induced environmental stress. There is a general consensus on the causes of this case-history, namely excess CO2 derived from the construction of the Ontong Java-Manihiki LIP. Multi- and inter-disciplinary studies of the OAE1a have pointed out C, O, Os, Sr isotopic anomalies, a biocalcification crisis in pelagic and neritic settings, enhanced fertility and primary productivity, as well as ocean acidification. Available cyclochronology allows high-resolution dating of biotic and environmental fluctuations, providing the precision necessary for understanding the role of volcanogenic CO2 on nannoplankton biocalcification, adaptations, evolutionary innovation and/or extinctions. The reconstructed sequence of volcanogenic CO2 pulses, and perhaps some clathrate melting, triggered a climate change to supergreenhouse conditions, anoxia and ocean acidification. The demise of heavily calcified nannoconids and reduced calcite paleofluxes marks beginning of the pre-OAE1a calcification crisis. Ephemeral coccolith

  4. The science of the lunar poles

    Science.gov (United States)

    Lucey, P. G.

    2011-12-01

    It was the great geochemist Harold Urey who first called attention to peculiar conditions at the poles of the Moon where the very small inclination of the lunar spin axis with respect to the sun causes craters and other depressions to be permanently shaded from sunlight allowing very low temperatures. Urey suggested that the expected low temperature surfaces could cold trap and collect any vapors that might transiently pass through the lunar environment. Urey's notion has led to studies of the poles as a new research area in lunar science. The conditions and science of the poles are utterly unlike those of the familiar Moon of Neil Armstrong, and the study of the poles is similar to our understanding of the Moon itself at the dawn of the space age, with possibilities outweighing current understanding. Broadly, we can treat the poles as a dynamic system of input, transport, trapping, and loss. Volatile sources range from continuous, including solar wind, the Earth's polar fountain and micrometeorites, to episodic, including comets and wet asteroids, to nearly unique events including late lunar outgassing and passage through giant molecular clouds. The lunar exosphere transports volatiles to the poles, complicated by major perturbances to the atmosphere by volatile-rich sources. Trapping includes cold trapping, but also in situ creation of more refractory species such as organics, clathrates and water-bearing minerals, as well as sequester by regolith overturn or burial by larger impacts. Finally, volatiles are lost to space by ionization and sweeping. Spacecraft results have greatly added to the understanding of the polar system. Temperatures have been precisely measured by LRO, and thermal models now allow determination of temperature over the long evolution of the lunar orbit, and show very significant changes in temperature and temperature distribution with time and depth. Polar topography is revealed in detail by Selene and LRO laser altimeters while direct

  5. Zintl and intermetallic phases grown from calcium/lithium flux

    Science.gov (United States)

    Blankenship, Trevor

    , (Im-3, a = 9.6055(8)A) which contains C 34- units. A very similar phase, Ba12InC 18H4 (Im-3,a = 11.1415(8) A), was grown from the reaction of indium, carbon, and LiH in Ba/Li flux. This compound also includes C34- units. Preliminary Ca/Li flux reactions of aluminum with other main group elements have produced several new phases: a hydride clathrate Ca31Al2H25 in cubic Fd-3m (a=18.0835(15) A), Ca24Al2(C 1-xHx)N2H16 in tetragonal P42/nmc (a=15.9069(12) A, c=13.7323(10) A, and Ca 4Al2N5 in orthorhombic Pna21 (a = 11.2331(1) A, b=9.0768(8) A, c=6.0093(5) A.

  6. Comet 67P's Pitted Surface

    Science.gov (United States)

    Kohler, Susanna

    2015-11-01

    High-resolution imagery of comet 67P ChuryumovGerasimenko has revealed that its surface is covered in active pits some measuring hundreds of meters both wide and deep! But what processes caused these pits to form?Pitted LandscapeESAs Rosetta mission arrived at comet 67P in August 2014. As the comet continued its journey around the Sun, Rosetta extensively documented 67Ps surface through high-resolution images taken with the on-board instrument NavCam. These images have revealed that active, circular depressions are a common feature on the comets surface.In an attempt to determine how these pits formed, an international team of scientists led by Olivier Mousis (Laboratory of Astrophysics of Marseille) has run a series of simulations of a region of the comet the Seth region that contains a 200-meter-deep pit. These simulations include the effects of various phase transitions, heat transfer through the matrix of ices and dust, and gas diffusion throughout the porous material.Escaping VolatilesAdditional examples of pitted areas on 67Ps northern-hemisphere surface include the Ash region and the Maat region (both imaged September 2014 by NavCam) [Mousis et al. 2015]Previous studies have already eliminated two potential formation mechanisms for the pits: impacts (the sizes of the pits werent right) and erosion due to sunlight (the pits dont have the right shape). Mousis and collaborators assume that the pits are instead caused by the depletion of volatile materials chemical compounds with low boiling points either via explosive outbursts at the comets surface, or via sinkholes opening from below the surface. But what process causes the volatiles to deplete when the comet heats?The authors simulations demonstrate that volatiles trapped beneath the comets surface either in icy structures called clathrates or within amorphous ice can be suddenly released as the comet warms up. The team shows that the release of volatiles from these two structures can create 200-meter

  7. Global climate change linkage with episodic methane release even in the western north Pacific in the last glacial period

    International Nuclear Information System (INIS)

    The remarkable similarity of late Quaternary atmospheric methane and temperature variations recorded in ice cores suggests that methane has played a significant role in millennial-scale climatic oscillations, especially Dansgaard-Oeschger (D-O) interstadial. Variations in the size and distribution of marine-sedimentary reservoirs of methane on the continental margins throughout the world's oceans are thought to be one of the important factors controlling the global methane cycle. Marine sediments can act as hosts to gas hydrates under appropriate conditions of high pressure and/or low temperature, and sufficient organic carbon; on the other hand, they show a significant sensitivity to small perturbations in the physical and chemical conditions within the reservoir. During the Last Glacial, direct and indirect evidence accumulated from geochemical data suggests that methane episodically released from hydrate trapped in the seafloor sediments. Recently, Kennett and coworkers interpreted δ13C variations of planktonic and benthic foraminifera found in Last Glacial sediments in the Santa Barbara Basin (SBB) as evidence for periodic releases of methane, arising from the dissociation of methane hydrate, and its subsequent oxidation in bottom- and/or surface-water environments. This result provided the basis for the 'Clathrate Gun Hypothesis', which highlights the potential role of methane hydrate in Quaternary variations in atmospheric methane concentrations. According to recent observations of anomalous bottom-simulating reflections(BSR), the northwest Pacific marginal sediments around Japan main islands bear large abundances of methane hydrate. In this study, the piston cores from the continental slope sediments in the Oyashio current region, which recently is found to bear immense amounts of methane hydrate, have been investigated about planktonic and benthic foraminiferal carbon isotope records during the past 34 cal. kyr BP. Moreover, in order to investigate

  8. Highly efficient molecular simulation methods for evaluation of thermodynamic properties of crystalline phases

    Science.gov (United States)

    Moustafa, Sabry Gad Al-Hak Mohammad

    Molecular simulation (MS) methods (e.g. Monte Carlo (MC) and molecular dynamics (MD)) provide a reliable tool (especially at extreme conditions) to measure solid properties. However, measuring them accurately and efficiently (smallest uncertainty for a given time) using MS can be a big challenge especially with ab initio-type models. In addition, comparing with experimental results through extrapolating properties from finite size to the thermodynamic limit can be a critical obstacle. We first estimate the free energy (FE) of crystalline system of simple discontinuous potential, hard-spheres (HS), at its melting condition. Several approaches are explored to determine the most efficient route. The comparison study shows a considerable improvement in efficiency over the standard MS methods that are known for solid phases. In addition, we were able to accurately extrapolate to the thermodynamic limit using relatively small system sizes. Although the method is applied to HS model, it is readily extended to more complex hard-body potentials, such as hard tetrahedra. The harmonic approximation of the potential energy surface is usually an accurate model (especially at low temperature and large density) to describe many realistic solid phases. In addition, since the analysis is done numerically the method is relatively cheap. Here, we apply lattice dynamics (LD) techniques to get the FE of clathrate hydrates structures. Rigid-bonds model is assumed to describe water molecules; this, however, requires additional orientation degree-of-freedom in order to specify each molecule. However, we were able to efficiently avoid using those degrees of freedom through a mathematical transformation that only uses the atomic coordinates of water molecules. In addition, the proton-disorder nature of hydrate water networks adds extra complexity to the problem, especially when extrapolating to the thermodynamic limit is needed. The finite-size effects of the proton disorder contribution is

  9. Tracking the MSL-SAM methane detection source location Through Mars Regional Atmospheric Modeling System (MRAMS)

    Science.gov (United States)

    Pla-García, Jorge

    2016-04-01

    1. Introduction: The putative in situ detection of methane by Sample Analysis at Mars (SAM) instrument suite on Curiosi-ty at Gale crater has garnered significant attention because of the potential implications for the presence of geological methane sources or indigenous Martian organisms [1, 2]. SAM reported detection of back-ground levels of atmospheric methane of mean value 0.69±0.25 parts per billion by volume (ppbv) at the 95% confidence interval (CI). Additionally, in four sequential measurements spanning a 60-sol period, SAM observed elevated levels of methane of 7.2±2.1 ppbv (95% CI), implying that Mars is episodically producing methane from an additional unknown source. There are many major unresolved questions regard-ing this detection: 1) What are the potential sources of the methane release? 2) What causes the rapid decrease in concentration? and 3) Where is the re-lease location? 4) How spatially extensive is the re-lease? 5) For how long is CH4 released? Regarding the first question, the source of methane, is so far not identified. It could be related with geo-logical process like methane release from clathrates [3], serpentinisation [4] and volcanism [5]; or due to biological activity from methanogenesis [6]. To answer the second question, the rapid decrease in concentration, it is important to note that the photo-chemical lifetime of methane is of order 100 years, much longer than the atmospheric mixing time scale, and thus the gas should tend to be well mixed except near a source or shortly after an episodic release. The observed spike of 7 ppb from the background of year, simulations were con-ducted at Ls 0, 90, 180 and 270. Two additional sim-ulations at Ls 225 and 315 were explored to better understand the unique meteorological setting cen-tered around Ls 270. Ls 270 was shown to be an anomalous season when air within and outside the crater was well mixed by strong, flushing, northerly flow and large amplitude breaking mountain waves: air

  10. Global Methane Biogeochemistry

    Science.gov (United States)

    Reeburgh, W. S.

    2003-12-01

    impact of CH4 on climate. The Intergovernmental Panel on Climate Change (IPCC) has published periodic updates (see, e.g., IPCC, 2001).Substantial advances have resulted from research aimed at understanding the global CH4 mixing ratio increase. Time-series measurements of atmospheric CH4 have continued, new CH4 flux measurements in a range of environments have been reported, and data allowing use of the stable isotope (13C/12C, 2H/1H) composition of CH4 as an independent budget constraint have increased. The importance of microbial oxidation of CH4 has been recognized and modeled; the possible role of CH4 clathrate hydrates in the global budget has been clarified with the introduction of new technology. Studies of CH4 trapped in ice cores from the Greenland and Antarctic ice caps have continued, resulting in higher-resolution records and new interpretations of past conditions. There have been few recent changes in our understanding of the atmospheric chemistry of CH4, and since this is covered in Cicerone and Oremland (1988) it will not be covered here. The aim here is not to repeat information contained in the reviews mentioned above, but to present results that have appeared in the literature since their publication, to outline major questions, and to point to promising new approaches.

  11. 基于葫芦[8]脲主-客体作用的温度及pH敏感壳聚糖超分子凝胶制备与性能%Preparation and Properties of Temperature and pH Sensitive Chitosan Supramolecular Gel Based on Host-guest Interaction of Cucurbit[8]uril

    Institute of Scientific and Technical Information of China (English)

    林友文; 李立凡; 李光文

    2012-01-01

    壳聚糖侧链改性合成N-(4-二甲氨基苯甲基)壳聚糖(MBCS),通过葫芦[8]脲(Q[8])与MBCS侧链之间的主客体作用制得Q[8]/MBCS超分子凝胶.利用红外光谱、紫外光谱、1H NMR、X-射线粉末衍射(XRD)、热重分析(TG)和差示扫描量热(DSC)等技术对改性壳聚糖及凝胶进行表征.以5-氟尿嘧啶(5-Fu)为模型药物,研究载药凝胶在不同pH环境下的释药行为.结果表明Q[8]/MBCS体系在酸性条件下,可组装形成超分子凝胶,该凝胶体系具有温敏性和pH敏感性.扫描电镜(SEM)图显示凝胶具有网状交联结构,1H NMR谱显示,在酸性条件下,Q[8]与MBCS含氮侧链基团间发生主客体包合作用是超分子凝胶形成的主要原因.Q[8]/MBCS载药凝胶在酸性介质中对药物具有明显的缓释作用.%Chitosan(CS) which is a non-toxic,biocompatible,and biodegradable material and a good candidate for hydrogel formation was modified.A chitosan derivative,N-(4-dimethylaminobenzyl)chitosan(MBCS),was synthesized by the reaction of 4-(dimethylamino)benzaldehyde and chitosan to fabricate supramolecular gel system.The new family of macrocyclic host molecules,cucurbit[n]urils(Q[n],n=6~8) with its hydrophobic central cavity and negatively charged carbonyl portals,can bind to a variety of cationic organic guest molecules and neutral species to form the clathrate compounds with high affinity,and shows great potential applications in drug delivery system due to its low toxicity and good thermal stability.Cucurbit[8]uril(Q[8]) has a larger hydrophobic cavity volume of 479 3 and can include two aromatic rings.In this paper a novel supramolecular gel was prepared by utilizing the host-guest interaction between Q[8] and MBCS.The physical properties and structure of supramolecular gel and MBCS were characterized via IR,UV,1H NMR,X-ray powder diffraction(XRD),thermogravimetric method(TG) and differential scanning calorimetry(DSC).The morphology of network

  12. EDITORIAL: Van der Waals interactions in advanced materials, in memory of David C Langreth Van der Waals interactions in advanced materials, in memory of David C Langreth

    Science.gov (United States)

    Hyldgaard, Per; Rahman, Talat S.

    2012-10-01

    forces by examining the impact their inclusion has on predictions of material properties. On the other hand, the experimental and theoretical study of Casimir forces also plays a vital role in the exploration of material behavior. vdW forces are related to the Casimir force but lack retardation effects. While the vdW bonding depends on additional effects (for example, the multipole contributions that reflect image-plane effects), the study of Casimir forces provides direct (and not indirect) measurements of the nature of interactions. Klimchitskaya et al note that to reconcile explicit measurements of the Casmir forces between semiconductor fragments within the Lifshitz description, it is relevant to question the Drude-like description of the contributions from free carriers and instead proceed with a formulation based only on optical observations of the permittivity. This optical response can be seen as a reflection of a more plasmon-like behavior. The authors suggest an experiment involving the study of the impact on the Casimir forces by a Mott transition in doped semiconductors. Such an experiment would permit explicit testing of the validity of the present model for Casimir forces and hence provide additional perspectives on the nature of dispersive interactions. There is an effort to store energy, e.g. H2 or CO2, inside a range of open cage-like structures, such as metal organics frameworks (MOF) or clathrates. The fact that the internal molecular adhesion is dominated by vdW forces suggests that the storage and retrieval costs could perhaps be lowered as compared to an approach that involves more traditional chemical compounds. Nijem et al have provided spectroscopic characterization of vdW interactions of both hydrogen molecules and CO in a specific MOF. The study includes a vdW-DF calculation of structure and a theoretical prediction of expected infrared activity. The potential applications to energy materials have motivated more theoretical characterizations