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Sample records for actinide trichloride hydrate

  1. Dehydration of plutonium or neptunium trichloride hydrate

    DOEpatents

    Foropoulos, Jr., Jerry; Avens, Larry R.; Trujillo, Eddie A.

    1992-01-01

    A process of preparing anhydrous actinide metal trichlorides of plutonium or neptunium by reacting an aqueous solution of an actinide metal trichloride selected from the group consisting of plutonium trichloride or neptunium trichloride with a reducing agent capable of converting the actinide metal from an oxidation state of +4 to +3 in a resultant solution, evaporating essentially all the solvent from the resultant solution to yield an actinide trichloride hydrate material, dehydrating the actinide trichloride hydrate material by heating the material in admixture with excess thionyl chloride, and recovering anhydrous actinide trichloride is provided.

  2. Dehydration of plutonium or neptunium trichloride hydrate

    DOEpatents

    Foropoulos, J. Jr.; Avens, L.R.; Trujillo, E.A.

    1992-03-24

    A process is described for preparing anhydrous actinide metal trichlorides of plutonium or neptunium by reacting an aqueous solution of an actinide metal trichloride selected from the group consisting of plutonium trichloride or neptunium trichloride with a reducing agent capable of converting the actinide metal from an oxidation state of +4 to +3 in a resultant solution, evaporating essentially all the solvent from the resultant solution to yield an actinide trichloride hydrate material, dehydrating the actinide trichloride hydrate material by heating the material in admixture with excess thionyl chloride, and recovering anhydrous actinide trichloride.

  3. Synthesis of Uranium Trichloride for the Pyrometallurgical Processing of Used Nuclear Fuel

    SciTech Connect

    B.R. Westphal; J.C. Price; R.D. Mariani

    2011-11-01

    The pyroprocessing of used nuclear fuel via electrorefining requires the continued addition of uranium trichloride to sustain operations. Uranium trichloride is utilized as an oxidant in the system to allow separation of uranium metal from the minor actinides and fission products. The inventory of uranium trichloride had diminished to a point that production was necessary to continue electrorefiner operations. Following initial experimentation, cupric chloride was chosen as a reactant with uranium metal to synthesize uranium trichloride. Despite the variability in equipment and charge characteristics, uranium trichloride was produced in sufficient quantities to maintain operations in the electrorefiner. The results and conclusions from several experiments are presented along with a set of optimized operating conditions for the synthesis of uranium trichloride.

  4. Hydrothermal method of preparation of actinide(IV) phosphate hydrogenphosphate hydrates and study of their conversion into actinide(IV) phosphate diphosphate solid solutions.

    PubMed

    Dacheux, N; Grandjean, S; Rousselle, J; Clavier, N

    2007-11-26

    Several compositions of Th2-x/2AnIVx/2(PO4)2(HPO4).H2O (An=U, Np, Pu) were prepared through hydrothermal precipitation from a mixture of nitric solutions containing cations and concentrated phosphoric acid. All the samples were fully characterized by X-ray diffraction, UV-vis, and infrared spectroscopies to check for the existence of thorium-actinide(IV) phosphate hydrogenphosphate hydrates solid solutions. Such compounds were obtained as single phases, up to x=4 for uranium, x=2 for neptunium, and x<4 for plutonium, the cations being fully maintained in the tetravalent oxidation state. In a second step, the samples obtained after heating crystallized precursors at high temperature (1100 degrees C) were characterized. Single-phase thorium-actinide(IV) phosphate-diphosphate solid solutions were obtained up to x=0.8 for Np(IV) and x=1.6 for Pu(IV). For higher substitution rates, polyphase systems composed by beta-TAnPD, An2O(PO4)2, and/or alpha-AnP2O7 were formed. Finally, this hydrothermal route of preparation was applied successfully to the synthesis of an original phosphate-based compound incorporating simultaneously tetravalent uranium, neptunium and plutonium. PMID:17973479

  5. Boron trichloride purification with a KrF excimer laser

    SciTech Connect

    Hyer, R.C.; Hartford, A. Jr.; Atencio, J.H.

    1980-01-01

    Selective ultraviolet photolysis using a KrF excimer laser has been used to substantially reduce the phosgene impurity in a binary mixture of boron trichloride and phosgene. Infrared spectroscopic analysis of the sample before and after irradiation shows that it is possible to highly purify commercially available boron trichloride with this technique.

  6. Method for removal of phosgene from boron trichloride

    DOEpatents

    Freund, Samuel M.

    1983-01-01

    Selective ultraviolet photolysis using an unfiltered mercury arc lamp has been used to substantially reduce the phosgene impurity in a mixture of boron trichloride and phosgene. Infrared spectrophotometric analysis of the sample before and after irradiation shows that is is possible to highly purify commercially available boron trichloride with this method.

  7. Method for removal of phosgene from boron trichloride

    DOEpatents

    Freund, S.M.

    1983-09-20

    Selective ultraviolet photolysis using an unfiltered mercury arc lamp has been used to substantially reduce the phosgene impurity in a mixture of boron trichloride and phosgene. Infrared spectrophotometric analysis of the sample before and after irradiation shows that it is possible to highly purify commercially available boron trichloride with this method. 5 figs.

  8. Synthesis and Structure of Technetium Trichloride

    SciTech Connect

    Poineau, Frederic; Johnstone, Erik V.; Weck, Philippe F.; Kim, Eunja; Forster, Paul M.; Scott, Brian L.; Sattelberger, Alfred P.; Czerwinski, Kenneth R.

    2010-12-07

    Technetium trichloride has been synthesized by reaction of Tc{sub 2}(O{sub 2}CCH{sub 3}){sub 4}Cl{sub 2} with HCl(g) at 300 C. The mechanism of formation mimics the one described earlier in the literature for rhenium. Tc{sub 2}(O{sub 2}CCH{sub 3}){sub 2}Cl{sub 4} [P{sub T}; a = 6.0303(12) {angstrom}, b = 6.5098(13) {angstrom}, c = 8.3072(16) {angstrom}, {alpha} = 112.082(2){sup o}, {beta} = 96.667(3){sup o}, {gamma} = 108.792(3){sup o}; Tc-Tc = 2.150(1) {angstrom}] is formed as an intermediate in the reaction at 100 C. Technetium trichloride is formed above 250 C and is isostructural with its rhenium homologue. The structure consists of Tc{sub 3}Cl{sub 9} clusters [R{sub 3}m; a = b = 10.1035(19) {angstrom}, c = 20.120(8) {angstrom}], and the Tc-Tc separation is 2.444(1) {angstrom}. Calculations on TcX{sub 3} (X = Cl, Br) have confirmed the stability of TcCl{sub 3} and suggest the existence of a polymorph of TcBr{sub 3} with the ReBr{sub 3} structure.

  9. 15. SOUTH PLANT PIPELINES AND RAIL LINES FROM ARSENIC TRICHLORIDE ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    15. SOUTH PLANT PIPELINES AND RAIL LINES FROM ARSENIC TRICHLORIDE DRY STORAGE TANKS. VIEW TO EAST. - Rocky Mountain Arsenal, Bounded by Ninety-sixth Avenue & Fifty-sixth Avenue, Buckley Road, Quebec Street & Colorado Highway 2, Commerce City, Adams County, CO

  10. 41. SOUTH PLANT NORTHCENTER RAILROAD SPUR, WITH ARSENIC TRICHLORIDE MANUFACTURING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    41. SOUTH PLANT NORTH-CENTER RAILROAD SPUR, WITH ARSENIC TRICHLORIDE MANUFACTURING BUILDING (BUILDING 523) AT LEFT FOREGROUND AND PROCESS PIPING AT CENTER. VIEW TO EAST - Rocky Mountain Arsenal, Bounded by Ninety-sixth Avenue & Fifty-sixth Avenue, Buckley Road, Quebec Street & Colorado Highway 2, Commerce City, Adams County, CO

  11. Method for removal of phosgene from boron trichloride. [DOE patent application; mercury arc lamp

    DOEpatents

    Freund, S.M.

    1981-09-03

    Selective ultraviolet photolysis using an unfiltered mercury arc lamp has been used to substantially reduce the phosgene impurity in a mixture of boron trichloride and phosgene. Infrared spectrophotometric analysis of the sample before and after irradiation shows that it is possible to highly purify commercially available boron trichloride with this method.

  12. Actinides-1981

    SciTech Connect

    Not Available

    1981-09-01

    Abstracts of 134 papers which were presented at the Actinides-1981 conference are presented. Approximately half of these papers deal with electronic structure of the actinides. Others deal with solid state chemistry, nuclear physic, thermodynamic properties, solution chemistry, and applied chemistry.

  13. Research in actinide chemistry

    SciTech Connect

    Not Available

    1989-01-01

    Research continued to be focused broadly on the chemistry of the actinide cations in solution. While the direct concern is the actinide elements, their radioactivity limits the techniques which can be applied to their study. A major area of interest continues to be the thermodynamics of interaction of the f-elements with a broad spectrum of inorganic and organic ligands. Solvent extraction (for tracer levels), potentiometric and calorimetric titration and absorption spectrometry have been used to obtain stability constants and the associated enthalpy and entropy changes for complexation. A number of studies were performed to provide a better data base and a better understanding of the more significant species determining the behavior of actinides in natural waters (e.g., hydrolysis and silicate interaction). A second major area has been kinetics. NpO{sub 2}{sup 2+} reduction by hydroxy and carboxylic acids was studied to obtain an understanding of how such functional groups in humic substances may influence actinyl redox. The kinetics of dissociation of UO{sub 2}{sup 2+} and Ln{sup 3+} (La{sup 3+} = lanthanide element cations) from synthetic polyelectrolytes and humics provided significantly increased understanding of actinide complexation by these macromolecules. A third area of activity used laser induced fluorescence to study the hydration state of Eu(III) in a number of systems. Finally, several other studies, not in these major areas, were conducted. These included investigation of NpO{sub 2}{sup +} cation-cation complexes, the extraction of Am(III) by MX (M = Li, Na, NH{sub 4}{sup +}, K{sup +}; X = ClO{sub 4}{sup {minus}}, Cl{sup {minus}}, NO{sub 3}{sup {minus}}, BrO{sub 3}{sup {minus}}) over a concentration range from 0.01 M to saturated and the thermodynamics of synergistic extraction of actinides by crown ethers and {beta}-diketonates. 23 refs., 1 fig.

  14. Syntheses of neptunium trichloride and measurements of its melting temperature

    NASA Astrophysics Data System (ADS)

    Hayashi, Hirokazu; Takano, Masahide; Kurata, Masaki; Minato, Kazuo

    2013-09-01

    Neptunium trichloride (NpCl3) of high purity was synthesized by the solid state reaction of neptunium nitride with cadmium chloride. Lattice parameters of hexagonal NpCl3 were determined from the powder X-ray diffraction pattern to be a = 0.7428 ± 0.0001 nm and c = 0.4262 ± 0.0003 nm, which fairly agree with the reported values. The melting temperature of NpCl3 was measured on a sample of about 1 mg, hermetically encapsulated in a gold crucible with a differential thermal analyzer. The value determined was 1070 ± 3 K which is close to the recommended value (1075 ± 30 K) derived from the mean value of the melting temperature of UCl3 and of PuCl3.

  15. Hydrate detection

    SciTech Connect

    Dillon, W.P.; Ahlbrandt, T.S.

    1992-01-01

    Project objectives were: (1) to create methods of analyzing gas hydrates in natural sea-floor sediments, using available data, (2) to make estimates of the amount of gas hydrates in marine sediments, (3) to map the distribution of hydrates, (4) to relate concentrations of gas hydrates to natural processes and infer the factors that control hydrate concentration or that result in loss of hydrate from the sea floor. (VC)

  16. Hydrate detection

    SciTech Connect

    Dillon, W.P.; Ahlbrandt, T.S.

    1992-06-01

    Project objectives were: (1) to create methods of analyzing gas hydrates in natural sea-floor sediments, using available data, (2) to make estimates of the amount of gas hydrates in marine sediments, (3) to map the distribution of hydrates, (4) to relate concentrations of gas hydrates to natural processes and infer the factors that control hydrate concentration or that result in loss of hydrate from the sea floor. (VC)

  17. Actinide metal processing

    DOEpatents

    Sauer, Nancy N.; Watkin, John G.

    1992-01-01

    A process of converting an actinide metal such as thorium, uranium, or plnium to an actinide oxide material by admixing the actinide metal in an aqueous medium with a hypochlorite as an oxidizing agent for sufficient time to form the actinide oxide material and recovering the actinide oxide material is provided together with a low temperature process of preparing an actinide oxide nitrate such as uranyl nitrte. Additionally, a composition of matter comprising the reaction product of uranium metal and sodium hypochlorite is provided, the reaction product being an essentially insoluble uranium oxide material suitable for disposal or long term storage.

  18. Actinide metal processing

    SciTech Connect

    Sauer, N.N.; Watkin, J.G.

    1992-03-24

    A process for converting an actinide metal such as thorium, uranium, or plutonium to an actinide oxide material by admixing the actinide metal in an aqueous medium with a hypochlorite as an oxidizing agent for sufficient time to form the actinide oxide material and recovering the actinide oxide material is described together with a low temperature process for preparing an actinide oxide nitrate such as uranyl nitrate. Additionally, a composition of matter comprising the reaction product of uranium metal and sodium hypochlorite is provided, the reaction product being an essentially insoluble uranium oxide material suitable for disposal or long term storage.

  19. Actinide metal processing

    SciTech Connect

    Sauer, N.N.; Watkin, J.G.

    1991-04-05

    This invention is comprised of a process of converting an actinide metal such as thorium, uranium, or plutonium to an actinide oxide material by admixing the actinide metal in an aqueous medium with a hypochlorite as an oxidizing agent for sufficient time to form the actinide oxide material and recovering the actinide oxide material is provided together with a low temperature process of preparing an actinide oxide nitrate such as uranyl nitrate. Additionally, a composition of matter comprising the reaction product of uranium metal and sodium hypochlorite is provided, the reaction product being an essentially insoluble uranium oxide material suitable for disposal or long term storage.

  20. Actinide sulfite tetrahydrate and actinide oxysulfite tetrahydrate

    SciTech Connect

    Baugh, D.; Watt, G.

    1980-07-08

    A compound is prepared that comprises an actinide sulfite tetrahydrate selected from the group consisting of uranium (IV) sulfite tetrahydrate and plutonium (IV) sulfite tetrahydrate. A compound is also prepared that comprises an actinide oxysulfite tetrahydrate selected from the group consisting of uranium (IV) oxysulfite tetrahydrate and plutonium (IV) oxysulfite tetrahydrate

  1. Chloral Hydrate

    MedlinePlus

    Chloral hydrate, a sedative, is used in the short-term treatment of insomnia (to help you fall asleep and ... Chloral hydrate comes as a capsule and liquid to take by mouth and as a suppository to insert rectally. ...

  2. Raman spectrometric studies of selected lanthanide tribromides and trichlorides

    SciTech Connect

    Daniel, J.F.

    1988-03-01

    Laser Raman spectroscopy was used to identify the crystal structures of lanthanide and actinide compounds. The phonon Raman spectrum is characteristic of the particular crystal structure. GdCl/sub 3/ exhibits two crystal structures, the UCl/sub 3/-type hexagonal and the PuBr/sub 3/-type orthorhombic. In the literature it is reported that the low temperature form is orthorhombic; results of experiments here suggest that it is hexagonal. Interconversion between these two forms can be accomplished with temperature andor pressure. In the present work laser Raman spectrometry was used to monitor crystal structure changes in GdCl/sub 3/ as a function of temperature or pressure to determine the temperature or pressure at which the hexagonal-to-orthorhombic transformation occurs. Raman spectroscopy was also used to determine the symmetry assignments for the Raman-active bands of a single crystal. Raman spectra of polycrystalline NdBr/sub 3/ have been recorded at room temperature and pressure and at approximately 100/degree/K. In addition, polarized Raman spectra of a single crystal NdBr/sub 3/ have been measured. Based on these polarization measurements, symmetry assignments of eight Raman-active modes were made. These assignments are useful in interpreting the phonon Raman spectrum of any compound exhibiting the PuBr/sub 3/-type orthorhombic structure. 24 figs., 5 tabs.

  3. Actinide-ion sensor

    DOEpatents

    Li, Shelly X; Jue, Jan-fong; Herbst, Ronald Scott; Herrmann, Steven Douglas

    2015-01-13

    An apparatus for the real-time, in-situ monitoring of actinide-ion concentrations. A working electrolyte is positioned within the interior of a container. The working electrolyte is separated from a reference electrolyte by a separator. A working electrode is at least partially in contact with the working electrolyte. A reference electrode is at least partially in contact with the reference electrolyte. A voltmeter is electrically connected to the working electrode and the reference electrode. The working electrolyte comprises an actinide-ion of interest. The separator is ionically conductive to the actinide-ion of interest. The separator comprises an actinide, Zr, and Nb. Preferably, the actinide of the separator is Am or Np, more preferably Pu. In one embodiment, the actinide of the separator is the actinide of interest. In another embodiment, the separator further comprises P and O.

  4. The kinetics of electron transfer reaction of methylene green and titanium trichloride in different solvents

    NASA Astrophysics Data System (ADS)

    Saeed, Rehana; Nadeem, Syed Muhammad Saqib

    2016-06-01

    The kinetics of the electron transfer reaction of methylene green and titanium trichloride was investigated in different solvents by spectrophotometry at different temperatures. The the reaction rate was determined by monitoring the absorbance as a function of time at λmax 655 nm. The reaction is pseudo-first order, dependent only on the concentration of titanium trichloride at a fixed concentration of methylene green. The effect of an aqueous alcoholic solvent was studied in the acidic range of pH from 4 to 7. It was observed that the reaction rate increased with an increase in polarity of the reaction medium. The the reaction rate was high in acidic conditions and decreased with a further increase in acidity. The increase in temperature increased the rate of the electron transfer reaction of methylene green and titanium trichloride. The activation energy ( E a) was calculated by the Arrhenius relation. The absence of any reaction intermediate was confirmed by spectroscopic and kinetic investigations. A plausible mechanism for the reaction in line with outer-sphere reaction pathway has been proposed. Thermodynamic parameters such as the activation energy ( E a), enthalpy change (Δ H), free energy change (Δ G), and entropy change (Δ S) were also evaluated

  5. Actinide extraction methods

    DOEpatents

    Peterman, Dean R [Idaho Falls, ID; Klaehn, John R [Idaho Falls, ID; Harrup, Mason K [Idaho Falls, ID; Tillotson, Richard D [Moore, ID; Law, Jack D [Pocatello, ID

    2010-09-21

    Methods of separating actinides from lanthanides are disclosed. A regio-specific/stereo-specific dithiophosphinic acid having organic moieties is provided in an organic solvent that is then contacted with an acidic medium containing an actinide and a lanthanide. The method can extend to separating actinides from one another. Actinides are extracted as a complex with the dithiophosphinic acid. Separation compositions include an aqueous phase, an organic phase, dithiophosphinic acid, and at least one actinide. The compositions may include additional actinides and/or lanthanides. A method of producing a dithiophosphinic acid comprising at least two organic moieties selected from aromatics and alkyls, each moiety having at least one functional group is also disclosed. A source of sulfur is reacted with a halophosphine. An ammonium salt of the dithiophosphinic acid product is precipitated out of the reaction mixture. The precipitated salt is dissolved in ether. The ether is removed to yield the dithiophosphinic acid.

  6. Research in actinide chemistry

    SciTech Connect

    Choppin, G.R.

    1993-01-01

    This research studies the behavior of the actinide elements in aqueous solution. The high radioactivity of the transuranium actinides limits the concentrations which can be studied and, consequently, limits the experimental techniques. However, oxidation state analogs (trivalent lanthanides, tetravalent thorium, and hexavalent uranium) do not suffer from these limitations. Behavior of actinides in the environment are a major USDOE concern, whether in connection with long-term releases from a repository, releases from stored defense wastes or accidental releases in reprocessing, etc. Principal goal of our research was expand the thermodynamic data base on complexation of actinides by natural ligands (e.g., OH[sup [minus

  7. METHOD FOR OBTAINING PLUTONIUM METAL AND ALLOYS OF PLUTONIUM FROM PLUTONIUM TRICHLORIDE

    DOEpatents

    Reavis, J.G.; Leary, J.A.; Maraman, W.J.

    1962-11-13

    A process is given for both reducing plutonium trichloride to plutonium metal using cerium as the reductant and simultaneously alloying such plutonium metal with an excess of cerium or cerium and cobalt sufficient to yield the desired nuclear reactor fuel composition. The process is conducted at a temperature from about 550 to 775 deg C, at atmospheric pressure, without the use of booster reactants, and a substantial decontamination is effected in the product alloy of any rare earths which may be associated with the source of the plutonium. (AEC)

  8. Actinide recovery process

    DOEpatents

    Muscatello, Anthony C.; Navratil, James D.; Saba, Mark T.

    1987-07-28

    Process for the removal of plutonium polymer and ionic actinides from aqueous solutions by absorption onto a solid extractant loaded on a solid inert support such as polystyrenedivinylbenzene. The absorbed actinides can then be recovered by incineration, by stripping with organic solvents, or by acid digestion. Preferred solid extractants are trioctylphosphine oxide and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and the like.

  9. Thermodynamic Properties of Actinides and Actinide Compounds

    NASA Astrophysics Data System (ADS)

    Konings, Rudy J. M.; Morss, Lester R.; Fuger, Jean

    The necessity of obtaining accurate thermodynamic quantities for the actinide elements and their compounds was recognized at the outset of the Manhattan Project, when a dedicated team of scientists and engineers initiated the program to exploit nuclear energy for military purposes. Since the end of World War II, both fundamental and applied objectives have motivated a great deal of further study of actinide thermodynamics. This chapter brings together many research papers and critical reviews on this subject. It also seeks to assess, to systematize, and to predict important properties of the actinide elements, ions, and compounds, especially for species in which there is significant interest and for which there is an experimental basis for the prediction.

  10. Method for preparing actinide nitrides

    DOEpatents

    Bryan, G.H.; Cleveland, J.M.; Heiple, C.R.

    1975-12-01

    Actinide nitrides, and particularly plutonium and uranium nitrides, are prepared by reacting an ammonia solution of an actinide compound with an ammonia solution of a reactant or reductant metal, to form finely divided actinide nitride precipitate which may then be appropriately separated from the solution. The actinide nitride precipitate is particularly suitable for forming nuclear fuels.

  11. Research in actinide chemistry

    SciTech Connect

    Not Available

    1991-01-01

    This report contains research results on studies of inorganic and organic complexes of actinide and lanthanide elements. Special attention is given to complexes of humic acids and to spectroscopic studies.

  12. Thermochemistry of the actinides

    SciTech Connect

    Kleinschmidt, P.D.

    1993-10-01

    The measurement of equilibria by Knudsen effusion techniques and the enthalpy of formation of the actinide atoms is briefly discussed. Thermochemical data on the sublimation of the actinide fluorides is used to calculate the enthalpies of formation and entropies of the gaseous species. Estimates are made for enthalpies and entropies of the tetrafluorides and trifluorides for those systems where data is not available. The pressure of important species in the tetrafluoride sublimation processes is calculated based on this thermochemical data.

  13. PRODUCTION OF ACTINIDE METAL

    DOEpatents

    Knighton, J.B.

    1963-11-01

    A process of reducing actinide oxide to the metal with magnesium-zinc alloy in a flux of 5 mole% of magnesium fluoride and 95 mole% of magnesium chloride plus lithium, sodium, potassium, calcium, strontium, or barium chloride is presented. The flux contains at least 14 mole% of magnesium cation at 600-- 900 deg C in air. The formed magnesium-zinc-actinide alloy is separated from the magnesium-oxide-containing flux. (AEC)

  14. Actinide recovery process

    DOEpatents

    Muscatello, A.C.; Navratil, J.D.; Saba, M.T.

    1985-06-13

    Process for the removal of plutonium polymer and ionic actinides from aqueous solutions by absorption onto a solid extractant loaded on a solid inert support such as polystyrene-divinylbenzene. The absorbed actinides can then be recovered by incineration, by stripping with organic solvents, or by acid digestion. Preferred solid extractants are trioctylphosphine oxide and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and the like. 2 tabs.

  15. KNa 3(UO 2) 2(Si 4O 10) 2(H 2O) 4, a new compound formed during vapor hydration of an actinide-bearing borosilicate waste glass

    NASA Astrophysics Data System (ADS)

    Burns, Peter C.; Olson, Rudolph A.; Finch, Robert J.; Hanchar, John M.; Thibault, Yves

    2000-02-01

    Vapor hydration experiments on a U-doped borosilicate waste glass at 200°C produced a novel uranium silicate. Single crystal X-ray structure analysis of this phase indicate the ideal formula KNa 3(UO 2) 2(Si 4O 10) 2(H 2O) 4, although the compound shows some compositional variability. It is monoclinic, space group C2, Z=2, a=1.2782(1) , b=1.3654(1), c=0.82677(8) nm, β=119.240(1)°. The structure was solved by direct methods and refined to an agreement index ( R) of 3.6% for 2239 unique observed (| F0|⩾4 σF) reflections and a goodness-of-fit of 1.05. The structure contains vertex-sharing silicate tetrahedra arranged in four and eight-membered rings that are linked to give sheets parallel to (0 0 1). The sheets are cross-linked by vertex-sharing with UrO 4 square bipyramids [Ur=(UO 2) 2+ uranyl ion], forming a framework of polyhedra of higher bond-valence. The title phase is the major sink for U during glass corrosion at 200°C after approximately 60 days in a saturated vapor environment. Consideration of the structural sites reveals the potential of this compound to incorporate radionuclides from a variety of nuclear-waste glasses over a wide range of environmental conditions.

  16. Actinide Dioxides in Water: Interactions at the Interface

    SciTech Connect

    Alexandrov, Vitaly; Shvareva, Tatiana Y.; Hayun, Shmuel; Asta, Mark; Navrotsky, Alexandra

    2011-12-15

    A comprehensive understanding of chemical interactions between water and actinide dioxide surfaces is critical for safe operation and storage of nuclear fuels. Despite substantial previous research, understanding the nature of these interactions remains incomplete. In this work, we combine accurate calorimetric measurements with first-principles computational studies to characterize surface energies and adsorption enthalpies of water on two fluorite-structured compounds, ThO₂ and CeO₂, that are relevant for understanding the behavior of water on actinide oxide surfaces more generally. We determine coverage-dependent adsorption enthalpies and demonstrate a mixed molecular and dissociative structure for the first hydration layer. The results show a correlation between the magnitude of the anhydrous surface energy and the water adsorption enthalpy. Further, they suggest a structural model featuring one adsorbed water molecule per one surface cation on the most stable facet that is expected to be a common structural signature of water adsorbed on actinide dioxide compounds.

  17. Nonaqueous actinide hydride dissolution and production of actinide $beta$- diketonates

    DOEpatents

    Crisler, L.R.

    1975-11-11

    Actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a hydride of the actinide material in a mixture of carbon tetrachloride and methanol. (auth)

  18. Chloral hydrate

    Integrated Risk Information System (IRIS)

    Chloral hydrate ; CASRN 302 - 17 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

  19. Iron Trichloride and Air Mediated Guanylation of Acylthioureas. An Ecological Route to Acylguanidines: Scope and Mechanistic Insights.

    PubMed

    Pape, Simon; Wessig, Pablo; Brunner, Heiko

    2016-06-01

    Recently we introduced iron trichloride as an environmentally benign and cost-efficient reagent for the synthesis of N-benzoylguanidines. This highly attractive synthetic approach grants access to a broad spectrum of N-benzoylguanidines under mild conditions in short reaction times. In this work we present an extended scope of our methodology along with the results obtained from mechanistic studies via in situ IR spectroscopy in combination with LC (liquid chromatography)-MS analyses. On the basis of these new mechanistic insights we were able to optimize the synthetic protocol and to develop an alternative mechanistic proposal. In this context the symbiotic roles of iron trichloride and oxygen in the guanylation process are highlighted. PMID:27181741

  20. Complexation of actinides with derivatives of oxydiaceticacid

    SciTech Connect

    Rao, Linfeng; Tian, Guoxin

    2006-01-04

    Complexation of Np(V), U(VI) and Nd(III) with dimethyl-3-oxa-glutaramic acid (DMOGA) and tetramethyl-3-oxa-glutaramide (TMOGA) was studied in comparison with the complexation with oxydiacetic acid (ODA). Stability constants and enthalpy of complexation were determined by potentiometry, spectrophotometry and calorimetry. Thermodynamic parameters, in conjunction with structural information of solid compounds, indicate that DMOGA and TMOGA form tridentate complexes with the ether-oxygen participating in bonding with actinide/lanthanide ions. The trends in the stability constants, enthalpy and entropy of complexation are discussed in terms of the difference in the hydration of the amide groups and carboxylate groups and the difference in the charge density of the metal ions.

  1. Hydrate habitat

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    Whoever said there is nothing new under the sun did not delve deeply enough to the bottom of the ocean. There in the Gulf of Mexico, about 150 miles south of New Orleans, scientists have just discovered what could be a new species of centipede—like worms living on or within gas hydrates— mounds of methane ice— rising from the ocean floor.Scientists have previously recognized an association between some bacteria and these hydrates. However, this is the first discovery of a higher life form there.

  2. Large Scale Testing and Development of Gadolinium Trichloride for Use in Neutron Detection in Large Water

    SciTech Connect

    Mark Vagine

    2007-09-18

    Water Cherenkov detectors have been used for many years as inexpensive, effective detectors for neutrino interactions and nucleon decay searches. While many important measurements have been made with these detectors a major drawback has been their inability to detect the absorption of thermal neutrons. We believe an inexpensive, effective technique could be developed to overcome this situation via the addition to water of a solute with a large neutron cross section and energetic gamma daughters which would make neutrons detectable. Gadolinium seems an excellent candidate especially since in recent years it has become very inexpensive, now less than $8 per kilogram in the form of commercially-available gadolinium trichloride, GdCl{sub 3}. This non-toxic, non-reactive substance is highly soluble in water. Neutron capture on gadolinium yields a gamma cascade which would be easily seen in detectors like Super-Kamiokande. We have begun to investigate the use of GdCl{sub 3} as a possible upgrade for the Super-Kamiokande detector with a view toward improving its performance as a detector for atmospheric neutrinos, supernova neutrinos, wrong-sign solar neutrinos, reactor neutrinos, proton decay, and also as a target for the coming T2K long-baseline neutrino experiment. This large-scale investigation, conducted in the one kiloton water Cherenkov detector built for the K2K long-baseline experiment, follows up on highly promising benchtop-scale work previously carried out with the assistance of a 2003 Advanced Detector Research Program grant.

  3. Pulmonary response of Fischer 344 rats to acute nose-only inhalation of indium trichloride.

    PubMed

    Blazka, M E; Tepper, J S; Dixon, D; Winsett, D W; O'Connor, R W; Luster, M I

    1994-10-01

    We have previously shown that rats dosed intratracheally with indium trichloride (InCl3) develop severe lung damage and fibrosis. However, it is not clear what pulmonary effects would result following accidental occupational exposure to low concentrations of indium by inhalation. The present study uses a model of acute lung injury based on single 1-hr nose-only exposures to 0.2, 2.0, or 20 mg InCl3/m3. Exposure to 0.2 mg InCl3/m3 was capable of initiating an inflammatory response. Seven days following inhalation of 20 mg InCl3/m3 the total cell number, fibronectin, and TNF alpha levels in the bronchial alveolar lavage fluid were 8, 40, and 5 times higher than the control, respectively. Commensurate with the level of lung injury 7 days after exposure, an acute restrictive lung lesion and increased airway responsiveness to acetylcholine were observed. Forty-two days after exposure a compensatory increase in lung volume and carbon monoxide diffusing capacity in the 20 mg InCl3/m3 group suggested recovery from the lung injury. Lung collagen levels were increased in a concentration-dependent manner 42 days postexposure. These data indicate that inhalation of InCl3/m3 causes acute inflammatory changes in the lung. PMID:7925195

  4. Comparative teratogenicity of di-n-butyltin diacetate with n-butyltin trichloride in rats.

    PubMed

    Noda, T; Yamano, T; Shimizu, M; Saitoh, M; Nakamura, T; Yamada, A; Morita, S

    1992-08-01

    Teratological tests were conducted on di-n-butyltin diacetate (DBTA), and n-butyltin trichloride (MBTC). Pregnant Wistar rats were treated orally with DBTA at doses of 0, 1.7, 5.0, 10.0, and 15.0 mg/kg/day or with MBTC at doses of 0, 50, 100, 200, and 400 mg/kg/day during days 7-17 of gestation. Cesarean sections were performed on day 20 of gestation. Thymic atrophy of the pregnant rats was observed in a dose-dependent manner by DBTA treatment. The incidence of dead or resorbed fetuses and total resorption fetuses increased at the highest dose of DBTA. The incidence of fetuses with external malformations, such as cleft mandible, cleft lower lip, ankyloglossia (tongue-tie) and schistoglossia (cleft tongue), increased in a dose-dependent manner by DBTA treatment. The incidence of fetuses with skeletal malformations such as anomaly of mandibular fixation, fused ribs, fused cervical vertebral arches and fused thoracic vertebral arches also increased at 10.0 and 15.0 mg/kg. However, MBTC, one of the main metabolites of di-n-butyltin, failed to show any evidence of tetatogenic activity at any doses tested. The results indicate that DBTA has potent teratogenic effects on rat fetuses, and DBTA is different from MBTC with respect to teratogenic effects. PMID:1514842

  5. Selective Filtration of Gadolinium Trichloride for Use in Neutron Detection in Large Water Cherenkov Detectors

    SciTech Connect

    Vagins, Mark R.

    2013-04-10

    Water Cherenkov detectors have been used for many years as inexpensive, effective detectors for neutrino interactions and nucleon decay searches. While many important measurements have been made with these detectors a major drawback has been their inability to detect the absorption of thermal neutrons. We believe an inexpensive, effective technique could be developed to overcome this situation via the addition to water of a solute with a large neutron cross section and energetic gamma daughters which would make neutrons detectable. Gadolinium seems an excellent candidate especially since in recent years it has become very inexpensive, now less than $8 per kilogram in the form of commercially-available gadolinium trichloride, GdCl{sub 3}. This non-toxic, non-reactive substance is highly soluble in water. Neutron capture on gadolinium yields a gamma cascade which would be easily seen in detectors like Super-Kamiokande. We have been investigating the use of GdCl{sub 3} as a possible upgrade for the Super-Kamiokande detector with a view toward improving its performance as a detector for atmospheric neutrinos, supernova neutrinos, wrong-sign solar neutrinos, reactor neutrinos, proton decay, and also as a target for the coming T2K long-baseline neutrino experiment. This focused study of selective water filtration and GdCl{sub 3} extraction techniques, conducted at UC Irvine, followed up on highly promising benchtop-scale and kiloton-scale work previously carried out with the assistance of 2003 and 2005 Advanced Detector Research Program grants.

  6. Device for Detecting Actinides, Method for Detecting Actinides

    SciTech Connect

    Stevens, Fred J.; Wilkins-Stevens, Priscilla

    1998-10-29

    A heavy metal detector is provided comprising a first molecule and a second molecule, whereby the first and second molecules interact in a predetermined manner; a first region on the first molecule adapted to interact with an actinide; and a second region on the second molecule adapted to interact with the actinide, whereby the interactions of the actinide with the regions effect the predetermined manner of interaction between the molecules.

  7. Novel Separation of Actinides

    SciTech Connect

    Mariella, R

    2011-02-17

    The separation of actinides and other elements of interest for nuclear forensics and threat reduction is currently performed using decades-old chemistries and ion-exchange columns. We propose to determine the technical feasibility of a novel method for separating actinide ions in solution. This method is based upon isotachophoresis (ITP), which has been applied in the purification of pharmaceuticals and other biochemical applications. This technique has the potential to separate inorganic ions more effectively than existing methods, which is key to analyzing very small samples. We will perform a quantitative assessment of the effectiveness of specific isotachophoretic approaches including predicting the physical and chemical properties, such as ion mobility, of inorganic ions under specific solvent conditions using a combination of ab initio calculations and semi-empirical methods. We expect to obtain a thorough understanding of the analytical systems parameters under which ITP is most effective for the separation of inorganic samples, including the influence of the double layer surrounding actinide ions, the Debye length for different ions and ion complexes, and Debye-Hueckel limits. Inorganic separations are key to nuclear forensics for countering terrorism and nuclear proliferation. If found to be feasible and potentially superior to currently used separation approaches, ITP could provide the conceptual basis for an improved means to separate samples of nuclear explosion debris for nuclear forensic analysis, in support of the Laboratory's missions in homeland and national security.

  8. Environmental speciation of actinides.

    PubMed

    Maher, Kate; Bargar, John R; Brown, Gordon E

    2013-04-01

    Although minor in abundance in Earth's crust (U, 2-4 ppm; Th, 10-15 ppm) and in seawater (U, 0.003 ppm; Th, 0.0007 ppm), light actinides (Th, Pa, U, Np, Pu, Am, and Cm) are important environmental contaminants associated with anthropogenic activities such as the mining and milling of uranium ores, generation of nuclear energy, and storage of legacy waste resulting from the manufacturing and testing of nuclear weapons. In this review, we discuss the abundance, production, and environmental sources of naturally occurring and some man-made light actinides. As is the case with other environmental contaminants, the solubility, transport properties, bioavailability, and toxicity of actinides are dependent on their speciation (composition, oxidation state, molecular-level structure, and nature of the phase in which the contaminant element or molecule occurs). We review the aqueous speciation of U, Np, and Pu as a function of pH and Eh, their interaction with common inorganic and organic ligands in natural waters, and some of the common U-containing minerals. We also discuss the interaction of U, Np, Pu, and Am solution complexes with common Earth materials, including minerals, colloids, gels, natural organic matter (NOM), and microbial organisms, based on simplified model system studies. These surface interactions can inhibit (e.g., sorption to mineral surfaces, formation of insoluble biominerals) or enhance (e.g., colloid-facilitated transport) the dispersal of light actinides in the biosphere and in some cases (e.g., interaction with dissimilatory metal-reducing bacteria, NOM, or Mn- and Fe-containing minerals) can modify the oxidation states and, consequently, the behavior of redox-sensitive light actinides (U, Np, and Pu). Finally, we review the speciation of U and Pu, their chemical transformations, and cleanup histories at several U.S. Department of Energy field sites that have been used to mill U ores, produce fissile materials for reactors and weapons, and store

  9. Superabsorbing gel for actinide, lanthanide, and fission product decontamination

    DOEpatents

    Kaminski, Michael D.; Mertz, Carol J.

    2016-06-07

    The present invention provides an aqueous gel composition for removing actinide ions, lanthanide ions, fission product ions, or a combination thereof from a porous surface contaminated therewith. The composition comprises a polymer mixture comprising a gel forming cross-linked polymer and a linear polymer. The linear polymer is present at a concentration that is less than the concentration of the cross-linked polymer. The polymer mixture is at least about 95% hydrated with an aqueous solution comprising about 0.1 to about 3 percent by weight (wt %) of a multi-dentate organic acid chelating agent, and about 0.02 to about 0.6 molar (M) carbonate salt, to form a gel. When applied to a porous surface contaminated with actinide ions, lanthanide ions, and/or other fission product ions, the aqueous gel absorbs contaminating ions from the surface.

  10. PROCESS OF PRODUCING ACTINIDE METALS

    DOEpatents

    Magel, T.T.

    1959-07-14

    The preparation of actinide metals in workable, coherent form is described. In general, the objects of the invention are achieved by heating a mixture of an oxide and a halide of an actinide metal such as uranium with an alkali metal on alkaline earth metal reducing agent in the presence of iodine.

  11. Actinide halide complexes

    DOEpatents

    Avens, L.R.; Zwick, B.D.; Sattelberger, A.P.; Clark, D.L.; Watkin, J.G.

    1992-11-24

    A compound is described of the formula MX[sub n]L[sub m] wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands. A compound of the formula MX[sub n] wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds are described including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant.

  12. Actinide halide complexes

    DOEpatents

    Avens, Larry R.; Zwick, Bill D.; Sattelberger, Alfred P.; Clark, David L.; Watkin, John G.

    1992-01-01

    A compound of the formula MX.sub.n L.sub.m wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands, a compound of the formula MX.sub.n wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant, are provided.

  13. Kinetics and mechanisms of the base decomposition of nitrogen trichloride in aqueous solution

    SciTech Connect

    Kumar, K.; Shinness, R.W.; Margerum, D.W.

    1987-10-21

    The rate expression for the base decomposition of nitrogen trichloride is -d(NCl/sub 3/)dt = 2(k/sub 0/ + k/sub 1/(OH/sup -/) + k/sub HB/(HB)(OH/sup -/) + k/sub 2/(OH/sup -/)/sup 2/)(NCl/sub 3/), based on the stoichiometry 2NCl/sub 3/ + 6OH/sup -/ ..-->.. N/sub 2/ + 3OCl/sup -/ + 3Cl/sup -/ + 3H/sub 2/O. Values of the rate constants (25.0/sup 0/C, ..mu.. = 0.5) are 1.6 x 10/sup -6/ s/sup -1/ for k/sub 0/, 8 M/sup -1/ s/sup -1/ for k/sub 1/, and 890 M/sup -2/ for k/sub 2/. The specific-basegeneral-acid-catalyzed path gives k/sub HB/ values (M/sup -2/ s/sup -1/) of 2.1 x 10/sup 3/ for H/sub 2/PO/sub 4//sup -/, 7.6 x 10/sup 2/ for B(OH)/sub 3/, 65 for HCO/sub 3//sup -/, and 128 for HPO/sub 4//sup 2 -/. In the proposed mechanism Cl/sub 2/NClOH/sup -/ is a common reactive intermediate that can react with acids (H/sub 3/O/sup +/, HB and H/sub 2/O with a Broensted ..cap alpha.. value of 0.48) to form HNCl/sub 2/ and HOCl or it can react with an additional OH/sup -/ to release OCl/sup -/. The HNCl/sub 2/ so formed reacts rapidly with a second NCl/sub 3/ to give products. Kinetics data allow an equilibrium constant of 1.6 x 10/sup 8/ M/sup -1/ (25.0/sup 0/C, ..mu.. = 0.5) to be calculated for the reaction NHCl/sub 2/ + HOCl reversible NCl/sub 3/ + H/sub 2/O.

  14. Managing Inventories of Heavy Actinides

    SciTech Connect

    Wham, Robert M; Patton, Bradley D

    2011-01-01

    The Department of Energy (DOE) has stored a limited inventory of heavy actinides contained in irradiated targets, some partially processed, at the Savannah River Site (SRS) and Oak Ridge National Laboratory (ORNL). The 'heavy actinides' of interest include plutonium, americium, and curium isotopes; specifically 242Pu and 244Pu, 243Am, and 244/246/248Cm. No alternate supplies of these heavy actinides and no other capabilities for producing them are currently available. Some of these heavy actinide materials are important for use as feedstock for producing heavy isotopes and elements needed for research and commercial application. The rare isotope 244Pu is valuable for research, environmental safeguards, and nuclear forensics. Because the production of these heavy actinides was made possible only by the enormous investment of time and money associated with defense production efforts, the remaining inventories of these rare nuclear materials are an important part of the legacy of the Nuclear Weapons Program. Significant unique heavy actinide inventories reside in irradiated Mark-18A and Mark-42 targets at SRS and ORNL, with no plans to separate and store the isotopes for future use. Although the costs of preserving these heavy actinide materials would be considerable, for all practical purposes they are irreplaceable. The effort required to reproduce these heavy actinides today would likely cost billions of dollars and encompass a series of irradiation and chemical separation cycles for at least 50 years; thus, reproduction is virtually impossible. DOE has a limited window of opportunity to recover and preserve these heavy actinides before they are disposed of as waste. A path forward is presented to recover and manage these irreplaceable National Asset materials for future use in research, nuclear forensics, and other potential applications.

  15. Actinide Burning in CANDU Reactors

    SciTech Connect

    Hyland, B.; Dyck, G.R.

    2007-07-01

    Actinide burning in CANDU reactors has been studied as a method of reducing the actinide content of spent nuclear fuel from light water reactors, and thereby decreasing the associated long term decay heat load. In this work simulations were performed of actinides mixed with natural uranium to form a mixed oxide (MOX) fuel, and also mixed with silicon carbide to form an inert matrix (IMF) fuel. Both of these fuels were taken to a higher burnup than has previously been studied. The total transuranic element destruction calculated was 40% for the MOX fuel and 71% for the IMF. (authors)

  16. Actinide solubility-controlling phases during the dissolution of phosphate ceramics

    NASA Astrophysics Data System (ADS)

    Du Fou de Kerdaniel, E.; Clavier, N.; Dacheux, N.; Terra, O.; Podor, R.

    2007-05-01

    Phosphate ceramics (britholites, monazite/brabantite solid solutions, thorium phosphate diphosphate, i.e. β-TPD, and associated β-TPD/monazite composites) are often considered as potential candidates to immobilize tri- and tetravalent actinides. In order to study the properties of such materials on the retention of actinides during aqueous alteration, phosphate-based neoformed phases were prepared using under- and over-saturation processes then extensively characterized (involving grazing XRD, EPMA, μ-Raman, IR or SEM). In over-saturation conditions, lanthanides (used as surrogates of trivalent actinides) are quickly precipitated as three hydrated forms (monazite, rhabdophane or xenotime) depending on the temperature, the heating time and the ionic radius of the element. Moreover, as already described for thorium, tetravalent actinides (Th, U, Np, Pu) are more often immobilized as phosphate hydrogenphosphate compounds. However, samples of (Ln,Ca,Th)-rhabdophane can also precipitate in the presence of large concentrations of calcium. Such neoformed phases were also precipitated at the surface of leached phosphate-based ceramics during under-saturation experiments. The associated thermodynamic solubility constants at infinite dilution were estimated. Due to their rapid precipitation and their very low solubility constants, these actinide phosphate solubility-controlling phases appear of significant interest in the field of the evaluation of the long-term performance of actinide-doped phosphate ceramics.

  17. Environmental research on actinide elements

    SciTech Connect

    Pinder, J.E. III; Alberts, J.J.; McLeod, K.W.; Schreckhise, R.G.

    1987-08-01

    The papers synthesize the results of research sponsored by DOE's Office of Health and Environmental Research on the behavior of transuranic and actinide elements in the environment. Separate abstracts have been prepared for the 21 individual papers. (ACR)

  18. Gas hydrate and humans

    USGS Publications Warehouse

    Kvenvolden, K.A.

    2000-01-01

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

  19. Understanding gas hydrate dissolution

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

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

  20. 33rd Actinide Separations Conference

    SciTech Connect

    McDonald, L M; Wilk, P A

    2009-05-04

    Welcome to the 33rd Actinide Separations Conference hosted this year by the Lawrence Livermore National Laboratory. This annual conference is centered on the idea of networking and communication with scientists from throughout the United States, Britain, France and Japan who have expertise in nuclear material processing. This conference forum provides an excellent opportunity for bringing together experts in the fields of chemistry, nuclear and chemical engineering, and actinide processing to present and discuss experiences, research results, testing and application of actinide separation processes. The exchange of information that will take place between you, and other subject matter experts from around the nation and across the international boundaries, is a critical tool to assist in solving both national and international problems associated with the processing of nuclear materials used for both defense and energy purposes, as well as for the safe disposition of excess nuclear material. Granlibakken is a dedicated conference facility and training campus that is set up to provide the venue that supports communication between scientists and engineers attending the 33rd Actinide Separations Conference. We believe that you will find that Granlibakken and the Lake Tahoe views provide an atmosphere that is stimulating for fruitful discussions between participants from both government and private industry. We thank the Lawrence Livermore National Laboratory and the United States Department of Energy for their support of this conference. We especially thank you, the participants and subject matter experts, for your involvement in the 33rd Actinide Separations Conference.

  1. Kinetics of actinide complexation reactions

    SciTech Connect

    Nash, K.L.; Sullivan, J.C.

    1997-09-01

    Though the literature records extensive compilations of the thermodynamics of actinide complexation reactions, the kinetics of complex formation and dissociation reactions of actinide ions in aqueous solutions have not been extensively investigated. In light of the central role played by such reactions in actinide process and environmental chemistry, this situation is somewhat surprising. The authors report herein a summary of what is known about actinide complexation kinetics. The systems include actinide ions in the four principal oxidation states (III, IV, V, and VI) and complex formation and dissociation rates with both simple and complex ligands. Most of the work reported was conducted in acidic media, but a few address reactions in neutral and alkaline solutions. Complex formation reactions tend in general to be rapid, accessible only to rapid-scan and equilibrium perturbation techniques. Complex dissociation reactions exhibit a wider range of rates and are generally more accessible using standard analytical methods. Literature results are described and correlated with the known properties of the individual ions.

  2. Actinides and Life's Origins

    NASA Astrophysics Data System (ADS)

    Adam, Zachary

    2007-12-01

    There are growing indications that life began in a radioactive beach environment. A geologic framework for the origin or support of life in a Hadean heavy mineral placer beach has been developed, based on the unique chemical properties of the lower-electronic actinides, which act as nuclear fissile and fertile fuels, radiolytic energy sources, oligomer catalysts, and coordinating ions (along with mineralogically associated lanthanides) for prototypical prebiotic homonuclear and dinuclear metalloenzymes. A four-factor nuclear reactor model was constructed to estimate how much uranium would have been required to initiate a sustainable fission reaction within a placer beach sand 4.3 billion years ago. It was calculated that about 1-8 weight percent of the sand would have to have been uraninite, depending on the weight percent, uranium enrichment, and quantity of neutron poisons present within the remaining placer minerals. Radiolysis experiments were conducted with various solvents with the use of uranium- and thorium-rich minerals (metatorbernite and monazite, respectively) as proxies for radioactive beach sand in contact with different carbon, hydrogen, oxygen, and nitrogen reactants. Radiation bombardment ranged in duration of exposure from 3 weeks to 6 months. Low levels of acetonitrile (estimated to be on the order of parts per billion in concentration) were conclusively identified in 2 setups and tentatively indicated in a 3rd by gas chromatography/mass spectrometry. These low levels have been interpreted within the context of a Hadean placer beach prebiotic framework to demonstrate the promise of investigating natural nuclear reactors as power production sites that might have assisted the origins of life on young rocky planets with a sufficiently differentiated crust/mantle structure. Future investigations are recommended to better quantify the complex relationships between energy release, radioactive grain size, fissionability, reactant phase, phosphorus

  3. Actinides and Life's Origins.

    PubMed

    Adam, Zachary

    2007-12-01

    There are growing indications that life began in a radioactive beach environment. A geologic framework for the origin or support of life in a Hadean heavy mineral placer beach has been developed, based on the unique chemical properties of the lower-electronic actinides, which act as nuclear fissile and fertile fuels, radiolytic energy sources, oligomer catalysts, and coordinating ions (along with mineralogically associated lanthanides) for prototypical prebiotic homonuclear and dinuclear metalloenzymes. A four-factor nuclear reactor model was constructed to estimate how much uranium would have been required to initiate a sustainable fission reaction within a placer beach sand 4.3 billion years ago. It was calculated that about 1-8 weight percent of the sand would have to have been uraninite, depending on the weight percent, uranium enrichment, and quantity of neutron poisons present within the remaining placer minerals. Radiolysis experiments were conducted with various solvents with the use of uraniumand thorium-rich minerals (metatorbernite and monazite, respectively) as proxies for radioactive beach sand in contact with different carbon, hydrogen, oxygen, and nitrogen reactants. Radiation bombardment ranged in duration of exposure from 3 weeks to 6 months. Low levels of acetonitrile (estimated to be on the order of parts per billion in concentration) were conclusively identified in 2 setups and tentatively indicated in a 3(rd) by gas chromatography/mass spectrometry. These low levels have been interpreted within the context of a Hadean placer beach prebiotic framework to demonstrate the promise of investigating natural nuclear reactors as power production sites that might have assisted the origins of life on young rocky planets with a sufficiently differentiated crust/mantle structure. Future investigations are recommended to better quantify the complex relationships between energy release, radioactive grain size, fissionability, reactant phase, phosphorus

  4. Nuclear waste forms for actinides

    PubMed Central

    Ewing, Rodney C.

    1999-01-01

    The disposition of actinides, most recently 239Pu from dismantled nuclear weapons, requires effective containment of waste generated by the nuclear fuel cycle. Because actinides (e.g., 239Pu and 237Np) are long-lived, they have a major impact on risk assessments of geologic repositories. Thus, demonstrable, long-term chemical and mechanical durability are essential properties of waste forms for the immobilization of actinides. Mineralogic and geologic studies provide excellent candidate phases for immobilization and a unique database that cannot be duplicated by a purely materials science approach. The “mineralogic approach” is illustrated by a discussion of zircon as a phase for the immobilization of excess weapons plutonium. PMID:10097054

  5. Actinide cation-cation complexes

    SciTech Connect

    Stoyer, N.J.; Seaborg, G.T.

    1994-12-01

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO{sub 2}{sup +}) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO{sub 2}{sup +}; therefore, cation-cation complexes indicate something unique about AnO{sub 2}{sup +} cations compared to actinide cations in general. The first cation-cation complex, NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO{sub 2}{sup +} species, the cation-cation complexes of NpO{sub 2}{sup +} have been studied most extensively while the other actinides have not. The only PuO{sub 2}{sup +} cation-cation complexes that have been studied are with Fe{sup 3+} and Cr{sup 3+} and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, NpO{sub 2}{sup +}{center_dot}Th{sup 4+}, PuO{sub 2}{sup +}{center_dot}UO{sub 2}{sup 2+}, and PuO{sub 2}{sup +}{center_dot}Th{sup 4+} at an ionic strength of 6 M using LIPAS are 2.4 {plus_minus} 0.2, 1.8 {plus_minus} 0.9, 2.2 {plus_minus} 1.5, and {approx}0.8 M{sup {minus}1}.

  6. Origins of hydration lubrication

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  7. Methane Hydrate Field Program

    SciTech Connect

    2013-12-31

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

  8. Origins of hydration lubrication.

    PubMed

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

    2015-01-01

    Why is friction in healthy hips and knees so low? Hydration lubrication, according to which hydration shells surrounding charges act as lubricating elements in boundary layers (including those coating cartilage in joints), has been invoked to account for the extremely low sliding friction between surfaces in aqueous media, but not well understood. Here we report the direct determination of energy dissipation within such sheared hydration shells. By trapping hydrated ions in a 0.4-1 nm gap between atomically smooth charged surfaces as they slide past each other, we are able to separate the dissipation modes of the friction and, in particular, identify the viscous losses in the subnanometre hydration shells. Our results shed light on the origins of hydration lubrication, with potential implications both for aqueous boundary lubricants and for biolubrication. PMID:25585501

  9. Actinide Thermodynamics at Elevated Temperatures

    SciTech Connect

    Friese, Judah I.; Rao, Linfeng; Xia, Yuanxian; Bachelor, Paula P.; Tian, Guoxin

    2007-11-16

    The postclosure chemical environment in the proposed Yucca Mountain repository is expected to experience elevated temperatures. Predicting migration of actinides is possible if sufficient, reliable thermodynamic data on hydrolysis and complexation are available for these temperatures. Data are scarce and scattered for 25 degrees C, and nonexistent for elevated temperatures. This collaborative project between LBNL and PNNL collects thermodynamic data at elevated temperatures on actinide complexes with inorganic ligands that may be present in Yucca Mountain. The ligands include hydroxide, fluoride, sulfate, phosphate and carbonate. Thermodynamic parameters of complexation, including stability constants, enthalpy, entropy and heat capacity of complexation, are measured with a variety of techniques including solvent extraction, potentiometry, spectrophotometry and calorimetry

  10. Density functional theory investigations of the trivalent lanthanide and actinide extraction complexes with diglycolamides.

    PubMed

    Wang, Cong-Zhi; Lan, Jian-Hui; Wu, Qun-Yan; Zhao, Yu-Liang; Wang, Xiang-Ke; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-06-21

    At present, designing novel ligands for efficient actinide extraction in spent nuclear fuel reprocessing is extremely challenging due to the complicated chemical behaviors of actinides, the similar chemical properties of minor actinides (MA) and lanthanides, and the vulnerability of organic ligands in acidic radioactive solutions. In this work, a quantum chemical study on Am(III), Cm(III) and Eu(III) complexes with N,N,N',N'-tetraoctyl diglycolamide (TODGA) and N,N'-dimethyl-N,N'-diheptyl-3-oxapentanediamide (DMDHOPDA) has been carried out to explore the extraction behaviors of trivalent actinides (An) and lanthanides (Ln) with diglycolamides from acidic media. It has been found that in the 1 : 1 (ligand : metal) and 2 : 1 stoichiometric complexes, the carbonyl oxygen atoms have stronger coordination ability than the ether oxygen atoms, and the interactions between metal cations and organic ligands are substantially ionic. The neutral ML(NO3)3 (M = Am, Cm, Eu) complexes seem to be the most favorable species in the extraction process, and the predicted relative selectivities are in agreement with experimental results, i.e., the diglycolamide ligands have slightly higher selectivity for Am(III) over Eu(III). Such a thermodynamical priority is probably caused by the higher stabilities of Eu(III) hydration species and Eu(III)-L complexes in aqueous solution compared to their analogues. In addition, our thermodynamic analysis from water to organic medium confirms that DMDHOPDA has higher extraction ability for the trivalent actinides and lanthanides than TODGA, which may be due to the steric hindrance of the bulky alkyl groups of TODGA ligands. This work might provide an insight into understanding the origin of the actinide selectivity and a theoretical basis for designing highly efficient extractants for actinide separation. PMID:24769618

  11. Separations of actinides, lanthanides and other metals

    DOEpatents

    Smith, Barbara F.; Jarvinen, Gordon D.; Ensor, Dale D.

    1995-01-01

    An organic extracting solution comprised of a bis(acylpyrazolone or a substituted bis(acylpyrazolone) and an extraction method useful for separating certain elements of the actinide series of the periodic table having a valence of four from one other, and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also from one or more of the substances in a group consisting of hexavalent actinides, trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals and also useful for separating hexavalent actinides from one or more of the substances in a group consisting of trivalent actinides, trivalent lanthanides, trivalent iron, trivalent aluminum, divalent metals, and monovalent metals.

  12. TOUGH-Fx/Hydrate

    2005-02-01

    TOUGH-Fx/HYORATL can model the non-isothermal gas release. phase behavior and flow of fluids and heat in complex geologic media. The code can simulate production from natural gas hydrate deposits in the subsurtace (i.e., in the permafrost and in deep ocean sediments), as well as laboratory experiments of hydrate dissociation/formation in porous/fractured media. T006H-Fx/HYDRATE vi .0 includes both an equilibrium and a kinetic model of hydrate Ibmiation and dissociation. The model accounts for heat and upmore » to four mass components-- i.e., water, CH4, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dIssociation or formation, phase changes, and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects, and inhibItor-Induced effects.« less

  13. ENHANCED CHEMICAL CLEANING OF SRS WASTE TANKS TO IMPROVE ACTINIDE SOLUBILITY

    SciTech Connect

    Rudisill, T.; Thompson, M.

    2011-09-20

    Processes for the removal of residual sludge from SRS waste tanks have historically used solutions containing up to 0.9 M oxalic acid to dissolve the remaining material following sludge removal. The selection of this process was based on a comparison of a number of studies performed to evaluate the dissolution of residual sludge. In contrast, the dissolution of the actinide mass, which represents a very small fraction of the waste, has not been extensively studied. The Pu, Np, and Am in the sludge is reported to be present as hydrated and crystalline oxides. To identify aqueous solutions which have the potential to increase the solubility of the actinides, the alkaline and mildly acidic test solutions shown below were selected as candidates for use in a series of solubility experiments. The efficiency of the solutions in solubilizing the actinides was evaluated using a simulated sludge prepared by neutralizing a HNO{sub 3} solution containing Pu, Np, and Am. The hydroxide concentration was adjusted to a 1.2 M excess and the solids were allowed to age for several weeks prior to starting the experiments. The sludge was washed with 0.01 M NaOH to prepare the solids for use. Following the addition of an equal portion of the solids to each test solution, the concentrations of Pu, Np, and Am were measured as a function of time over a 792 h (33 day) period to provide a direct comparison of the efficiency of each solution in solubilizing the actinide elements. Although the composition of the sludge was limited to the hydrated actinide oxides (and did not contain other components of demonstrated importance), the results of the study provides guidance for the selection of solutions which should be evaluated in subsequent tests with a more realistic surrogate sludge and actual tank waste.

  14. Analysis of an explosion accident of nitrogen trichloride in a waste liquid containing ammonium ion and platinum black.

    PubMed

    Okada, Ken; Akiyoshi, Miyako; Ishizaki, Keiko; Sato, Hiroyasu; Matsunaga, Takehiro

    2014-08-15

    Five liters of sodium hypochlorite aqueous solution (12 mass%) was poured into 300 L of liquid waste containing ammonium ion of about 1.8 mol/L in a 500 L tank in a plant area; then, two minutes later the solution exploded with a flash on March 30th, 2005. The tank cover, the fluorescent lamp and the air duct were broken by the blast wave. Thus, we have conducted 40 runs of laboratory-scale explosion tests under various conditions (solution concentrations of (NH4)2SO4 and NaClO, temperatures, Pt catalysts, pH, etc.) to investigate the causes for such an explosion. When solutions of ammonium sulfate and sodium hypochlorite are mixed in the presence of platinum black, explosions result. This is ascribable to the formation of explosive nitrogen trichloride (NCl3). In the case where it is necessary to mix these 2 solutions (ammonium sulfate and sodium hypochlorite) in the presence of platinum black, the following conditions would reduce a probability of explosion; the initial concentration of NH4(+) should be less than 3 mol/L and the pH should be higher than 6. The hypochlorite solution (in 1/10 in volume) to be added at room temperature is recommended to be less than 0.6 mol/L. PMID:24953938

  15. Enhanced hole injection in phosphorescent organic light-emitting diodes by thermally evaporating a thin indium trichloride layer.

    PubMed

    Gao, Chun-Hong; Cai, Shi-Duan; Gu, Wei; Zhou, Dong-Ying; Wang, Zhao-Kui; Liao, Liang-Sheng

    2012-10-24

    An ultrathin layer of indium trichloride (InCl(3)) is thermally evaporated on the indium tin oxide (ITO) anode to enhance the hole injection in simplified phosphorescent organic light-emitting diodes (PHOLEDs). Comparing with the device with ultraviolet (UV)-ozone treatment, the device modified by InCl(3) exhibits a maximum current efficiency of 82.2 cd/A measured at about 2000 cd/cm(2) and 36% improvement in power efficiency measured at 20 mA/cm(2). More importantly, more than three times improvement in half lifetime estimated at an initial luminance of 1000 cd/cm(2) is achieved. The investigations using ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and the bias- and temperature-dependent current density-voltage characteristics in the related hole-dominated devices have revealed that the improved device performance is mainly attributed to the enhanced hole injection resulting from the lowered hole injection barrier height in the InCl(3)-modified devices. PMID:23003119

  16. Iron trichloride as oxidizer in acid slurry for chemical mechanical polishing of Ge2Sb2Te5

    NASA Astrophysics Data System (ADS)

    Yan, Wei-Xia; Wang, Liang-Yong; Zhang, Ze-Fang; Liu, Wei-Li; Song, Zhi-Tang

    2014-04-01

    The effect of iron trichloride (FeCl3) on chemical mechanical polishing (CMP) of Ge2Sb2Te5 (GST) film is investigated in this paper. The polishing rate of GST increases from 38 nm/min to 144 nm/min when the FeCl3 concentration changes from 0.01 wt% to 0.15 wt%, which is much faster than 20 nm/min for the 1 wt% H2O2-based slurry. This polishing rate trends are inversely correlated with the contact angle data of FeCl3-based slurry on the GST film surface. Thus, it is hypothesized that the hydrophilicity of the GST film surface is associated with the polishing rate during CMP. Atomic force microscope (AFM) and optical microscope (OM) are used to characterize the surface quality after CMP. The chemical mechanism is studied by potentiodynamic measurements such as Ecorr and Icorr to analyze chemical reaction between FeCl3 and GST surface. Finally, it is verified that slurry with FeCl3 has no influence on the electrical property of the post-CMP GST film by the resistivity-temperature (RT) tests.

  17. "Computational Modeling of Actinide Complexes"

    SciTech Connect

    Balasubramanian, K

    2007-03-07

    We will present our recent studies on computational actinide chemistry of complexes which are not only interesting from the standpoint of actinide coordination chemistry but also of relevance to environmental management of high-level nuclear wastes. We will be discussing our recent collaborative efforts with Professor Heino Nitsche of LBNL whose research group has been actively carrying out experimental studies on these species. Computations of actinide complexes are also quintessential to our understanding of the complexes found in geochemical, biochemical environments and actinide chemistry relevant to advanced nuclear systems. In particular we have been studying uranyl, plutonyl, and Cm(III) complexes are in aqueous solution. These studies are made with a variety of relativistic methods such as coupled cluster methods, DFT, and complete active space multi-configuration self-consistent-field (CASSCF) followed by large-scale CI computations and relativistic CI (RCI) computations up to 60 million configurations. Our computational studies on actinide complexes were motivated by ongoing EXAFS studies of speciated complexes in geo and biochemical environments carried out by Prof Heino Nitsche's group at Berkeley, Dr. David Clark at Los Alamos and Dr. Gibson's work on small actinide molecules at ORNL. The hydrolysis reactions of urnayl, neputyl and plutonyl complexes have received considerable attention due to their geochemical and biochemical importance but the results of free energies in solution and the mechanism of deprotonation have been topic of considerable uncertainty. We have computed deprotonating and migration of one water molecule from the first solvation shell to the second shell in UO{sub 2}(H{sub 2}O){sub 5}{sup 2+}, UO{sub 2}(H{sub 2}O){sub 5}{sup 2+}NpO{sub 2}(H{sub 2}O){sub 6}{sup +}, and PuO{sub 2}(H{sub 2}O){sub 5}{sup 2+} complexes. Our computed Gibbs free energy(7.27 kcal/m) in solution for the first time agrees with the experiment (7.1 kcal

  18. Hydration rate of obsidian.

    PubMed

    Friedman, I; Long, W

    1976-01-30

    The hydration rates of 12 obsidian samples of different chemical compositions were measured at temperatures from 95 degrees to 245 degrees C. An expression relating hydration rate to temperature was derived for each sample. The SiO(2) content and refractive index are related to the hydration rate, as are the CaO, MgO, and original water contents. With this information it is possible to calculate the hydration rate of a sample from its silica content, refractive index, or chemical index and a knowledge of the effective temperature at which the hydration occurred. The effective hydration temperature can be either measured or approximated from weather records. Rates have been calculated by both methods, and the results show that weather records can give a good approximation to the true EHT, particularly in tropical and subtropical climates. If one determines the EHT by any of the methods suggested, and also measures or knows the rate of hydration of the particular obsidian used, it should be possible to carry out absolute dating to +/- 10 percent of the true age over periods as short as several years and as long as millions of years. PMID:17782901

  19. Combustion of Methane Hydrate

    NASA Astrophysics Data System (ADS)

    Roshandell, Melika

    A significant methane storehouse is in the form of methane hydrates on the sea floor and in the arctic permafrost. Methane hydrates are ice-like structures composed of water cages housing a guest methane molecule. This caged methane represents a resource of energy and a potential source of strong greenhouse gas. Most research related to methane hydrates has been focused on their formation and dissociation because they can form solid plugs that complicate transport of oil and gas in pipelines. This dissertation explores the direct burning of these methane hydrates where heat from the combustion process dissociates the hydrate into water and methane, and the released methane fuels the methane/air diffusion flame heat source. In contrast to the pipeline applications, very little research has been done on the combustion and burning characteristics of methane hydrates. This is the first dissertation on this subject. In this study, energy release and combustion characteristics of methane hydrates were investigated both theoretically and experimentally. The experimental study involved collaboration with another research group, particularly in the creation of methane hydrate samples. The experiments were difficult because hydrates form at high pressure within a narrow temperature range. The process can be slow and the resulting hydrate can have somewhat variable properties (e.g., extent of clathration, shape, compactness). The experimental study examined broad characteristics of hydrate combustion, including flame appearance, burning time, conditions leading to flame extinguishment, the amount of hydrate water melted versus evaporated, and flame temperature. These properties were observed for samples of different physical size. Hydrate formation is a very slow process with pure water and methane. The addition of small amounts of surfactant increased substantially the hydrate formation rate. The effects of surfactant on burning characteristics were also studied. One finding

  20. Methane Hydrates: Chapter 8

    USGS Publications Warehouse

    Boswell, Ray; Yamamoto, Koji; Lee, Sung-Rock; Collett, Timothy S.; Kumar, Pushpendra; Dallimore, Scott

    2008-01-01

    Gas hydrate is a solid, naturally occurring substance consisting predominantly of methane gas and water. Recent scientific drilling programs in Japan, Canada, the United States, Korea and India have demonstrated that gas hydrate occurs broadly and in a variety of forms in shallow sediments of the outer continental shelves and in Arctic regions. Field, laboratory and numerical modelling studies conducted to date indicate that gas can be extracted from gas hydrates with existing production technologies, particularly for those deposits in which the gas hydrate exists as pore-filling grains at high saturation in sand-rich reservoirs. A series of regional resource assessments indicate that substantial volumes of gas hydrate likely exist in sand-rich deposits. Recent field programs in Japan, Canada and in the United States have demonstrated the technical viability of methane extraction from gas-hydrate-bearing sand reservoirs and have investigated a range of potential production scenarios. At present, basic reservoir depressurisation shows the greatest promise and can be conducted using primarily standard industry equipment and procedures. Depressurisation is expected to be the foundation of future production systems; additional processes, such as thermal stimulation, mechanical stimulation and chemical injection, will likely also be integrated as dictated by local geological and other conditions. An innovative carbon dioxide and methane swapping technology is also being studied as a method to produce gas from select gas hydrate deposits. In addition, substantial additional volumes of gas hydrate have been found in dense arrays of grain-displacing veins and nodules in fine-grained, clay-dominated sediments; however, to date, no field tests, and very limited numerical modelling, have been conducted with regard to the production potential of such accumulations. Work remains to further refine: (1) the marine resource volumes within potential accumulations that can be

  1. Process for recovering actinide values

    DOEpatents

    Horwitz, E. Philip; Mason, George W.

    1980-01-01

    A process for rendering actinide values recoverable from sodium carbonate scrub waste solutions containing these and other values along with organic compounds resulting from the radiolytic and hydrolytic degradation of neutral organophosphorous extractants such as tri-n butyl phosphate (TBP) and dihexyl-N,N-diethyl carbamylmethylene phosphonate (DHDECAMP) which have been used in the reprocessing of irradiated nuclear reactor fuels. The scrub waste solution is preferably made acidic with mineral acid, to form a feed solution which is then contacted with a water-immiscible, highly polar organic extractant which selectively extracts the degradation products from the feed solution. The feed solution can then be processed to recover the actinides for storage or recycled back into the high-level waste process stream. The extractant is recycled after stripping the degradation products with a neutral sodium carbonate solution.

  2. Actinide abundances in ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Hagee, B.; Bernatowicz, T. J.; Podosek, F. A.; Johnson, M. L.; Burnett, D. S.

    1990-01-01

    Measurements of actinide and light REE (LREE) abundances and of phosphate abundances in equilibrated ordinary chondrites were obtained and were used to define the Pu abundance in the solar system and to determine the degree of variation of actinide and LREE abundances. The results were also used to compare directly the Pu/U ratio with the earlier obtained ratio determined indirectly, as (Pu/Nd)x(Nd/U), assuming that Pu behaves chemically as a LREE. The data, combined with high-accuracy isotope-dilution data from the literature, show that the degree of gram-scale variability of the Th, U, and LREE abundances for equilibrated ordinary chondrites is a factor of 2-3 for absolute abundances and up to 50 percent for relative abundances. The observed variations are interpreted as reflecting the differences in the compositions and/or proportions of solar nebula components accreted to ordinary chondrite parent bodies.

  3. Actinide chemistry in ionic liquids.

    PubMed

    Takao, Koichiro; Bell, Thomas James; Ikeda, Yasuhisa

    2013-04-01

    This Forum Article provides an overview of the reported studies on the actinide chemistry in ionic liquids (ILs) with a particular focus on several fundamental chemical aspects: (i) complex formation, (ii) electrochemistry, and (iii) extraction behavior. The majority of investigations have been dedicated to uranium, especially for the 6+ oxidation state (UO2(2+)), because the chemistry of uranium in ordinary solvents has been well investigated and uranium is the most abundant element in the actual nuclear fuel cycles. Other actinides such as thorium, neptunium, plutonium, americium, and curiumm, although less studied, are also of importance in fully understanding the nuclear fuel engineering process and the safe geological disposal of radioactive wastes. PMID:22873132

  4. Actinide Studies with Ultracold Neutrons

    NASA Astrophysics Data System (ADS)

    Broussard, Leah

    2014-03-01

    Understanding the effects of sputtering due to nuclear fission is crucial to the nuclear industry and has wide-reaching applications, including nuclear energy, space science, and national defense. A new program at the Los Alamos Neutron Science Center uses ultracold neutrons (UCN) to induce fission in actinides such as uranium and plutonium. UCN are an ideal tool for finely controlling induced fission as a function of depth in an actinide sample. The mechanism for fission-induced surface damage is not well understood, especially regarding the effect of a surface oxide layer. We will discuss our experimental strategy for studies of UCN-induced fission and the ejected material, and present preliminary data from enriched and depleted uranium. We gratefully acknowledge the support of the G. T. Seaborg Institute for Transactinium Science and the U.S. Department of Energy through the LANL/LDRD Program for this work.

  5. Actinide Waste Forms and Radiation Effects

    NASA Astrophysics Data System (ADS)

    Ewing, R. C.; Weber, W. J.

    Over the past few decades, many studies of actinides in glasses and ceramics have been conducted that have contributed substantially to the increased understanding of actinide incorporation in solids and radiation effects due to actinide decay. These studies have included fundamental research on actinides in solids and applied research and development related to the immobilization of the high level wastes (HLW) from commercial nuclear power plants and processing of nuclear weapons materials, environmental restoration in the nuclear weapons complex, and the immobilization of weapons-grade plutonium as a result of disarmament activities. Thus, the immobilization of actinides has become a pressing issue for the twenty-first century (Ewing, 1999), and plutonium immobilization, in particular, has received considerable attention in the USA (Muller et al., 2002; Muller and Weber, 2001). The investigation of actinides and

  6. Actinide recovery techniques utilizing electromechanical processes

    SciTech Connect

    Westphal, B.R.; Benedict, R.W.

    1994-01-01

    Under certain conditions, the separation of actinides using electromechanical techniques may be an effective means of residue processing. The separation of granular mixtures of actinides and other materials discussed in this report is based on appreciable differences in the magnetic and electrical properties of the actinide elements. In addition, the high density of actinides, particularly uranium and plutonium, may render a simultaneous separation based on mutually complementary parameters. Both high intensity magnetic separation and electrostatic separation have been investigated for the concentration of an actinide waste stream. Waste stream constituents include an actinide metal alloy and broken quartz shards. The investigation of these techniques is in support of the Integral Fast Reactor (IFR) concept currently being developed at Argonne National Laboratory under the auspices of the Department of Energy.

  7. Withdrawing Nutrition, Hydration

    Cancer.gov

    Module eleven of the EPEC-O Self-Study Original Version discusses the general aspects of withholding or withdrawing of life-sustaining therapies, and presents a specific application to artificial nutrition and hydration.

  8. Transformations in methane hydrates

    PubMed Central

    Chou, I-Ming; Sharma, Anurag; Burruss, Robert C.; Shu, Jinfu; Mao, Ho-kwang; Hemley, Russell J.; Goncharov, Alexander F.; Stern, Laura A.; Kirby, Stephen H.

    2000-01-01

    Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) Å and volume V = 5051.3(13) Å3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) Å, c = 9.992(3) Å, and V = 1241.9(5) Å3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins. PMID:11087836

  9. Hydrate morphology: Physical properties of sands with patchy hydrate saturation

    USGS Publications Warehouse

    Dai, S.; Santamarina, J.C.; Waite, William F.; Kneafsey, T.J.

    2012-01-01

    The physical properties of gas hydrate-bearing sediments depend on the volume fraction and spatial distribution of the hydrate phase. The host sediment grain size and the state of effective stress determine the hydrate morphology in sediments; this information can be used to significantly constrain estimates of the physical properties of hydrate-bearing sediments, including the coarse-grained sands subjected to high effective stress that are of interest as potential energy resources. Reported data and physical analyses suggest hydrate-bearing sands contain a heterogeneous, patchy hydrate distribution, whereby zones with 100% pore-space hydrate saturation are embedded in hydrate-free sand. Accounting for patchy rather than homogeneous hydrate distribution yields more tightly constrained estimates of physical properties in hydrate-bearing sands and captures observed physical-property dependencies on hydrate saturation. For example, numerical modeling results of sands with patchy saturation agree with experimental observation, showing a transition in stiffness starting near the series bound at low hydrate saturations but moving toward the parallel bound at high hydrate saturations. The hydrate-patch size itself impacts the physical properties of hydrate-bearing sediments; for example, at constant hydrate saturation, we find that conductivity (electrical, hydraulic and thermal) increases as the number of hydrate-saturated patches increases. This increase reflects the larger number of conductive flow paths that exist in specimens with many small hydrate-saturated patches in comparison to specimens in which a few large hydrate saturated patches can block flow over a significant cross-section of the specimen.

  10. Synergistic efficacy of γ-radiation together with gallium trichloride and/or doxorubicin against Ehrlich carcinoma in female mice.

    PubMed

    Kandil, Eman; Aziz, Nahed Abdel

    2016-02-01

    Combining chemotherapy with radiotherapy represents a key oncology strategy for a more comprehensive attack toward cancers and improves treatment outcome for various solid tumor malignancies. The present study aims to evaluate the synergistic antitumor effect of γ-radiation together with gallium trichloride (GaCl3) and/or doxorubicin (DOX) against solid Ehrlich carcinoma (EC) in female mice. GaCl3 (300 mg/kg body weight (b.w.)) was administered by gavages daily on the seventh day after tumor inoculation, while the cytotoxic drug DOX (4 mg/kg b.w.) was administered intraperitoneally once a week. Whole-body γ-radiation was carried out at a dose 2 Gy once a week. Biochemical analysis showed that solid EC induced a significant increase in malondialdehyde (MDA) content with a significant decrease in the antioxidant state (glutathione peroxidase (GPx) and catalase (CAT) activities) and depleted serum iron concentration compared to normal control. Moreover, a significant increase was observed in calcium level and caspase-3 concentrations in both serum and tumor homogenate respectively associated with a significant alteration in heart, liver, and kidney functions, as compared to control. Treatment of EC-bearing mice with GaCl3and/or DOX combined with γ-radiation exposure significantly reduced tumor volume and displayed a significant improvement in most studied markers which may indicate a synergistic effect of this combination against organ dysfunction and cellular injury. The histopathologically investigation showed that treatment of animals bearing EC with GaCl3and/or DOX with γ-radiation exposure showed shrinkage in tumor lesions and wide zones of apoptotic cells with signs of regenerations. It was concluded that the combination of GaCl3and/or DOX with γ-radiation exposure resulted in super-additive cytotoxic effects on treatment of cancer cells. PMID:26318299

  11. Analysis of large soil samples for actinides

    DOEpatents

    Maxwell, III; Sherrod L.

    2009-03-24

    A method of analyzing relatively large soil samples for actinides by employing a separation process that includes cerium fluoride precipitation for removing the soil matrix and precipitates plutonium, americium, and curium with cerium and hydrofluoric acid followed by separating these actinides using chromatography cartridges.

  12. Prompt fission neutron spectra of actinides

    DOE PAGESBeta

    Capote, R.; Chen, Y. -J.; Hambsch, F. -J.; Kornilov, N. V.; Lestone, J. P.; Litaize, O.; Morillon, B.; Neudecker, D.; Oberstedt, S.; Ohsawa, T.; et al

    2016-01-06

    Here, the energy spectrum of prompt neutrons emitted in fission (PFNS) plays a very important role in nuclear science and technology. A Coordinated Research Project (CRP) "Evaluation of Prompt Fission Neutron Spectra of Actinides" was established by the IAEA Nuclear Data Section in 2009, with the major goal to produce new PFNS evaluations with uncertainties for actinide nuclei.

  13. Minor Actinides Recycling in PWRs

    SciTech Connect

    Delpech, M.; Golfier, H.; Vasile, A.; Varaine, F.; Boucher, L.; Greneche, D.

    2006-07-01

    Recycling of minor actinides in current and near future PWR is considered as one of the options of the general waste management strategy. This paper presents the analysis of this option both from the core physics and fuel cycle point of view. A first indicator of the efficiency of different neutron spectra for transmutation purposes is the capture to fission cross sections ratio which is less favourable by a factor between 5 to 10 in PWRs compared to fast reactors. Another indicator presented is the production of high ranking isotopes like Curium, Berkelium or Californium in the thermal or epithermal spectrum conditions of PWR cores by successive neutron captures. The impact of the accumulation of this elements on the fabrication process of such PWR fuels strongly penalizes this option. The main constraint on minor actinides loadings in PWR (or fast reactors) fuels are related to their direct impact (or the impact of their transmutation products) on the reactivity coefficients, the reactivity control means and the core kinetics parameters. The main fuel cycle physical parameters like the neutron source, the alpha decay power, the gamma and neutrons dose rate and the criticality aspects are also affected. Recent neutronic calculations based on a reference core of the Evolutionary Pressurized Reactor (EPR), indicates typical maximum values of 1 % loadings. Different fuel design options for minor actinides transmutation purposes in PWRs are presented: UOX and MOX, homogeneous and heterogeneous assemblies. In this later case, Americium loading is concentrated in specific pins of a standard UOX assembly. Recycling of Neptunium in UOX and MOX fuels was also studied to improve the proliferation resistance of the fuel. The impact on the core physics and penalties on Uranium enrichment were underlined in this case. (authors)

  14. Actinide abundances in ordinary chondrites

    USGS Publications Warehouse

    Hagee, B.; Bernatowicz, T.J.; Podosek, F.A.; Johnson, M.L.; Burnett, D.S.; Tatsumoto, M.

    1990-01-01

    Measurements of 244Pu fission Xe, U, Th, and light REE (LREE) abundances, along with modal petrographic determinations of phosphate abundances, were carried out on equilibrated ordinary chondrites in order to define better the solar system Pu abundance and to determine the degree of variation of actinide and LREE abundances. Our data permit comparison of the directly measured Pu/ U ratio with that determined indirectly as (Pu/Nd) ?? (Nd/U) assuming that Pu behaves chemically as a LREE. Except for Guaren??a, and perhaps H chondrites in general, Pu concentrations are similar to that determined previously for St. Se??verin, although less precise because of higher trapped Xe contents. Trapped 130Xe 136Xe ratios appear to vary from meteorite to meteorite, but, relative to AVCC, all are similar in the sense of having less of the interstellar heavy Xe found in carbonaceous chondrite acid residues. The Pu/U and Pu/Nd ratios are consistent with previous data for St. Se??verin, but both tend to be slightly higher than those inferred from previous data on Angra dos Reis. Although significant variations exist, the distribution of our Th/U ratios, along with other precise isotope dilution data for ordinary chondrites, is rather symmetric about the CI chondrite value; however, actinide/(LREE) ratios are systematically lower than the CI value. Variations in actinide or LREE absolute and relative abundances are interpreted as reflecting differences in the proportions and/or compositions of more primitive components (chondrules and CAI materials?) incorporated into different regions of the ordinary chondrite parent bodies. The observed variations of Th/U, Nd/U, or Ce/U suggest that measurements of Pu/U on any single equilibrated ordinary chondrite specimen, such as St. Se??verin, should statistically be within ??20-30% of the average solar system value, although it is also clear that anomalous samples exist. ?? 1990.

  15. Separation of actinides from lanthanides

    DOEpatents

    Smith, Barbara F.; Jarvinen, Gordon D.; Ryan, Robert R.

    1989-01-01

    An organic extracting solution and an extraction method useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).

  16. Separation of actinides from lanthanides

    DOEpatents

    Smith, B.F.; Jarvinen, G.D.; Ryan, R.R.

    1988-03-31

    An organic extracting solution and an extraction method useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form is described. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4- dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).

  17. Exploring actinide materials through synchrotron radiation techniques.

    PubMed

    Shi, Wei-Qun; Yuan, Li-Yong; Wang, Cong-Zhi; Wang, Lin; Mei, Lei; Xiao, Cheng-Liang; Zhang, Li; Li, Zi-Jie; Zhao, Yu-Liang; Chai, Zhi-Fang

    2014-12-10

    Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of actinide-based materials. This trend is partially driven by the basic needs for multi-scale actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X-ray absorption spectroscopy, X-ray diffraction and scattering spectroscopy, which are powerful tools to characterize actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with actinides are illustrated as well. PMID:25169914

  18. Actinide ion sensor for pyroprocess monitoring

    DOEpatents

    Jue, Jan-fong; Li, Shelly X.

    2014-06-03

    An apparatus for real-time, in-situ monitoring of actinide ion concentrations which comprises a working electrode, a reference electrode, a container, a working electrolyte, a separator, a reference electrolyte, and a voltmeter. The container holds the working electrolyte. The voltmeter is electrically connected to the working electrode and the reference electrode and measures the voltage between those electrodes. The working electrode contacts the working electrolyte. The working electrolyte comprises an actinide ion of interest. The reference electrode contacts the reference electrolyte. The reference electrolyte is separated from the working electrolyte by the separator. The separator contacts both the working electrolyte and the reference electrolyte. The separator is ionically conductive to the actinide ion of interest. The reference electrolyte comprises a known concentration of the actinide ion of interest. The separator comprises a beta double prime alumina exchanged with the actinide ion of interest.

  19. Actinide co-conversion by internal gelation

    SciTech Connect

    Robisson, Anne-Charlotte; Dauby, Jacques; Dumont-Shintu, Corinne; Machon, Estelle; Grandjean, Stephane

    2007-07-01

    Suitable microstructures and homogenous microspheres of actinide compounds are of interest for future nuclear fuel or transmutation target concepts to prevent the generation and dispersal of actinide powder. Sol-gel routes are being investigated as one of the possible solutions for producing these compounds. Preliminary work is described involving internal gelation to synthesize mixed compounds including minor actinides, particularly mixed actinide or mixed actinide-inert element compounds. A parameter study is discussed to highlight the importance of the initial broth composition for obtaining gel microspheres without major defects (cracks, craters, etc.). In particular, conditions are defined to produce gel beads from Zr(IV)/Y(III)/Ce(III) or Zr(IV)/An(III) systems. After gelation, the heat treatment of these microspheres is described for the purpose of better understanding the formation of cracks after calcination and verifying the effective synthesis of an oxide solid-solution. (authors)

  20. HYDRATE CORE DRILLING TESTS

    SciTech Connect

    John H. Cohen; Thomas E. Williams; Ali G. Kadaster; Bill V. Liddell

    2002-11-01

    The ''Methane Hydrate Production from Alaskan Permafrost'' project is a three-year endeavor being conducted by Maurer Technology Inc. (MTI), Noble, and Anadarko Petroleum, in partnership with the U.S. DOE National Energy Technology Laboratory (NETL). The project's goal is to build on previous and ongoing R&D in the area of onshore hydrate deposition. The project team plans to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope includes drilling and coring one well on Anadarko leases in FY 2003 during the winter drilling season. A specially built on-site core analysis laboratory will be used to determine some of the physical characteristics of the hydrates and surrounding rock. Prior to going to the field, the project team designed and conducted a controlled series of coring tests for simulating coring of hydrate formations. A variety of equipment and procedures were tested and modified to develop a practical solution for this special application. This Topical Report summarizes these coring tests. A special facility was designed and installed at MTI's Drilling Research Center (DRC) in Houston and used to conduct coring tests. Equipment and procedures were tested by cutting cores from frozen mixtures of sand and water supported by casing and designed to simulate hydrate formations. Tests were conducted with chilled drilling fluids. Tests showed that frozen core can be washed out and reduced in size by the action of the drilling fluid. Washing of the core by the drilling fluid caused a reduction in core diameter, making core recovery very difficult (if not impossible). One successful solution was to drill the last 6 inches of core dry (without fluid circulation). These tests demonstrated that it will be difficult to capture core when drilling in permafrost or hydrates without implementing certain safeguards. Among the coring tests was a simulated hydrate formation comprised of coarse, large

  1. Rapid actinide-separation methods

    SciTech Connect

    Maxwell, S.L. III

    1997-12-31

    New high-speed actinide-separation methods have been developed by the Savannah River Site Central Laboratory that can be applied to nuclear materials process samples, waste solutions and environmental samples. As part of a reengineering effort to improve efficiencies and reduce operating costs, solvent extraction methods (TTA, Hexone, TBP and TIOA) used for over thirty years in the SRS Central Laboratory were replaced with new rapid extraction column methods able to handle a variety of difficult sample matrices and actinide levels. Significant costs savings were realized and costly mixed-waste controls were avoided by using applied vacuum and 50-100 micron particle-size resins from Eichrom Industries. TEVA Resin{reg_sign}, UTEVA Resin{reg_sign}, and TRU Resin{reg_sign} columns are used with flow rates of approximately two to three milliliters per minute to minimize sample turnaround times. Single-column, dual-column and sequential-cartridge methods for plutonium, uranium, neptunium, americium and curium were developed that enable rapid, cost-effective separations prior to alpha-particle counting, thermal ionization and inductively coupled plasma mass spectrometry, and laser phosphorescence measurements.

  2. Dynamics of protein hydration water

    NASA Astrophysics Data System (ADS)

    Wolf, M.; Emmert, S.; Gulich, R.; Lunkenheimer, P.; Loidl, A.

    2015-09-01

    We present the frequency- and temperature-dependent dielectric properties of lysozyme solutions in a broad concentration regime, measured at subzero temperatures, and compare the results with measurements above the freezing point of water and on hydrated lysozyme powder. Our experiments allow examining the dynamics of unfreezable hydration water in a broad temperature range. The obtained results prove the bimodality of the hydration shell dynamics. In addition, we find indications of a fragile-to-strong transition of hydration water.

  3. Dynamics of protein hydration water.

    PubMed

    Wolf, M; Emmert, S; Gulich, R; Lunkenheimer, P; Loidl, A

    2015-09-01

    We present the frequency- and temperature-dependent dielectric properties of lysozyme solutions in a broad concentration regime, measured at subzero temperatures, and compare the results with measurements above the freezing point of water and on hydrated lysozyme powder. Our experiments allow examining the dynamics of unfreezable hydration water in a broad temperature range. The obtained results prove the bimodality of the hydration shell dynamics. In addition, we find indications of a fragile-to-strong transition of hydration water. PMID:26465518

  4. Phosphinate chemistry in the 21st century: a viable alternative to the use of phosphorus trichloride in organophosphorus synthesis.

    PubMed

    Montchamp, Jean-Luc

    2014-01-21

    Organophosphorus compounds are important in everyday applications ranging from agriculture to medicine and are used in flame retardants and other materials. Although organophosphorus chemistry is known as a mature and specialized area, researchers would like to develop new methods for synthesizing organophosphorus compounds to improve the safety and sustainability of these chemical processes. The vast majority of compounds that contain a phosphorus-carbon bond are manufactured using phosphorus trichloride (PCl3) as an intermediate. However, these reactions require chlorine, and researchers would like to avoid the use of PCl3 and develop safer chemistry that also decreases energy consumption and minimizes waste. Researchers have already proposed and discussed two primary strategies based on elemental phosphorus (P4 or Pred) or on phosphine (PH3) as alternatives to PCl3. However, phosphinates, an important class of phosphorus compounds defined as any compound with a phosphorus atom attached to two oxygens, R(1)R(2)P(O)(OR) (R(1)/R(2) = hydrogen/carbon), offer another option. This Account discusses the previously neglected potential of these phosphinates as replacements of PCl3 for the preparation of organophosphorus compounds. Because of their strong reductive properties, industry currently uses the simplest members of this class of compounds, hypophosphites, for one major application: electroless plating. In comparison with other proposed PCl3 surrogates, hypophosphorous derivatives can offer improved stability, lower toxicity, higher solubility, and increased atom economy. When their reducing power is harnessed to form phosphorus-carbon or phosphorus-oxygen bonds, these compounds are also rich and versatile precursors to organophosphorus compounds. This Account examines the use of transition metal-catalyzed reactions such as cross-coupling and hydrophosphinylation for phosphorus-carbon bond formation. Because the most important industrial organophosphorus compounds

  5. Changes in serum pneumoproteins caused by short-term exposures to nitrogen trichloride in indoor chlorinated swimming pools.

    PubMed

    Carbonnelle, Sylviane; Francaux, Marc; Doyle, Ian; Dumont, Xavier; de Burbure, Claire; Morel, Georges; Michel, Olivier; Bernard, Alfred

    2002-01-01

    Nitrogen trichloride (NCl(3)) is an irritant gas released in the air of indoor pools sanitized with chlorine-based disinfectants. In the present study we investigated the effects of NCl(3) on the pulmonary epithelium of pool attendees by measuring the leakage into serum of three lung-specific proteins (pneumoproteins): the alveolar surfactant-associated proteins A and B (SP-A and SP-B) and the bronchiolar 16 kDa Clara cell protein (CC16). These pneumoproteins were measured in the serum of 29 recreational swimmers (16 children and 13 adults) before and after attending a chlorinated pool with a mean NCl(3) concentration of 490 microg m(-3). Pneumoprotein changes in serum were also studied in 14 trained swimmers performing an intensive 45 min standardized swimming session in a chlorinated pool (mean NCl(3) concentration of 355 microg m(-3)) and for the purposes of comparison in a non-chlorinated pool sanitized by the copper/silver method. Serum CC16 was not increased in recreational swimmers, but in trained swimmers serum levels of this protein peaked immediately after strenuous exercise, both in the copper/silver pool and in the chlorinated pool. This acute increase in airway permeability is probably the consequence of the mechanical stress on the epithelial barrier caused by overinflation and/or hyperventilation during intense exercise. Serum levels of SP-A and SP-B were unaffected by strenuous exercise in the copper/silver pool. The two proteins were, however, significantly increased in a time-dependent manner in recreational and trained swimmers attending the chlorinated pool. The intravascular leakage of SP-A and SP-B was already statistically significant after only 1 h of exposure to pool air without exercising and remained elevated for 12 h after. These changes were not associated with decrements in lung function. The ability of NCl(3) to acutely disrupt the lung epithelium barrier was confirmed in mice using serum CC16 and plasma proteins in bronchoalveolar

  6. Aluminum Sulfate 18 Hydrate

    ERIC Educational Resources Information Center

    Young, Jay A.

    2004-01-01

    A chemical laboratory information profile (CLIP) of the chemical, aluminum sulfate 18 hydrate, is presented. The profile lists physical and harmful properties, exposure limits, reactivity risks, and symptoms of major exposure for the benefit of teachers and students using the chemical in the laboratory.

  7. Decontamination of matrices containing actinide oxides

    SciTech Connect

    Villarreal, Robert

    1997-12-01

    There is provided a method for removing actinides and actinide oxides, particularly fired actinides, from soil and other contaminated matrices, comprising: (a) contacting a contaminated material with a solution of at least one inhibited fluoride and an acid to form a mixture; (b) heating the mixture of contaminated material and solution to a temperature in the range from about 30 C to about 90 C while stirring; (c) separating the solution from any undissolved matrix material in the mixture; (d) washing the undissolved matrix material to remove any residual materials; and (e) drying and returning the treated matrix material to the environment.

  8. Experimental studies of actinides in molten salts

    SciTech Connect

    Reavis, J.G.

    1985-06-01

    This review stresses techniques used in studies of molten salts containing multigram amounts of actinides exhibiting intense alpha activity but little or no penetrating gamma radiation. The preponderance of studies have used halides because oxygen-containing actinide compounds (other than oxides) are generally unstable at high temperatures. Topics discussed here include special enclosures, materials problems, preparation and purification of actinide elements and compounds, and measurements of various properties of the molten volts. Property measurements discussed are phase relationships, vapor pressure, density, viscosity, absorption spectra, electromotive force, and conductance. 188 refs., 17 figs., 6 tabs.

  9. Actinide removal from spent salts

    DOEpatents

    Hsu, Peter C.; von Holtz, Erica H.; Hipple, David L.; Summers, Leslie J.; Adamson, Martyn G.

    2002-01-01

    A method for removing actinide contaminants (uranium and thorium) from the spent salt of a molten salt oxidation (MSO) reactor is described. Spent salt is removed from the reactor and analyzed to determine the contaminants present and the carbonate concentration. The salt is dissolved in water, and one or more reagents are added to precipitate the thorium as thorium oxide and/or the uranium as either uranium oxide or as a diuranate salt. The precipitated materials are filtered, dried and packaged for disposal as radioactive waste. About 90% of the thorium and/or uranium present is removed by filtration. After filtration, salt solutions having a carbonate concentration >20% can be dried and returned to the reactor for re-use. Salt solutions containing a carbonate concentration <20% require further clean-up using an ion exchange column, which yields salt solutions that contain less than 0.1 ppm of thorium or uranium.

  10. PF-4 actinide disposition strategy

    SciTech Connect

    Margevicius, Robert W

    2010-05-28

    The dwindling amount of Security Category I processing and storage space across the DOE Complex has driven the need for more effective storage of nuclear materials at LANL's Plutonium Facility's (PF-4's) vault. An effort was begun in 2009 to create a strategy, a roadmap, to identify all accountable nuclear material and determine their disposition paths, the PF-4 Actinide Disposition Strategy (PADS). Approximately seventy bins of nuclear materials with similar characteristics - in terms of isotope, chemical form, impurities, disposition location, etc. - were established in a database. The ultimate disposition paths include the material to remain at LANL, disposition to other DOE sites, and disposition to waste. If all the actions described in the document were taken, over half of the containers currently in the PF-4 vault would been eliminated. The actual amount of projected vault space will depend on budget and competing mission requirements, however, clearly a significant portion of the current LANL inventory can be either dispositioned or consolidated.

  11. Subsurface interactions of actinide species and microorganisms : implications for the bioremediation of actinide-organic mixtures.

    SciTech Connect

    Banaszak, J.E.; Reed, D.T.; Rittmann, B.E.

    1999-02-12

    By reviewing how microorganisms interact with actinides in subsurface environments, we assess how bioremediation controls the fate of actinides. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinide's oxidation state or its speciation. We describe how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility. We explain why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions. Due to the complex interactions of the microbiological and chemical phenomena, mathematical modeling is an essential tool for research on and application of bioremediation involving co-contamination with actinides. We describe the development of mathematical models that link microbiological and geochemical reactions. Throughout, we identify the key research needs.

  12. Overview of actinide chemistry in the WIPP

    SciTech Connect

    Borkowski, Marian; Lucchini, Jean - Francois; Richmann, Michael K; Reed, Donald T; Khaing, Hnin; Swanson, Juliet

    2009-01-01

    The year 2009 celebrates 10 years of safe operations at the Waste Isolation Pilot Plant (WIPP), the only nuclear waste repository designated to dispose defense-related transuranic (TRU) waste in the United States. Many elements contributed to the success of this one-of-the-kind facility. One of the most important of these is the chemistry of the actinides under WIPP repository conditions. A reliable understanding of the potential release of actinides from the site to the accessible environment is important to the WIPP performance assessment (PA). The environmental chemistry of the major actinides disposed at the WIPP continues to be investigated as part of the ongoing recertification efforts of the WIPP project. This presentation provides an overview of the actinide chemistry for the WIPP repository conditions. The WIPP is a salt-based repository; therefore, the inflow of brine into the repository is minimized, due to the natural tendency of excavated salt to re-seal. Reducing anoxic conditions are expected in WIPP because of microbial activity and metal corrosion processes that consume the oxygen initially present. Should brine be introduced through an intrusion scenario, these same processes will re-establish reducing conditions. In the case of an intrusion scenario involving brine, the solubilization of actinides in brine is considered as a potential source of release to the accessible environment. The following key factors establish the concentrations of dissolved actinides under subsurface conditions: (1) Redox chemistry - The solubility of reduced actinides (III and IV oxidation states) is known to be significantly lower than the oxidized forms (V and/or VI oxidation states). In this context, the reducing conditions in the WIPP and the strong coupling of the chemistry for reduced metals and microbiological processes with actinides are important. (2) Complexation - For the anoxic, reducing and mildly basic brine systems in the WIPP, the most important

  13. Electronic structure and correlation effects in actinides

    SciTech Connect

    Albers, R.C.

    1998-12-01

    This report consists of the vugraphs given at a conference on electronic structure. Topics discussed are electronic structure, f-bonding, crystal structure, and crystal structure stability of the actinides and how they are inter-related.

  14. Advanced Aqueous Separation Systems for Actinide Partitioning

    SciTech Connect

    Nash, Kenneth L.; Clark, Sue; Meier, G Patrick; Alexandratos, Spiro; Paine, Robert; Hancock, Robert; Ensor, Dale

    2012-03-21

    One of the most challenging aspects of advanced processing of spent nuclear fuel is the need to isolate transuranium elements from fission product lanthanides. This project expanded the scope of earlier investigations of americium (Am) partitioning from the lanthanides with the synthesis of new separations materials and a centralized focus on radiochemical characterization of the separation systems that could be developed based on these new materials. The primary objective of this program was to explore alternative materials for actinide separations and to link the design of new reagents for actinide separations to characterizations based on actinide chemistry. In the predominant trivalent oxidation state, the chemistry of lanthanides overlaps substantially with that of the trivalent actinides and their mutual separation is quite challenging.

  15. BWR Assembly Optimization for Minor Actinide Recycling

    SciTech Connect

    G. Ivan Maldonado; John M. Christenson; J.P. Renier; T.F. Marcille; J. Casal

    2010-03-22

    The Primary objective of the proposed project is to apply and extend the latest advancements in LWR fuel management optimization to the design of advanced boiling water reactor (BWR) fuel assemblies specifically for the recycling of minor actinides (MAs).

  16. Joint Actinide Shock Physics Experimental Research - JASPER

    ScienceCinema

    None

    2015-01-09

    Commonly known as JASPER the Joint Actinide Shock Physics Experimental Research facility is a two stage light gas gun used to study the behavior of plutonium and other materials under high pressures, temperatures, and strain rates.

  17. Joint Actinide Shock Physics Experimental Research - JASPER

    SciTech Connect

    2014-10-31

    Commonly known as JASPER the Joint Actinide Shock Physics Experimental Research facility is a two stage light gas gun used to study the behavior of plutonium and other materials under high pressures, temperatures, and strain rates.

  18. Preparation of actinide targets by electrodeposition

    NASA Astrophysics Data System (ADS)

    Trautmann, N.; Folger, H.

    1989-10-01

    Actinide targets with varying thicknesses on different substrates have been prepared by electrodeposition either from aqueous solutions or from solutions of their nitrates in isopropyl alcohol. With these techniques the actinides can be deposited almost quantitatively on various backing materials within 15 to 30 min. Targets of thorium, uranium, neptunium, plutonium, americium, curium and californium with areal densities from almost carrier-free up to 1.4 mg/cm 2 on thin beryllium, carbon, titanium, tantalum and platinum foils have been prepared. In most cases, prior to the deposition, the actinides had to be purified chemically and for some of them, due to the limited amount of material available, recycling procedures were required. Applications of actinide targets in heavy-ion reactions are briefly discussed.

  19. PREPARATION OF ACTINIDE-ALUMINUM ALLOYS

    DOEpatents

    Moore, R.H.

    1962-09-01

    BS>A process is given for preparing alloys of aluminum with plutonium, uranium, and/or thorium by chlorinating actinide oxide dissolved in molten alkali metal chloride with hydrochloric acid, chlorine, and/or phosgene, adding aluminum metal, and passing air and/or water vapor through the mass. Actinide metal is formed and alloyed with the aluminum. After cooling to solidification, the alloy is separated from the salt. (AEC)

  20. Transmutation of actinides in power reactors.

    PubMed

    Bergelson, B R; Gerasimov, A S; Tikhomirov, G V

    2005-01-01

    Power reactors can be used for partial short-term transmutation of radwaste. This transmutation is beneficial in terms of subsequent storage conditions for spent fuel in long-term storage facilities. CANDU-type reactors can transmute the main minor actinides from two or three reactors of the VVER-1000 type. A VVER-1000-type reactor can operate in a self-service mode with transmutation of its own actinides. PMID:16604724

  1. Synergism of trivalent actinides and lanthanides

    SciTech Connect

    Mathur, J.N.

    1983-01-01

    The synergism of trivalent actinides and lanthanides has been reviewed critically. Different systems including ..beta..-di-ketones and several other chelating agents with various neutral donors have been discussed. The thermodynamic parameters, effect of diluents, auto-synergism and synergism with eutectic mixtures have been discussed in the case of trivalent actinides and lanthanides. Also the mechanism of synergism and the various possible uses of this phenomenon have been referred to with the possible data available. 160 references, 4 tables.

  2. Structural and magnetic characterization of actinide materials

    SciTech Connect

    Cort, B.; Allen, T.H.; Lawson, A.C.

    1998-12-31

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The authors have successfully used neutron scattering techniques to investigate physicochemical properties of elements, compounds, and alloys of the light actinides. The focus of this work is to extend the fundamental research capability and to address questions of practical importance to stockpile integrity and long-term storage of nuclear material. Specific subject areas are developing neutron diffraction techniques for smaller actinide samples; modeling of inelastic scattering data for actinide metal hydrides; characterizing actinide oxide structures; and investigating aging effects in actinides. These studies utilize neutron scattering supported by equilibrium studies, kinetics, and x-ray diffraction. Major accomplishments include (1) development of encapsulation techniques for small actinide samples and neutron diffraction studies of AmD{sub 2.4} and PuO{sub 2.3}; (2) refinement of lattice dynamics model to elucidate hydrogen-hydrogen and hydrogen-metal interactions in rare-earth and actinide hydrides; (3) kinetic studies with PuO{sub 2} indicating that the recombination reaction is faster than radiolytic decomposition of adsorbed water but a chemical reaction produces H{sub 2}; (4) PVT studies of the reaction between PuO{sub 2} and water demonstrate that PuO{sub 2+x} and H{sub 2} form and that PuO{sub 2} is not the thermodynamically stable form of the oxide in air; and (5) model calculations of helium in growth in aged plutonium predicting bubble formation only at grain boundaries at room temperature. The work performed in this project has application to fundamental properties of actinides, aging, and long-term storage of plutonium.

  3. Rapid determination of actinides in seawater samples

    DOE PAGESBeta

    Maxwell, Sherrod L.; Culligan, Brian K.; Hutchison, Jay B.; Utsey, Robin C.; McAlister, Daniel R.

    2014-03-09

    A new rapid method for the determination of actinides in seawater samples has been developed at the Savannah River National Laboratory. The actinides can be measured by alpha spectrometry or inductively-coupled plasma mass spectrometry. The new method employs novel pre-concentration steps to collect the actinide isotopes quickly from 80 L or more of seawater. Actinides are co-precipitated using an iron hydroxide co-precipitation step enhanced with Ti+3 reductant, followed by lanthanum fluoride co-precipitation. Stacked TEVA Resin and TRU Resin cartridges are used to rapidly separate Pu, U, and Np isotopes from seawater samples. TEVA Resin and DGA Resin were used tomore » separate and measure Pu, Am and Cm isotopes in seawater volumes up to 80 L. This robust method is ideal for emergency seawater samples following a radiological incident. It can also be used, however, for the routine analysis of seawater samples for oceanographic studies to enhance efficiency and productivity. In contrast, many current methods to determine actinides in seawater can take 1–2 weeks and provide chemical yields of ~30–60 %. This new sample preparation method can be performed in 4–8 h with tracer yields of ~85–95 %. By employing a rapid, robust sample preparation method with high chemical yields, less seawater is needed to achieve lower or comparable detection limits for actinide isotopes with less time and effort.« less

  4. Recent progress in actinide borate chemistry

    SciTech Connect

    Wang, Shuao; Alekseev, Evgeny V.; Depmeier, Wulf; Albrecht-Schmitt, Thomas E.

    2011-01-01

    The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties. [ThB₅O₆(OH)₆][BO(OH)₂]·2.5H₂O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO4- Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials.

  5. Recent progress in actinide borate chemistry.

    PubMed

    Wang, Shuao; Alekseev, Evgeny V; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2011-10-21

    The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties. [ThB(5)O(6)(OH)(6)][BO(OH)(2)]·2.5H(2)O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO(4)(-). Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials. PMID:21915396

  6. Rapid determination of actinides in seawater samples

    SciTech Connect

    Maxwell, Sherrod L.; Culligan, Brian K.; Hutchison, Jay B.; Utsey, Robin C.; McAlister, Daniel R.

    2014-03-09

    A new rapid method for the determination of actinides in seawater samples has been developed at the Savannah River National Laboratory. The actinides can be measured by alpha spectrometry or inductively-coupled plasma mass spectrometry. The new method employs novel pre-concentration steps to collect the actinide isotopes quickly from 80 L or more of seawater. Actinides are co-precipitated using an iron hydroxide co-precipitation step enhanced with Ti+3 reductant, followed by lanthanum fluoride co-precipitation. Stacked TEVA Resin and TRU Resin cartridges are used to rapidly separate Pu, U, and Np isotopes from seawater samples. TEVA Resin and DGA Resin were used to separate and measure Pu, Am and Cm isotopes in seawater volumes up to 80 L. This robust method is ideal for emergency seawater samples following a radiological incident. It can also be used, however, for the routine analysis of seawater samples for oceanographic studies to enhance efficiency and productivity. In contrast, many current methods to determine actinides in seawater can take 1–2 weeks and provide chemical yields of ~30–60 %. This new sample preparation method can be performed in 4–8 h with tracer yields of ~85–95 %. By employing a rapid, robust sample preparation method with high chemical yields, less seawater is needed to achieve lower or comparable detection limits for actinide isotopes with less time and effort.

  7. Methane Clathrate Hydrate Prospecting

    NASA Technical Reports Server (NTRS)

    Duxbury, N.; Romanovsky, V.

    2003-01-01

    A method of prospecting for methane has been devised. The impetus for this method lies in the abundance of CH4 and the growing shortages of other fuels. The method is intended especially to enable identification of subpermafrost locations where significant amounts of methane are trapped in the form of methane gas hydrate (CH4(raised dot)6H2O). It has been estimated by the U.S. Geological Survey that the total CH4 resource in CH4(raised dot) 6H2O exceeds the energy content of all other fossil fuels (oil, coal, and natural gas from non-hydrate sources). Also, CH4(raised dot)6H2O is among the cleanest-burning fuels, and CH4 is the most efficient fuel because the carbon in CH4 is in its most reduced state. The method involves looking for a proxy for methane gas hydrate, by means of the combination of a thermal-analysis submethod and a field submethod that does not involve drilling. The absence of drilling makes this method easier and less expensive, in comparison with prior methods of prospecting for oil and natural gas. The proposed method would include thermoprospecting in combination with one more of the other non-drilling measurement techniques, which could include magneto-telluric sounding and/or a subsurface-electrical-resistivity technique. The method would exploit the fact that the electrical conductivity in the underlying thawed region is greater than that in the overlying permafrost.

  8. Hydration-dependent dynamic crossover phenomenon in protein hydration water

    NASA Astrophysics Data System (ADS)

    Wang, Zhe; Fratini, Emiliano; Li, Mingda; Le, Peisi; Mamontov, Eugene; Baglioni, Piero; Chen, Sow-Hsin

    2014-10-01

    The characteristic relaxation time τ of protein hydration water exhibits a strong hydration level h dependence. The dynamic crossover is observed when h is higher than the monolayer hydration level hc=0.2-0.25 and becomes more visible as h increases. When h is lower than hc, τ only exhibits Arrhenius behavior in the measured temperature range. The activation energy of the Arrhenius behavior is insensitive to h, indicating a local-like motion. Moreover, the h dependence of the crossover temperature shows that the protein dynamic transition is not directly or solely induced by the dynamic crossover in the hydration water.

  9. Gas hydrate measurements at Hydrate Ridge using Raman spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2007-06-01

    Oceanic gas hydrates have been measured near the seafloor for the first time using a seagoing Raman spectrometer at Hydrate Ridge, Oregon, where extensive layers of hydrates have been found to occur near the seafloor. All of the hydrates analyzed were liberated from the upper meter of the sediment column near active gas venting sites in water depths of 770-780 m. Hydrate properties, such as structure and composition, were measured with significantly less disturbance to the sample than would be realized with core recovery. The natural hydrates measured were sI, with methane as the predominant guest component, and minor/trace amounts of hydrogen sulfide present in three of the twelve samples measured. Methane large-to-small cage occupancy ratios of the hydrates varied from 1.01 to 1.30, in good agreement with measurements of laboratory synthesized and recovered natural hydrates. Although the samples visually appeared to be solid, varying quantities of free methane gas were detected, indicating the possible presence of occluded gas in a hydrate bubble fabric.

  10. Partitioning of actinides from high level waste of PUREX origin using octylphenyl-N,N{prime}-diisobutylcarbamoylmethyl phosphine oxide (CMPO)-based supported liquid membrane

    SciTech Connect

    Ramanujam, A.; Dhami, P.S.; Gopalakrishnan, V.; Dudwadkar, N.L.; Chitnis, R.R.; Mathur, J.N.

    1999-06-01

    The present studies deal with the application of the supported liquid membrane (SLM) technique for partitioning of actinides from high level waste of PUREX origin. The process uses a solution of octylphenyl-N,N{prime}-diisobutylcarbamoylmethyl phosphine oxide (CMPO) in n-dodecane as a carrier with a polytetrafluoroethylene support and a mixture of citric acid, formic acid, and hydrazine hydrate as the receiving phase. The studies involve the investigation of such parameters as carrier concentration in SLM, acidity of the feed, and the feed composition. The studies indicated good transport of actinides like neptunium, americium, and plutonium across the membrane from nitric acid medium. A high concentration of uranium in the feed retards the transport of americium, suggesting the need for prior removal of uranium from the waste. The separation of actinides from uranium-lean simulated samples as well as actual high level waste has been found to be feasible using the above technique.

  11. Rapid gas hydrate formation process

    SciTech Connect

    Brown, Thomas D.; Taylor, Charles E.; Unione, Alfred J.

    2013-01-15

    The disclosure provides a method and apparatus for forming gas hydrates from a two-phase mixture of water and a hydrate forming gas. The two-phase mixture is created in a mixing zone which may be wholly included within the body of a spray nozzle. The two-phase mixture is subsequently sprayed into a reaction zone, where the reaction zone is under pressure and temperature conditions suitable for formation of the gas hydrate. The reaction zone pressure is less than the mixing zone pressure so that expansion of the hydrate-forming gas in the mixture provides a degree of cooling by the Joule-Thompson effect and provides more intimate mixing between the water and the hydrate-forming gas. The result of the process is the formation of gas hydrates continuously and with a greatly reduced induction time. An apparatus for conduct of the method is further provided.

  12. Clathrate hydrates for ozone preservation.

    PubMed

    Muromachi, Sanehiro; Ohmura, Ryo; Takeya, Satoshi; Mori, Yasuhiko H

    2010-09-01

    We report the experimental evidence for the preservation of ozone (O(3)) encaged in a clathrate hydrate. Although ozone is an unstable substance and is apt to decay to oxygen (O(2)), it may be preserved for a prolonged time if it is encaged in hydrate cavities in the form of isolated molecules. This possibility was assessed using a hydrate formed from an ozone + oxygen gas mixture coexisting with carbon tetrachloride or xenon. Each hydrate sample was stored in an air-filled container at atmospheric pressure and a constant temperature in the range between -20 and 2 degrees C and was continually subjected to iodometric measurements of its fractional ozone content. Such chronological measurements and structure analysis using powder X-ray diffraction have revealed that ozone can be preserved in a hydrate-lattice structure for more than 20 days at a concentration on the order of 0.1% (hydrate-mass basis). PMID:20707330

  13. Gas hydrate cool storage system

    DOEpatents

    Ternes, M.P.; Kedl, R.J.

    1984-09-12

    The invention presented relates to the development of a process utilizing a gas hydrate as a cool storage medium for alleviating electric load demands during peak usage periods. Several objectives of the invention are mentioned concerning the formation of the gas hydrate as storage material in a thermal energy storage system within a heat pump cycle system. The gas hydrate was formed using a refrigerant in water and an example with R-12 refrigerant is included. (BCS)

  14. TUCS/phosphate mineralization of actinides

    SciTech Connect

    Nash, K.L.

    1997-10-01

    This program has as its objective the development of a new technology that combines cation exchange and mineralization to reduce the concentration of heavy metals (in particular actinides) in groundwaters. The treatment regimen must be compatible with the groundwater and soil, potentially using groundwater/soil components to aid in the immobilization process. The delivery system (probably a water-soluble chelating agent) should first concentrate the radionuclides then release the precipitating anion, which forms thermodynamically stable mineral phases, either with the target metal ions alone or in combination with matrix cations. This approach should generate thermodynamically stable mineral phases resistant to weathering. The chelating agent should decompose spontaneously with time, release the mineralizing agent, and leave a residue that does not interfere with mineral formation. For the actinides, the ideal compound probably will release phosphate, as actinide phosphate mineral phases are among the least soluble species for these metals. The most promising means of delivering the precipitant would be to use a water-soluble, hydrolytically unstable complexant that functions in the initial stages as a cation exchanger to concentrate the metal ions. As it decomposes, the chelating agent releases phosphate to foster formation of crystalline mineral phases. Because it involves only the application of inexpensive reagents, the method of phosphate mineralization promises to be an economical alternative for in situ immobilization of radionuclides (actinides in particular). The method relies on the inherent (thermodynamic) stability of actinide mineral phases.

  15. Nonaqueous method for dissolving lanthanide and actinide metals

    DOEpatents

    Crisler, L.R.

    1975-11-11

    Lanthanide and actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a lanthanide or actinide element in the elemental metallic state in a mixture of carbon tetrachloride and methanol.

  16. Ultratrace analysis of transuranic actinides by laser-induced fluorescence

    DOEpatents

    Miller, S.M.

    1983-10-31

    Ultratrace quantities of transuranic actinides are detected indirectly by their effect on the fluorescent emissions of a preselected fluorescent species. Transuranic actinides in a sample are coprecipitated with a host lattice material containing at least one preselected fluorescent species. The actinide either quenches or enhances the laser-induced fluorescence of the preselected fluorescent species. The degree of enhancement or quenching is quantitatively related to the concentration of actinide in the sample.

  17. Ultratrace analysis of transuranic actinides by laser-induced fluorescence

    DOEpatents

    Miller, Steven M.

    1988-01-01

    Ultratrace quantities of transuranic actinides are detected indirectly by their effect on the fluorescent emissions of a preselected fluorescent species. Transuranic actinides in a sample are coprecipitated with a host lattice material containing at least one preselected fluorescent species. The actinide either quenches or enhances the laser-induced fluorescence of the preselected fluorescent species. The degree of enhancement or quenching is quantitatively related to the concentration of actinide in the sample.

  18. THEORY FOR THE XPS OF ACTINIDES

    SciTech Connect

    Bagus, Paul S.; Ilton, Eugene S.

    2013-08-01

    Two aspects of the electronic structure of actinide oxides that significantly affect the XPS spectra are described; these aspects are also important for the materials properties of the oxides. The two aspects considered are: (1) The spin-orbit coupling of the open 5f shell electrons in actinide cations and how this coupling affects the electronic structure. And, (2) the covalent character of the metal oxygen interaction in actinide compounds. Because of this covalent character, there are strong departures from the nominal oxidation states that are significantly larger in core-hole states than in the ground state. The consequences for the XPS of this covalent character are examined. A proper understanding of the way in which they influence the XPS makes it possible to use the XPS to correctly characterize the electronic structure of the oxides.

  19. Minior Actinide Doppler Coefficient Measurement Assessment

    SciTech Connect

    Nolan E. Hertel; Dwayne Blaylock

    2008-04-10

    The "Minor Actinide Doppler Coefficient Measurement Assessment" was a Department of Energy (DOE) U-NERI funded project intended to assess the viability of using either the FLATTOP or the COMET critical assembly to measure high temperature Doppler coefficients. The goal of the project was to calculate using the MCNP5 code the gram amounts of Np-237, Pu-238, Pu-239, Pu-241, AM-241, AM-242m, Am-243, and CM-244 needed to produce a 1E-5 in reactivity for a change in operating temperature 800C to 1000C. After determining the viability of using the assemblies and calculating the amounts of each actinide an experiment will be designed to verify the calculated results. The calculations and any doncuted experiments are designed to support the Advanced Fuel Cycle Initiative in conducting safety analysis of advanced fast reactor or acceoerator-driven transmutation systems with fuel containing high minor actinide content.

  20. Preparation of actinide-metal research materials

    SciTech Connect

    Aaron, W.S.; Culpepper, C.A.; Campbell, K.B.

    1986-01-01

    The preparation of actinide-metal research materials is one of many functions of the Isotope Research Materials Laboratory (IRML) at Oak Ridge National Laboratory. Research samples of uranium, plutonium, americium, and curium, typically from milligram quantities up to approx. 100 g, are prepared as pure metals or alloys to customer specifications. Larger quantities, up to many kilograms, of the lower activity actinides, such as /sup 235/U, /sup 238/U, and /sup 232/Th, are also fabricated into custom research forms. Physical forms of these metals include rolled foils or sheets, castings (ingot, rod, or special shapes), and evaporated or sputtered films. The actinide-metal processing capabilities of the IRML are continuing to be improved and applied to a wide variety of custom material preparations to meet the needs of the world-wide research community.

  1. The Actinide-Lanthanide Separation Process

    SciTech Connect

    Lumetta, Gregg J.; Gelis, Artem V.; Carter, Jennifer C.; Niver, Cynthia M.; Smoot, Margaret R.

    2014-02-21

    The Actinide-Lanthanide SEParation (ALSEP) process is described. The process uses an extractant phase consisting of either N,N,N',N'-tetraoctyldiglycolamide (TODGA) or N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) combined with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). The neutral TODGA or T2EHDGA serves to co-extract the trivalent actinide and lanthanide ions from nitric acid media. Switching the aqueous phase chemistry to a citrate buffered diethylenetriaminepentaacetic acid (DTPA) solution at pH 2.5 to 4 results in selective transfer of the actinides to the aqueous phase, thus resulting in separation of these two groups of elements.

  2. FINAL REPORT. ACTINIDE-ALUMINATE SPECIATION IN ALKALINE RADIOACTIVE WASTE

    EPA Science Inventory

    Investigation of behavior of actinides in alkaline media containing Al(III) showed that no aluminate complexes of actinides in oxidation states (III-VII) were formed in alkaline solutions. At alkaline precipitation (pH 10-14) of actinides in presence of Al(III) formation of alumi...

  3. RECOVERY OF ACTINIDES FROM AQUEOUS NITRIC ACID SOLUTIONS

    DOEpatents

    Ader, M.

    1963-11-19

    A process of recovering actinides is presented. Tetravalent actinides are extracted from rare earths in an aqueous nitric acid solution with a ketone and back-extracted from the ketone into an aqueous medium. The aqueous actinide solution thus obtained, prior to concentration by boiling, is sparged with steam to reduce its ketone to a maximum content of 3 grams per liter. (AEC)

  4. Complexation of Actinides in Solution: Thermodynamic Measurementsand Structural Characterization

    SciTech Connect

    Rao, L.

    2007-02-01

    This paper presents a brief introduction of the studies of actinide complexation in solution at Lawrence Berkeley National Laboratory. An integrated approach of thermodynamic measurements and structural characterization is taken to obtain fundamental understanding of actinide complexation in solution that is of importance in predicting the behavior of actinides in separation processes and environmental transport.

  5. Bubble migration during hydrate formation

    NASA Astrophysics Data System (ADS)

    Shagapov, V. Sh.; Chiglintseva, A. S.; Rusinov, A. A.

    2015-03-01

    A model of the process of migration of methane bubbles in water under thermobaric conditions of hydrate formation is proposed. The peculiarities of the temperature field evolution, migration rate, and changes in the radius and volume fraction of gas hydrate bubbles are studied. It is shown that, with a constant mass flow of gas from the reservoir bottom, for all parameters of the surfacing gas hydrate disperse system, there is a quasistationary pattern in the form of a "step"-like wave. Depending on the relationship of the initial gas bubble density with the average gas density in the hydrate composition determined by the depth from which bubbles rise to the surface, the final radius of hydrate particles may be larger or smaller than the initial gas bubble radii. It is established that the speed at which gas hydrate inclusions rise to the surface decreases by several times due to an increase in their weight during hydrate formation. The influence of the depth of the water reservoir whose bottom is a gas flow source on the dynamics of hydrate formation is studied.

  6. Ductile flow of methane hydrate

    USGS Publications Warehouse

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

    2003-01-01

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

  7. Some thermodynamical aspects of protein hydration water

    SciTech Connect

    Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Vasi, Cirino; Stanley, H. Eugene; Chen, Sow-Hsin

    2015-06-07

    We study by means of nuclear magnetic resonance the self-diffusion of protein hydration water at different hydration levels across a large temperature range that includes the deeply supercooled regime. Starting with a single hydration shell (h = 0.3), we consider different hydrations up to h = 0.65. Our experimental evidence indicates that two phenomena play a significant role in the dynamics of protein hydration water: (i) the measured fragile-to-strong dynamic crossover temperature is unaffected by the hydration level and (ii) the first hydration shell remains liquid at all hydrations, even at the lowest temperature.

  8. Actinide Lanthanide Separation Process – ALSEP

    SciTech Connect

    Gelis, Artem V.; Lumetta, Gregg J.

    2014-01-29

    Separation of the minor actinides (Am, Cm) from the lanthanides at an industrial scale remains a significant technical challenge for closing the nuclear fuel cycle. To increase the safety of used nuclear fuel (UNF) reprocessing, as well as reduce associated costs, a novel solvent extraction process has been developed. The process allows for partitioning minor actinides, lanthanides and fission products following uranium/plutonium/neptunium removal; minimizing the number of separation steps, flowsheets, chemical consumption, and waste. This new process, Actinide Lanthanide SEParation (ALSEP), uses an organic solvent consisting of a neutral diglycolamide extractant, either N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) or N,N,N',N'-tetraoctyldiglycolamide (TODGA), and an acidic extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]), dissolved in an aliphatic diluent (e.g. n-dodecane). The An/Ln co-extraction is conducted from moderate-to-strong nitric acid, while the selective stripping of the minor actinides from the lanthanides is carried out using a polyaminocarboxylic acid/citrate buffered solution at pH anywhere between 3 and 4.5. The extraction and separation of the actinides from the fission products is very effective in a wide range of HNO3 concentrations and the minimum separation factors for lanthanide/Am exceed 30 for Nd/Am, reaching > 60 for Eu/Am under some conditions. The experimental results presented here demonstrate the great potential for a combined system, consisting of a neutral extractant such as T2EHDGA or TODGA, and an acidic extractant such as HEH[EHP], for separating the minor actinides from the lanthanides.

  9. Gas Hydrate Petroleum System Analysis

    NASA Astrophysics Data System (ADS)

    Collett, T. S.

    2012-12-01

    In a gas hydrate petroleum system, the individual factors that contribute to the formation of gas hydrate accumulations, such as (1) gas hydrate pressure-temperature stability conditions, (2) gas source, (3) gas migration, and (4) the growth of the gas hydrate in suitable host sediment can identified and quantified. The study of know and inferred gas hydrate accumulations reveal the occurrence of concentrated gas hydrate is mostly controlled by the presence of fractures and/or coarser grained sediments. Field studies have concluded that hydrate grows preferentially in coarse-grained sediments because lower capillary pressures in these sediments permit the migration of gas and nucleation of hydrate. Due to the relatively distal nature of the deep marine geologic settings, the overall abundance of sand within the shallow geologic section is usually low. However, drilling projects in the offshore of Japan, Korea, and in the Gulf of Mexico has revealed the occurrence of significant hydrate-bearing sand reservoirs. The 1999/2000 Japan Nankai Trough drilling confirmed occurrence of hydrate-bearing sand-rich intervals (interpreted as turbidite fan deposits). Gas hydrate was determined to fill the pore spaces in these deposits, reaching saturations up to 80% in some layers. A multi-well drilling program titled "METI Toaki-oki to Kumano-nada" also identified sand-rich reservoirs with pore-filling hydrate. The recovered hydrate-bearing sand layers were described as very-fine- to fine-grained turbidite sand layers measuring from several centimeters up to a meter thick. However, the gross thickness of the hydrate-bearing sand layers were up to 50 m. In 2010, the Republic of Korea conducted the Second Ulleung Basin Gas Hydrate (UBGH2) Drilling Expedition. Seismic data clearly showed the development of a thick, potential basin wide, sedimentary sections characterized by mostly debris flows. The downhole LWD logs and core data from Site UBGH2-5 reveal that each debris flows is

  10. Elevated concentrations of actinides in mono lake.

    PubMed

    Anderson, R F; Bacon, M P; Brewer, P G

    1982-04-30

    Tetravalent thorium, pentavalent protactinium, hexavalent uranium, and plutonium (oxidation state uncertain) are present in much higher concentrations in Mono Lake, a saline, alkaline lake in eastern central California, than in seawater. Low ratios of actinium to protactinium and of americium to plutonium indicate that the concentrations of trivalent actinides are not similarly enhanced. The elevated concentrations of the ordinarily very insoluble actinides are maintained in solution by natural ligands, which inhibit their chemical removal from the water column, rather than by an unusually large rate of supply. PMID:17735740

  11. Elevated concentrations of actinides in Mono Lake

    SciTech Connect

    Anderson, R.F.; Bacon, M.P.; Brewer, P.G.

    1982-04-30

    Tetravalent thorium, pentavalent protactinium, hexavalent uranium, and plutonium (oxidation state uncertain) are present in much higher concentrations in Mono Lake, a saline, alkaline lake in eastern central California, than in seawater. Low ratios of actinium to protactinium and of americium to plutonium indicate that the concentrations of trivalent actinides are not similarly enhanced. The elevated concentrations of the ordinarily very insoluble actinides are maintained in solution by natural ligands, which inhibit their chemical removal from the water column, rather than by an unusually large rate of supply.

  12. Strong correlations in actinide redox reactions

    NASA Astrophysics Data System (ADS)

    Horowitz, S. E.; Marston, J. B.

    2011-02-01

    Reduction-oxidation (redox) reactions of the redox couples An(VI)/An(V), An(V)/An(IV), and An(IV)/An(III), where An is an element in the family of early actinides (U, Np, and Pu), as well as Am(VI)/Am(V) and Am(V)/Am(III), are modeled by combining density functional theory with a generalized Anderson impurity model that accounts for the strong correlations between the 5f electrons. Diagonalization of the Anderson impurity model yields improved estimates for the redox potentials and the propensity of the actinide complexes to disproportionate.

  13. Stability of tetravalent actinides in perovskites

    SciTech Connect

    Williams, C.W.; Morss, L.R.; Choi, I.K.

    1983-01-01

    This paper reports the first determination of the enthalpy of formation of a complex actinide(IV) oxide: ..delta..H/sup 0//sub f/ (BaUO/sub 3/, s, 298 K) = -1690 +- 10 kJ mol/sup -1/. The preparation and properties of this and other actinide(IV) complex oxides are described and are compared with other perovskites BaMO/sub 3/. The relative stabilities of tetravalent and hexavalent uranium in various environments are compared in terms of the oxidation-reduction behavior of uranium in geological nuclear waste storage media; in perovskite, uranium(IV) is very unstable in comparison with uranium(VI).

  14. Systematization of actinides using cluster analysis

    SciTech Connect

    Kopyrin, A.A.; Terent`eva, T.N.; Khramov, N.N.

    1994-11-01

    A representation of the actinides in multidimensional property space is proposed for systematization of these elements using cluster analysis. Literature data for their atomic properties are used. Owing to the wide variation of published ionization potentials, medians are used to estimate them. Vertical dendograms are used for classification on the basis of distances between the actinides in atomic-property space. The properties of actinium and lawrencium are furthest removed from the main group. Thorium and mendelevium exhibit individualized properties. A cluster based on the einsteinium-fermium pair is joined by californium.

  15. Preparation of actinide-metal research

    SciTech Connect

    Aaron, W.S.; Culpepper, C.A.; Campbell, K.B.

    1986-01-01

    The preparation of actinide-metal research materials is one of many functions of the Isotope Research Materials Laboratory (IRML) at Oak Ridge National Lab. Research samples of uranium, plutonium, americium, and curium, typically from milligram quantities up to approx. 100 g, are prepared as pure metals or alloys to customer specifications. Larger quantities, up to many kilograms, of the lower activity actinides, such as /sup 235/U, /sup 238/U, and /sup 232/Th, are also fabricated into custom research forms. Physical forms of these metals include rolled foils or sheets, castings (ingot, rod, or special shapes), and evaporated or sputtered films.

  16. Spin-orbit coupling in actinide cations

    NASA Astrophysics Data System (ADS)

    Bagus, Paul S.; Ilton, Eugene S.; Martin, Richard L.; Jensen, Hans Jørgen Aa.; Knecht, Stefan

    2012-09-01

    The limiting case of Russell-Saunders coupling, which leads to a maximum spin alignment for the open shell electrons, usually explains the properties of high spin ionic crystals with transition metals. For actinide compounds, the spin-orbit splitting is large enough to cause a significantly reduced spin alignment. Novel concepts are used to explain the dependence of the spin alignment on the 5f shell occupation. We present evidence that the XPS of ionic actinide materials may provide direct information about the angular momentum coupling within the 5f shell.

  17. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates

    PubMed Central

    Pustovgar, Elizaveta; Sangodkar, Rahul P.; Andreev, Andrey S.; Palacios, Marta; Chmelka, Bradley F.; Flatt, Robert J.; d'Espinose de Lacaillerie, Jean-Baptiste

    2016-01-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of 29Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured. PMID:27009966

  18. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates.

    PubMed

    Pustovgar, Elizaveta; Sangodkar, Rahul P; Andreev, Andrey S; Palacios, Marta; Chmelka, Bradley F; Flatt, Robert J; d'Espinose de Lacaillerie, Jean-Baptiste

    2016-01-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of (29)Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured. PMID:27009966

  19. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates

    NASA Astrophysics Data System (ADS)

    Pustovgar, Elizaveta; Sangodkar, Rahul P.; Andreev, Andrey S.; Palacios, Marta; Chmelka, Bradley F.; Flatt, Robert J.; D'Espinose de Lacaillerie, Jean-Baptiste

    2016-03-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of 29Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured.

  20. Photonuclear reactions of actinide and pre-actinide nuclei at intermediate energies

    SciTech Connect

    Mukhopadhyay, Tapan; Basu, D. N.

    2007-12-15

    Photonuclear reaction is described with an approach based on the quasideuteron nuclear photoabsorption model followed by the process of competition between light particle evaporation and fission for the excited nucleus. Thus fission process is considered as a decay mode. The evaporation-fission process of the compound nucleus is simulated in a Monte Carlo framework. Photofission reaction cross sections are analysed in a systematic manner in the energy range {approx}50-70 MeV for the actinides {sup 232}Th, {sup 233}U, {sup 235}U, {sup 238}U, and {sup 237}Np and the pre-actinide nuclei {sup 208}Pb and {sup 209}Bi. The study reproduces satisfactorily well the available experimental data of photofission cross sections at energies {approx}50-70 MeV and the increasing trend of nuclear fissility with the fissility parameter Z{sup 2}/A for the actinides and pre-actinides at intermediate energies ({approx}20-140 MeV)

  1. Detection of leaking actinide hexafluoride storage cylinders

    NASA Astrophysics Data System (ADS)

    Beltz, James V.; Williams, Clayton W.

    2000-07-01

    Our spectroscopy and photophysics measurements on solid hydrated uranyl fluorides have shown that luminescence is a powerful method for detecting their presence. We report here the results of those studies and the development of a prototype luminescence imaging system that provides high sensitivity and is optimized for signature detection of hydrated uranyl fluorides. This system provides a high degree of selectivity in that its pulsed excitation source is variable as to wavelength and intensity, and detected luminescence is time-resolved using a spatial light modulator as a fast shutter and wavelength-resolved via bandpass optical filters. The features aid in signature detection of uranyl fluoride hydrates.

  2. Water, Hydration and Health

    PubMed Central

    Popkin, Barry M.; D’Anci, Kristen E.; Rosenberg, Irwin H.

    2010-01-01

    This review attempts to provide some sense of our current knowledge of water including overall patterns of intake and some factors linked with intake, the complex mechanisms behind water homeostasis, the effects of variation in water intake on health and energy intake, weight, and human performance and functioning. Water represents a critical nutrient whose absence will be lethal within days. Water’s importance for prevention of nutrition-related noncommunicable diseases has emerged more recently because of the shift toward large proportions of fluids coming from caloric beverages. Nevertheless, there are major gaps in knowledge related to measurement of total fluid intake, hydration status at the population level, and few longer-term systematic interventions and no published random-controlled longer-term trials. We suggest some ways to examine water requirements as a means to encouraging more dialogue on this important topic. PMID:20646222

  3. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  4. Trends in actinide processing at Hanford

    SciTech Connect

    Harmon, H.D.

    1993-09-01

    In 1989, the mission at the Hanford Site began a dramatic and sometimes painful transition. The days of production--as we used to know it--are over. Our mission officially has become waste management and environmental cleanup. This mission change didn`t eliminate many jobs--in fact, budgets have grown dramatically to support the new mission. Most all of the same skilled crafts, engineers, and scientists are still required for the new mission. This change has not eliminated the need for actinide processing, but it has certainly changed the focus that our actinide chemists and process engineers have. The focus used to be on such things as increasing capacity, improving separations efficiency, and product purity. Minimizing waste had become a more important theme in recent years and it is still a very important concept in the waste management and environmental cleanup arena. However, at Hanford, a new set of words dominates the actinide process scene as we work to deal with actinides that still reside in a variety of forms at the Hanford Site. These words are repackage, stabilize, remove, store and dispose. Some key activities in each of these areas are described in this report.

  5. Optical properties of actinide and lanthanide ions

    SciTech Connect

    Hessler, J.P.; Carnall, W.T.

    1980-01-01

    This paper reviews some of the recent developments in this area of spectroscopy, emphasizing the optical properties of the tripositive lanthanide and actinide ions. In particular, the single ion properties of line positon, intensity, width, and fluorescence lifetime are discussed. 53 reference, 3 figures, 4 tables.

  6. Actinide valences in xenotime and monazite

    NASA Astrophysics Data System (ADS)

    Vance, E. R.; Zhang, Y.; McLeod, T.; Davis, J.

    2011-02-01

    Tetravalent U, Np and Pu can be substituted by ceramic methods into the rare earth site of xenotime and monazite in air atmospheres using Ca ions as charge compensators, while no evidence of penta- or hexavalent actinide ions was found. Some Pu 3+ and Np 3+ can be incorporated in xenotime samples fired in a reducing atmosphere.

  7. Rapid determination of actinides in asphalt samples

    SciTech Connect

    Maxwell, Sherrod L.; Culligan, Brian K.; Hutchison, Jay B.

    2014-01-12

    A new rapid method for the determination of actinides in asphalt samples has been developed that can be used in emergency response situations or for routine analysis If a radiological dispersive device (RDD), Improvised Nuclear Device (IND) or a nuclear accident such as the accident at the Fukushima Nuclear Power Plant in March, 2011 occurs, there will be an urgent need for rapid analyses of many different environmental matrices, including asphalt materials, to support dose mitigation and environmental clean up. The new method for the determination of actinides in asphalt utilizes a rapid furnace step to destroy bitumen and organics present in the asphalt and sodium hydroxide fusion to digest the remaining sample. Sample preconcentration steps are used to collect the actinides and a new stacked TRU Resin + DGA Resin column method is employed to separate the actinide isotopes in the asphalt samples. The TRU Resin plus DGA Resin separation approach, which allows sequential separation of plutonium, uranium, americium and curium isotopes in asphalt samples, can be applied to soil samples as well.

  8. COMPLEXANTS FOR ACTINIDE ELEMENT COORDINATION AND IMMOBILIZATION

    EPA Science Inventory

    We propose that inorganic clusters known as polyoxoanions (POAs) can be exploited as complexants for actinide (An) ion coordination and immobilization. Our objective is to develop rugged, stoichiometrically well-defined POAs that act as molecular containers of An elements. Poly...

  9. Actinide measurements by AMS using fluoride matrices

    NASA Astrophysics Data System (ADS)

    Cornett, R. J.; Kazi, Z. H.; Zhao, X.-L.; Chartrand, M. G.; Charles, R. J.; Kieser, W. E.

    2015-10-01

    Actinides can be measured by alpha spectroscopy (AS), mass spectroscopy or accelerator mass spectrometry (AMS). We tested a simple method to separate Pu and Am isotopes from the sample matrix using a single extraction chromatography column. The actinides in the column eluent were then measured by AS or AMS using a fluoride target matrix. Pu and Am were coprecipitated with NdF3. The strongest AMS beams of Pu and Am were produced when there was a large excess of fluoride donor atoms in the target and the NdF3 precipitates were diluted about 6-8 fold with PbF2. The measured concentrations of 239,240Pu and 241Am agreed with the concentrations in standards of known activity and with two IAEA certified reference materials. Measurements of 239,240Pu and 241Am made at A.E. Lalonde AMS Laboratory agree, within their statistical uncertainty, with independent measurements made using the IsoTrace AMS system. This work demonstrated that fluoride targets can produce reliable beams of actinide anions and that the measurement of actinides using fluorides agree with published values in certified reference materials.

  10. Actinide Targets for Neutron Cross Section Measurements

    SciTech Connect

    John D. Baker; Christopher A. McGrath

    2006-10-01

    The Advanced Fuel Cycle Initiative (AFCI) and the Generation IV Reactor Initiative have demonstrated a lack of detailed neutron cross-sections for certain "minor" actinides, those other than the most common (235U, 238U, and 239Pu). For some closed-fuel-cycle reactor designs more than 50% of reactivity will, at some point, be derived from "minor" actinides that currently have poorly known or in some cases not measured (n,?) and (n,f) cross sections. A program of measurements under AFCI has begun to correct this. One of the initial hurdles has been to produce well-characterized, highly isotopically enriched, and chemically pure actinide targets on thin backings. Using a combination of resurrected techniques and new developments, we have made a series of targets including highly enriched 239Pu, 240Pu, and 242Pu. Thus far, we have electrodeposited these actinide targets. In the future, we plan to study reductive distillation to achieve homogeneous, adherent targets on thin metal foils and polymer backings. As we move forward, separated isotopes become scarcer, and safety concerns become greater. The chemical purification and electodeposition techniques will be described.

  11. Rapid determination of actinides in asphalt samples

    DOE PAGESBeta

    Maxwell, Sherrod L.; Culligan, Brian K.; Hutchison, Jay B.

    2014-01-12

    A new rapid method for the determination of actinides in asphalt samples has been developed that can be used in emergency response situations or for routine analysis If a radiological dispersive device (RDD), Improvised Nuclear Device (IND) or a nuclear accident such as the accident at the Fukushima Nuclear Power Plant in March, 2011 occurs, there will be an urgent need for rapid analyses of many different environmental matrices, including asphalt materials, to support dose mitigation and environmental clean up. The new method for the determination of actinides in asphalt utilizes a rapid furnace step to destroy bitumen and organicsmore » present in the asphalt and sodium hydroxide fusion to digest the remaining sample. Sample preconcentration steps are used to collect the actinides and a new stacked TRU Resin + DGA Resin column method is employed to separate the actinide isotopes in the asphalt samples. The TRU Resin plus DGA Resin separation approach, which allows sequential separation of plutonium, uranium, americium and curium isotopes in asphalt samples, can be applied to soil samples as well.« less

  12. Cross sections for actinide burner reactors

    SciTech Connect

    Difilippo, F.C.

    1991-01-01

    Recent studies have shown the feasibility of burning higher actinides (i.e., transuranium (TRU) elements excluding plutonium) in ad hoc designed reactors (Actinide Burner Reactors: ABR) which, because of their hard neutron spectra, enhance the fission of TRU. The transmutation of long-lived radionuclides into stable or short-lived isotopes reduces considerably the burden of handling high-level waste from either LWR or Fast Breeder Reactors (FBR) fuels. Because of the large concentrations of higher actinides in these novel reactor designs the Doppler effect due to TRU materials is the most important temperature coefficient from the point of view of reactor safety. Here we report calculations of energy group-averaged capture and fission cross sections as function of temperature and dilution for higher actinides in the resolved and unresolved resonance regions. The calculations were done with the codes SAMMY in the resolved region and URR in the unresolved regions and compared with an independent calculation. 4 refs., 2 figs., 2 tabs.

  13. Environmental Impact of the Nuclear Fuel Cycle: Fate of Actinides

    SciTech Connect

    Ewing, Rodney C.; Runde, W.; Albrecht-Schmitt, Thomas E.

    2011-01-31

    The resurgence of nuclear power as a strategy for reducing greenhouse gas (GHG) emissions has, in parallel, revived interest in the environmental impact of actinides. Just as GHG emissions are the main environmental impact of the combustion of fossil fuels, the fate of actinides, consumed and produced by nuclear reactions, determines whether nuclear power is viewed as an environmentally “friendly” source of energy. In this article, we summarize the sources of actinides in the nuclear fuel cycle, how actinides are separated by chemical processing, the development of actinide-bearing materials, and the behavior of actinides in the environment. At each stage, actinides present a unique and complicated behavior because of the 5f electronic configurations.

  14. 75 FR 9886 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-04

    ... Hydrate Advisory Committee AGENCY: Department of Energy, Office of Fossil Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... Methane Hydrate Advisory Committee is to provide advice on potential applications of methane hydrate...

  15. Obsidian Hydration: A New Paleothermometer

    SciTech Connect

    Anovitz, Lawrence {Larry} M; Riciputi, Lee R; Cole, David R; Fayek, Mostafa; Elam, J. Michael

    2006-01-01

    The natural hydration of obsidian was first proposed as a dating technique for young geological and archaeological specimens by Friedman and Smith (1960), who noted that the thickness of the hydrated layer on obsidian artifacts increases with time. This approach is, however, sensitive to temperature and humidity under earth-surface conditions. This has made obsidian hydration dating more difficult, but potentially provides a unique tool for paleoclimatic reconstructions. In this paper we present the first successful application of this approach, based on combining laboratory-based experimental calibrations with archaeological samples from the Chalco site in the Basin of Mexico, dated using stratigraphically correlated 14C results and measuring hydration depths by secondary ion mass spectrometry. The resultant data suggest, first, that this approach is viable, even given the existing uncertainties, and that a cooling trend occurred in the Basin of Mexico over the past 1450 yr, a result corroborated by other paleoclimatic data.

  16. Obsidian hydration dates glacial loading?

    PubMed

    Friedman, I; Pierce, K L; Obradovich, J D; Long, W D

    1973-05-18

    Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming. The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow. PMID:17806883

  17. Obsidian hydration dates glacial loading?

    USGS Publications Warehouse

    Friedman, I.; Pierce, K.L.; Obradovich, J.D.; Long, W.D.

    1973-01-01

    Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming . The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow.

  18. Hydrate control in deepwater drilling

    SciTech Connect

    1997-09-01

    Gas-hydrate formation during deepwater offshore drilling and production is a well-recognized operational hazard. In water depths greater than 1,000 ft, seabed conditions of pressure and temperature become conducive to gas-hydrate formation. In a well-control situation, although the kick fluid leaves the formation at a high temperature, it can cool to seabed temperature with an extended shut-in period. With high enough hydrostatic pressure at the mudline, hydrates could form in the blowout-preventer (BOP) stack and choke and kill lines, as has been observed in field operations. The current practice in deepwater drilling is to suppress the hydrate-formation temperature by use of highly saline drilling fluids formulated from NaCl or other salts. This solution is applicable for the Gulf of Mexico but insufficient for the conditions encountered in Norwegian deep waters. At extreme water depths or extremely low mudline temperatures, this thermodynamic inhibition alone may not be sufficient to prevent hydrate formation. Instead, the use of kinetic inhibitors or crystal modifiers, in conjunction with thermodynamic inhibitors, may allow successful operations in such an environment. The definition of kinetic inhibitors (to distinguish them from the classic thermodynamic inhibitors, such as polar compounds and electrolytes) comes from the effect of the chemicals on the nucleation and growth of natural gas hydrates, both of which are time-dependent, stochastic processes. The paper describes deepwater drilling fluids, polar and surface-active additives, kinetic inhibition and crystal modifiers, laboratory measurements, and test results.

  19. Synthesis of actinide nitrides, phosphides, sulfides and oxides

    DOEpatents

    Van Der Sluys, William G.; Burns, Carol J.; Smith, David C.

    1992-01-01

    A process of preparing an actinide compound of the formula An.sub.x Z.sub.y wherein An is an actinide metal atom selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, x is selected from the group consisting of one, two or three, Z is a main group element atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur and y is selected from the group consisting of one, two, three or four, by admixing an actinide organometallic precursor wherein said actinide is selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, a suitable solvent and a protic Lewis base selected from the group consisting of ammonia, phosphine, hydrogen sulfide and water, at temperatures and for time sufficient to form an intermediate actinide complex, heating said intermediate actinide complex at temperatures and for time sufficient to form the actinide compound, and a process of depositing a thin film of such an actinide compound, e.g., uranium mononitride, by subliming an actinide organometallic precursor, e.g., a uranium amide precursor, in the presence of an effectgive amount of a protic Lewis base, e.g., ammonia, within a reactor at temperatures and for time sufficient to form a thin film of the actinide compound, are disclosed.

  20. Sample preparation for actinide solid state research

    NASA Astrophysics Data System (ADS)

    Spirlet, J. C.

    1982-09-01

    The actinide elements (5f elements) and their compounds constitute a very interesting group for solid state research. The electronic properties of the 5f elements show intermediate behavior between the well-understood, completely localized 4f system (lanthanides) and the 3d system (transition elements). The possibility of understanding some unexplained properties of the 3d elements through a systematic investigation of the electronic structures of the actinides considerably increased interest in samples with well-defined composition and structure and with well-known purity. In some cases, single crystals of low defect densities and high purity levels are needed to allow sophisticated investigations of physical properties. Actinide compounds are easily obtained at a high purity level by direct synthesis from pure elements using noncontaminating techniques. Examples of these techniques are the reaction of the actinide metal powder with the vapor of an oxidant in a sealed quartz ampoule, leviation melting on a water-cooled pedestal or melting in a Huking crucible. Actinide metals are produced by metallothermic reduction of commercially available oxides or carbides or by the van Arkel purification process. The metals are refined to the desired purity level by evaporation in vacuum for the more volatile elements (Ac, Pu, Am, Cm, Bk) and by the van Arkel process for the metals with low vapor pressure. Single crystals of actinide compounds have been grown by chemical vapor transport methods (oxides, chalcogenides), high temperature solution growth techniques (oxides), and pulling from the melt by the Czochralski method (oxides, intermetallics). Thin solid films have been prepared by vacuum evaporation or by focused ion-beam sputtering. The materials are analyzed for trace-level impurity content by inductively-coupled plasma spectroscopy, by spark source mass spectroscopy and by secondary-ion mass spectroscopy. The chemical composition of the compounds is determined by

  1. Electrorecovery of actinides at room temperature

    SciTech Connect

    Stoll, Michael E; Oldham, Warren J; Costa, David A

    2008-01-01

    There are a large number of purification and processing operations involving actinide species that rely on high-temperature molten salts as the solvent medium. One such application is the electrorefining of impure actinide metals to provide high purity material for subsequent applications. There are some drawbacks to the electrodeposition of actinides in molten salts including relatively low yields, lack of accurate potential control, maintaining efficiency in a highly corrosive environment, and failed runs. With these issues in mind we have been investigating the electrodeposition of actinide metals, mainly uranium, from room temperature ionic liquids (RTILs) and relatively high-boiling organic solvents. The RTILs we have focused on are comprised of 1,3-dialkylimidazolium or quaternary ammonium cations and mainly the {sup -}N(SO{sub 2}CF{sub 3}){sub 2} anion [bis(trif1uoromethylsulfonyl)imide {equivalent_to} {sup -}NTf{sub 2}]. These materials represent a class of solvents that possess great potential for use in applications employing electrochemical procedures. In order to ascertain the feasibility of using RTILs for bulk electrodeposition of actinide metals our research team has been exploring the electron transfer behavior of simple coordination complexes of uranium dissolved in the RTIL solutions. More recently we have begun some fundamental electrochemical studies on the behavior of uranium and plutonium complexes in the organic solvents N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO). Our most recent results concerning electrodeposition will be presented in this account. The electrochemical behavior of U(IV) and U(III) species in RTILs and the relatively low vapor pressure solvents NMP and DMSO is described. These studies have been ongoing in our laboratory to uncover conditions that will lead to the successful bulk electrodeposition of actinide metals at a working electrode surface at room temperature or slightly elevated temperatures. The RTILs we

  2. Further insights in the ability of classical nonadditive potentials to model actinide ion-water interactions.

    PubMed

    Réal, Florent; Trumm, Michael; Schimmelpfennig, Bernd; Masella, Michel; Vallet, Valérie

    2013-04-01

    Pursuing our efforts on the development of accurate classical models to simulate radionuclides in complex environments (Réal et al., J. Phys. Chem. A 2010, 114, 15913; Trumm et al. J. Chem. Phys. 2012, 136, 044509), this article places a large emphasis on the discussion of the influence of models/parameters uncertainties on the computed structural, dynamical, and temporal properties. Two actinide test cases, trivalent curium and tetravalent thorium, have been studied with three different potential energy functions, which allow us to account for the polarization and charge-transfer effects occurring in hydrated actinide ion systems. The first type of models considers only an additive energy term for modeling ion/water charge-transfer effects, whereas the other two treat cooperative charge-transfer interactions with two different analytical expressions. Model parameters are assigned to reproduce high-level ab initio data concerning only hydrated ion species in gas phase. For the two types of cooperative charge-transfer models, we define two sets of parameters allowing or not to cancel out possible errors inherent to the force field used to model water/water interactions at the ion vicinity. We define thus five different models to characterize the solvation of each ion. For both ions, our cooperative charge-transfer models lead to close results in terms of structure in solution: the coordination number is included within 8 and 9, and the mean ion/water oxygen distances are 2.45 and 2.49 Å, respectively, for Th(IV) and Cm(III). PMID:23233426

  3. Actinide phosphonate complexes in aqueous solutions

    SciTech Connect

    Nash, K.L.

    1993-10-01

    Complexes formed by actinides with carboxylic acids, polycarboxylic acids, and aminopolycarboxylic acids play a central role in both the basic and process chemistry of the actinides. Recent studies of f-element complexes with phosphonic acid ligands indicate that new ligands incorporating doubly ionizable phosphonate groups (-PO{sub 3}H{sub 2}) have many properties which are unique chemically, and promise more efficient separation processes for waste cleanup and environmental restoration. Simple diphosphonate ligands form much stronger complexes than isostructural carboxylates, often exhibiting higher solubility as well. In this manuscript recent studies of the thermodynamics and kinetics of f-element complexation by 1,1 and 1,2 diphosphonic acid ligands are described.

  4. Microbial Transformations of Actinides and Other Radionuclides

    SciTech Connect

    Francis,A.J.; Dodge, C. J.

    2009-01-07

    Microorganisms can affect the stability and mobility of the actinides and other radionuclides released from nuclear fuel cycle and from nuclear fuel reprocessing plants. Under appropriate conditions, microorganisms can alter the chemical speciation, solubility and sorption properties and thus could increase or decrease the concentrations of radionuclides in solution in the environment and the bioavailability. Dissolution or immobilization of radionuclides is brought about by direct enzymatic action or indirect non-enzymatic action of microorganisms. Although the physical, chemical, and geochemical processes affecting dissolution, precipitation, and mobilization of radionuclides have been extensively investigated, we have only limited information on the effects of microbial processes and biochemical mechanisms which affect the stability and mobility of radionuclides. The mechanisms of microbial transformations of the major and minor actinides U, Pu, Cm, Am, Np, the fission products and other radionuclides such as Ra, Tc, I, Cs, Sr, under aerobic and anaerobic conditions in the presence of electron donors and acceptors are reviewed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  6. Energy resource potential of natural gas hydrates

    USGS Publications Warehouse

    Collett, T.S.

    2002-01-01

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

  7. In vitro removal of actinide (IV) ions

    DOEpatents

    Weitl, Frederick L.; Raymond, Kenneth N.

    1982-01-01

    A compound of the formula: ##STR1## wherein X is hydrogen or a conventional electron-withdrawing group, particularly --SO.sub.3 H or a salt thereof; n is 2, 3, or 4; m is 2, 3, or 4; and p is 2 or 3. The present compounds are useful as specific sequestering agents for actinide (IV) ions. Also described is a method for the 2,3-dihydroxybenzamidation of azaalkanes.

  8. Separation of Californium from other Actinides

    DOEpatents

    Mailen, J C; Ferris, L M

    1973-09-25

    A method is provided for separating californium from a fused fluoride composition containing californium and at least one element selected from the group consisting of plutonium, americium, curium, uranium, thorium, and protactinium which comprises contacting said fluoride composition with a liquid bismuth phase containing sufficient lithium or thorium to effect transfer of said actinides to the bismuth phase and then contacting the liquid bismuth phase with molten LiCl to effect selective transfer of californium to the chloride phase.

  9. Surrogate Reactions in the Actinide Region

    SciTech Connect

    Burke, J T; Bernstein, L A; Scielzo, N D; Bleuel, D L; Lesher, S R; Escher, J; Ahle, L; Dietrich, F S; Hoffman, R D; Norman, E B; Sheets, S A; Phair, L; Fallon, P; Clark, R M; Gibelin, J; Jewett, C; Lee, I Y; Macchiavelli, A O; McMahan, M A; Moretto, L G; Rodriguez-Vieitez, E; Wiedeking, M; Lyles, B F; Beausang, C W; Allmond, J M; Ai, H; Cizewski, J A; Hatarik, R; O'Malley, P D; Swan, T

    2008-01-30

    Over the past three years we have studied various surrogate reactions (d,p), ({sup 3}He,t), ({alpha},{alpha}{prime}) on several uranium isotopes {sup 234}U, {sup 235}U, {sup 236}U, and {sup 238}U. An overview of the STARS/LIBERACE surrogate research program as it pertains to the actinides is discussed. A summary of results to date will be presented along with a discussion of experimental difficulties encountered in surrogate experiments and future research directions.

  10. Actinide behavior in a freshwater pond

    SciTech Connect

    Trabalka, J.R.; Bogle, M.A.; Scott, T.G.

    1983-01-01

    Long-term investigations of solution chemistry in an alkaline freshwater pond have revealed that actinide oxidation state behavior, particularly that of plutonium, is complex. The Pu(V,VI) fraction was predominant in solution, but it varied over the entire range reported from other natural aquatic environments, in this case, as a result of intrinsic biological and chemical cycles (redox and pH-dependent phenomena). A strong positive correlation between plutonium (Pu), but not uranium (U), and hydroxyl ion over the observation period, especially when both were known to be in higher oxidation states, was particularly notable. Coupled with other examples of divergent U and Pu behavior, this result suggests that Pu(V), or perhaps a mixture of Pu(V,VI), was the prevalent oxidation state in solution. Observations of trivalent actinide sorption behavior during an algal bloom, coupled with the association with a high-molecular weight (nominally 6000 to 10,000 mol wt) organic fraction in solution, indicate that solution-detritus cycling of organic carbon, in turn, may be the primary mechanism in amercium-curium (Am-Cm) cycling. Sorption by sedimentary materials appears to predominate over other factors controlling effective actinide solubility and may explain, at least partially, the absence of an expected strong positive correlation between carbonate and dissolved U. 49 references, 6 figures, 12 tables.

  11. Actinide and lanthanide separation process (ALSEP)

    SciTech Connect

    Guelis, Artem V.

    2013-01-15

    The process of the invention is the separation of minor actinides from lanthanides in a fluid mixture comprising, fission products, lanthanides, minor actinides, rare earth elements, nitric acid and water by addition of an organic chelating aid to the fluid; extracting the fluid with a solvent comprising a first extractant, a second extractant and an organic diluent to form an organic extractant stream and an aqueous raffinate. Scrubbing the organic stream with a dicarboxylic acid and a chelating agent to form a scrubber discharge. The scrubber discharge is stripped with a simple buffering agent and a second chelating agent in the pH range of 2.5 to 6.1 to produce actinide and lanthanide streams and spent organic diluents. The first extractant is selected from bis(2-ethylhexyl)hydrogen phosphate (HDEHP) and mono(2-ethylhexyl)2-ethylhexyl phosphonate (HEH(EHP)) and the second extractant is selected from N,N,N,N-tetra-2-ethylhexyl diglycol amide (TEHDGA) and N,N,N',N'-tetraoctyl-3-oxapentanediamide (TODGA).

  12. Recovery of actinides from actinide-aluminium alloys by chlorination: Part II

    NASA Astrophysics Data System (ADS)

    Souček, P.; Cassayre, L.; Eloirdi, R.; Malmbeck, R.; Meier, R.; Nourry, C.; Claux, B.; Glatz, J.-P.

    2014-04-01

    A chlorination route is being investigated for recovery of actinides from actinide-aluminium alloys, which originate from pyrochemical recovery of actinides from spent metallic nuclear fuel by electrochemical methods in molten LiCl-KCl. In the present work, the most important steps of this route were experimentally tested using U-Pu-Al alloy prepared by electrodeposition of U and Pu on solid aluminium plate electrodes. The investigated processes were vacuum distillation for removal of the salt adhered on the electrode, chlorination of the alloy by chlorine gas and sublimation of the AlCl3 formed. The processes parameters were set on the base of a previous thermochemical study and an experimental work using pure UAl3 alloy. The present experimental results indicated high efficiency of salt distillation and chlorination steps, while the sublimation step should be further optimised.

  13. Development of the Actinide-Lanthanide Separation (ALSEP) Process

    SciTech Connect

    Lumetta, Gregg J.; Carter, Jennifer C.; Niver, Cynthia M.; Gelis, Artem V.

    2014-09-30

    Separating the minor actinide elements (Am and Cm) from acidic high-level raffinates arising from the reprocessing of irradiated nuclear fuel is an important step in closing the nuclear fuel cycle. Most proposed approaches to this problem involve two solvent extraction steps: 1) co-extraction of the trivalent lanthanides and actinides, followed by 2) separation of the actinides from the lanthanides. The objective of our work is to develop a single solvent-extraction process for isolating the minor actinide elements. We report here a solvent containing N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) combined with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) that can be used to separate the minor actinides in a single solvent-extraction process. T2EHDGA serves to co-extract the trivalent actinide and lanthanide ions from nitric acid solution. Switching the aqueous phase chemistry to a citrate buffered solution of N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid at pH 2.5 to 4 results in selective transfer of the actinides to the aqueous phase, thus affecting separation of the actinides from the lanthanides. Separation factors between the lanthanides and actinides are approximately 20 in the pH range of 3 to 4, and the distribution ratios are not highly dependent on the pH in this system.

  14. Bidentate organophosphorus solvent extraction process for actinide recovery and partition

    DOEpatents

    Schulz, Wallace W.

    1976-01-01

    A liquid-liquid extraction process for the recovery and partitioning of actinide values from acidic nuclear waste aqueous solutions, the actinide values including trivalent, tetravalent and hexavalent oxidation states is provided and includes the steps of contacting the aqueous solution with a bidentate organophosphorous extractant to extract essentially all of the actinide values into the organic phase. Thereafter the respective actinide fractions are selectively partitioned into separate aqueous solutions by contact with dilute nitric or nitric-hydrofluoric acid solutions. The hexavalent uranium is finally removed from the organic phase by contact with a dilute sodium carbonate solution.

  15. Impact of Including Higher Actinides in Fast Reactor Transmutation Analyses

    SciTech Connect

    B. Forget; M. Asgari; R. Ferrer; S. Bays

    2007-09-01

    Previous fast reactor transmutation studies generally disregarded higher mass minor actinides beyond Cm-246 due to various considerations including deficiencies in nuclear cross-section data. Although omission of these higher mass actinides does not significantly impact the neutronic calculations and fuel cycle performance parameters follow-on neutron dose calculations related to fuel recycling, transportation and handling are significantly impacted. This report shows that including the minor actinides in the equilibrium fast reactor calculations will increase the predicted neutron emission by about 30%. In addition a sensitivity study was initiated by comparing the impact of different cross-section evaluation file for representing these minor actinides.

  16. Hydration water in dynamics of a hydrated beta-lactoglobulin

    NASA Astrophysics Data System (ADS)

    Yoshida, K.; Yamaguchi, T.; Bellissent-Funel, M.-C.; Longeville, S.

    2007-02-01

    Incoherent spin-echo signals of a hydrated β-lactoglobulin protein were investigated, at 275 and 293 K. The intermediate scattering functions I(Q,t) were divided in two contributions from surface water and protein, respectively. On one hand, the dynamics of the surface water follows a KWW stretched exponential function (the exponent is ~0.5), on the other hand, that of the protein follows a single exponential. The present results are consistent with our previous results of hydrated C-phycocyanin combining elastic and quasielastic neutron scattering and by molecular dynamics simulation.

  17. Advanced Aqueous Separation Systems for Actinide Partitioning

    SciTech Connect

    Nash, Ken; Martin, Leigh; Lumetta, Gregg

    2015-04-02

    One of the most challenging aspects of advanced processing of used nuclear fuel is the separation of transplutonium actinides from fission product lanthanides. This separation is essential if actinide transmutation options are to be pursued in advanced fuel cycles, as lanthanides compete with actinides for neutrons in both thermal and fast reactors, thus limiting efficiency. The separation is difficult because the chemistry of Am3+ and Cm3+ is nearly identical to that of the trivalent lanthanides (Ln3+). The prior literature teaches that two approaches offer the greatest probability of devising a successful group separation process based on aqueous processes: 1) the application of complexing agents containing ligand donor atoms that are softer than oxygen (N, S, Cl-) or 2) changing the oxidation state of Am to the IV, V, or VI state to increase the essential differences between Am and lanthanide chemistry (an approach utilized in the PUREX process to selectively remove Pu4+ and UO22+ from fission products). The latter approach offers the additional benefit of enabling a separation of Am from Cm, as Cm(III) is resistant to oxidation and so can easily be made to follow the lanthanides. The fundamental limitations of these approaches are that 1) the soft(er) donor atoms that interact more strongly with actinide cations than lanthanides form substantially weaker bonds than oxygen atoms, thus necessitating modification of extraction conditions for adequate phase transfer efficiency, 2) soft donor reagents have been seen to suffer slow phase transfer kinetics and hydro-/radiolytic stability limitations and 3) the upper oxidation states of Am are all moderately strong oxidants, hence of only transient stability in media representative of conventional aqueous separations systems. There are examples in the literature of both approaches having been described. However, it is not clear at present that any extant process is sufficiently robust for application at the scale

  18. Well log evaluation of natural gas hydrates

    SciTech Connect

    Collett, T.S.

    1992-10-01

    Gas hydrates are crystalline substances composed of water and gas, in which a solid-water-lattice accommodates gas molecules in a cage-like structure. Gas hydrates are globally widespread in permafrost regions and beneath the sea in sediment of outer continental margins. While methane, propane, and other gases can be included in the clathrate structure, methane hydrates appear to be the most common in nature. The amount of methane sequestered in gas hydrates is probably enormous, but estimates are speculative and range over three orders of magnitude from about 100,000 to 270,000,000 trillion cubic feet. The amount of gas in the hydrate reservoirs of the world greedy exceeds the volume of known conventional gas reserves. Gas hydrates also represent a significant drilling and production hazard. A fundamental question linking gas hydrate resource and hazard issues is: What is the volume of gas hydrates and included gas within a given gas hydrate occurrence Most published gas hydrate resource estimates have, of necessity, been made by broad extrapolation of only general knowledge of local geologic conditions. Gas volumes that may be attributed to gas hydrates are dependent on a number of reservoir parameters, including the areal extent ofthe gas-hydrate occurrence, reservoir thickness, hydrate number, reservoir porosity, and the degree of gas-hydrate saturation. Two of the most difficult reservoir parameters to determine are porosity and degreeof gas hydrate saturation. Well logs often serve as a source of porosity and hydrocarbon saturation data; however, well-log calculations within gas-hydrate-bearing intervals are subject to error. The primary reason for this difficulty is the lack of quantitative laboratory and field studies. The primary purpose of this paper is to review the response of well logs to the presence of gas hydrates.

  19. Well log evaluation of natural gas hydrates

    SciTech Connect

    Collett, T.S.

    1992-10-01

    Gas hydrates are crystalline substances composed of water and gas, in which a solid-water-lattice accommodates gas molecules in a cage-like structure. Gas hydrates are globally widespread in permafrost regions and beneath the sea in sediment of outer continental margins. While methane, propane, and other gases can be included in the clathrate structure, methane hydrates appear to be the most common in nature. The amount of methane sequestered in gas hydrates is probably enormous, but estimates are speculative and range over three orders of magnitude from about 100,000 to 270,000,000 trillion cubic feet. The amount of gas in the hydrate reservoirs of the world greedy exceeds the volume of known conventional gas reserves. Gas hydrates also represent a significant drilling and production hazard. A fundamental question linking gas hydrate resource and hazard issues is: What is the volume of gas hydrates and included gas within a given gas hydrate occurrence? Most published gas hydrate resource estimates have, of necessity, been made by broad extrapolation of only general knowledge of local geologic conditions. Gas volumes that may be attributed to gas hydrates are dependent on a number of reservoir parameters, including the areal extent ofthe gas-hydrate occurrence, reservoir thickness, hydrate number, reservoir porosity, and the degree of gas-hydrate saturation. Two of the most difficult reservoir parameters to determine are porosity and degreeof gas hydrate saturation. Well logs often serve as a source of porosity and hydrocarbon saturation data; however, well-log calculations within gas-hydrate-bearing intervals are subject to error. The primary reason for this difficulty is the lack of quantitative laboratory and field studies. The primary purpose of this paper is to review the response of well logs to the presence of gas hydrates.

  20. Complex gas hydrate from the Cascadia margin.

    PubMed

    Lu, Hailong; Seo, Yu-taek; Lee, Jong-won; Moudrakovski, Igor; Ripmeester, John A; Chapman, N Ross; Coffin, Richard B; Gardner, Graeme; Pohlman, John

    2007-01-18

    Natural gas hydrates are a potential source of energy and may play a role in climate change and geological hazards. Most natural gas hydrate appears to be in the form of 'structure I', with methane as the trapped guest molecule, although 'structure II' hydrate has also been identified, with guest molecules such as isobutane and propane, as well as lighter hydrocarbons. A third hydrate structure, 'structure H', which is capable of trapping larger guest molecules, has been produced in the laboratory, but it has not been confirmed that it occurs in the natural environment. Here we characterize the structure, gas content and composition, and distribution of guest molecules in a complex natural hydrate sample recovered from Barkley canyon, on the northern Cascadia margin. We show that the sample contains structure H hydrate, and thus provides direct evidence for the natural occurrence of this hydrate structure. The structure H hydrate is intimately associated with structure II hydrate, and the two structures contain more than 13 different hydrocarbon guest molecules. We also demonstrate that the stability field of the complex gas hydrate lies between those of structure II and structure H hydrates, indicating that this form of hydrate is more stable than structure I and may thus potentially be found in a wider pressure-temperature regime than can methane hydrate deposits. PMID:17230188

  1. Protective effects of perindopril on d-galactose and aluminum trichloride induced neurotoxicity via the apoptosis of mitochondria-mediated intrinsic pathway in the hippocampus of mice.

    PubMed

    Yang, Weina; Shi, Lili; Chen, Lianji; Zhang, Bingyi; Ma, Kaige; Liu, Yong; Qian, Yihua

    2014-10-01

    Perindopril, an angiotensin converting enzyme inhibitor, has been reported to improve learning and memory in a mouse or rat model of Alzheimer's disease (AD) induced by injection of beta-amyloid protein. However, the exact mechanism of perindopril on the cognitive deficits is not fully understood. Our previous data have indicated that perindopril improves learning and memory in a mouse model of AD induced by D-galactose (D-gal) and aluminum trichloride (AlCl₃) via inhibition of acetylcholinesterase activity and oxidative stress. Whether perindopril also inhibit apoptosis to prevent cognitive decline remains unknown in mice. Therefore, the present study explored the protective effects of perindopril in the hippocampus of mice further. Perindopril (0.5 mg/kg/day) was administered intragastrically for 60 days after the mice were given a D-gal (150 mg/kg/day) and AlCl₃ (10 mg/kg/day) intraperitoneally for 90 days. Then the expression of Bcl-2, Bax, Fas, FasL, caspase-3, caspase-8 and caspase-9 were analyzed by RT-PCR and western blotting in the hippocampus. Perindopril significantly decreased caspase-3 and caspase-9 activities, and elevated Bcl-2/Bax ratio in the hippocampus. However, the expression of Fas, FasL and caspase-8 did not change in the hippocampus whether treatment with d-gal and AlCl₃ or perindopril. Taken together, the above findings indicated that perindopril inhibited apoptosis in the hippocampus may be another mechanism by which perindopril improves learning and memory functions in d-gal and AlCl₃ treated mice. PMID:25290208

  2. Gas Hydrate and Pore Pressure

    NASA Astrophysics Data System (ADS)

    Tinivella, Umberta; Giustiniani, Michela

    2014-05-01

    Many efforts have been devoted to quantify excess pore pressures related to gas hydrate dissociation in marine sediments below the BSR using several approaches. Dissociation of gas hydrates in proximity of the BSR, in response to a change in the physical environment (i.e., temperature and/or pressure regime), can liberate excess gas incrising the local pore fluid pressure in the sediment, so decreasing the effective normal stress. So, gas hydrate dissociation may lead to excess pore pressure resulting in sediment deformation or failure, such as submarine landslides, sediment slumping, pockmarks and mud volcanoes, soft-sediment deformation and giant hummocks. Moreover, excess pore pressure may be the result of gas hydrate dissociation due to continuous sedimentation, tectonic uplift, sea level fall, heating or inhibitor injection. In order to detect the presence of the overpressure below the BSR, we propose two approachs. The fist approach models the BSR depth versus pore pressure; in fact, if the free gas below the BSR is in overpressure condition, the base of the gas hydrate stability is deeper with respect to the hydrostatic case. This effect causes a discrepancy between seismic and theoretical BSR depths. The second approach models the velocities versus gas hydrate and free gas concentrations and pore pressure, considering the approximation of the Biot theory in case of low frequency, i.e. seismic frequency. Knowing the P and S seismic velocity from seismic data analysis, it is possibile to jointly estimate the gas hydrate and free gas concentrations and the pore pressure regime. Alternatively, if the S-wave velocity is not availbale (due to lack of OBS/OBC data), an AVO analysis can be performed in order to extract information about Poisson ratio. Our modeling suggests that the areas characterized by shallow waters (i.e., areas in which human infrastructures, such as pipelines, are present) are significantly affected by the presence of overpressure condition

  3. Natural Gas Hydrates Update 1998-2000

    EIA Publications

    2001-01-01

    Significant events have transpired on the natural gas hydrate research and development front since "Future Supply Potential of Natural Gas Hydrates" appeared in Natural Gas 1998 Issues and Trends and in the Potential Gas Committee's 1998 biennial report.

  4. Compact apparatus for photogeneration of hydrated electrons

    NASA Technical Reports Server (NTRS)

    Hart, E.; Schmidt, K.

    1970-01-01

    Flash-photolysis instrument generates hydrated electrons and studies their reactions. It has a three-dimensional, multiple-reaction cell and the capacity to produce up to .1 micromole hydrated electron in a single 40 microsec light pulse.

  5. Methods to determine hydration states of minerals and cement hydrates

    SciTech Connect

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

    2014-11-15

    This paper describes a novel approach to the quantitative investigation of the impact of varying relative humidity (RH) and temperature on the structure and thermodynamic properties of salts and crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The multi-method approach developed here is capable of deriving physico-chemical boundary conditions and the thermodynamic properties of hydrated phases, many of which are currently missing from or insufficiently reported in the literature. As an example the approach was applied to monosulfoaluminate, a phase typically found in hydrated cement pastes. New data on the dehydration and rehydration of monosulfoaluminate are presented. Some of the methods used were validated with the system Na{sub 2}SO{sub 4}–H{sub 2}O and new data related to the absorption of water by anhydrous sodium sulfate are presented. The methodology and data reported here should permit better modeling of the volume stability of cementitious systems exposed to various different climatic conditions.

  6. Development of Dodecaniobate Keggin Chain Materials as Alternative Sorbents for SR and Actinide Removal from High-Level Nuclear Waste Solutions

    SciTech Connect

    Nyman, May; Bonhomme, Francois

    2004-03-28

    The current baseline sorbent (monosodium titanate) for Sr and actinide removal from Savannah River Site's high level wastes has excellent adsorption capabilities for Sr but poor performance for the actinides. We are currently investigating the development of alternative materials that sorb radionuclides based on chemical affinity and/or size selectivity. The polyoxometalates, negatively-charged metal oxo clusters, have known metal binding properties and are of interest for radionuclide sequestration. We have developed a class of Keggin-ion based materials, where the Keggin ions are linked in 1- dimensional chains separated by hydrated, charge-balancing cations. These Nb-based materials are stable in the highly basic nuclear waste solutions and show good selectivity for Sr and Pu. Synthesis, characterization and structure of these materials in their native forms and Sr-exchanged forms will be presented.

  7. 77 FR 40032 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-07-06

    ... Methane Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice... Federal Officer; Welcome by the Chair of the Committee; Committee Business; Update on Prudhoe Bay Testing; FY 2012 Methane Hydrate Program Activities; Update on International Activity; Methane Hydrate...

  8. 76 FR 59667 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-09-27

    ... Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice of Open Meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... of the Committee: The purpose of the Methane Hydrate Advisory Committee is to provide advice...

  9. 78 FR 37536 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-06-21

    ... Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. The Federal... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of...

  10. Detailed calculations of minor actinide transmutation in a fast reactor

    SciTech Connect

    Takeda, Toshikazu

    2015-12-31

    The transmutation of minor actinides in a fast reactor is investigated by a new method to investigate the transmutation behavior of individual minor actinides. It is found that Np-237 and Am-241 mainly contributes to the transmutation rate though the transmutation behaviors are very different.

  11. POTENTIAL BENCHMARKS FOR ACTINIDE PRODUCTION IN HANFORD REACTORS

    SciTech Connect

    PUIGH RJ; TOFFER H

    2011-10-19

    A significant experimental program was conducted in the early Hanford reactors to understand the reactor production of actinides. These experiments were conducted with sufficient rigor, in some cases, to provide useful information that can be utilized today in development of benchmark experiments that may be used for the validation of present computer codes for the production of these actinides in low enriched uranium fuel.

  12. Process for making a ceramic composition for immobilization of actinides

    DOEpatents

    Ebbinghaus, Bartley B.; Van Konynenburg, Richard A.; Vance, Eric R.; Stewart, Martin W.; Walls, Philip A.; Brummond, William Allen; Armantrout, Guy A.; Herman, Connie Cicero; Hobson, Beverly F.; Herman, David Thomas; Curtis, Paul G.; Farmer, Joseph

    2001-01-01

    Disclosed is a process for making a ceramic composition for the immobilization of actinides, particularly uranium and plutonium. The ceramic is a titanate material comprising pyrochlore, brannerite and rutile. The process comprises oxidizing the actinides, milling the oxides to a powder, blending them with ceramic precursors, cold pressing the blend and sintering the pressed material.

  13. Process for Making a Ceramic Composition for Immobilization of Actinides

    SciTech Connect

    Ebbinghaus, Bartley B.; Van Konynenburg, Richard A.; Vance, Eric R.; Stewart, Martin W.; Walls, Philip A.; Brummond, William Allen; Armantrout, Guy A.; Curtis, Paul G.; Hobson, Beverly F.; Farmer, Joseph; Herman, Connie Cicero; Herman, David Thomas

    1999-06-22

    Disclosed is a process for making a ceramic composition for the immobilization of actinides, particularly uranium and plutonium. The ceramic is a titanate material comprising pyrochlore, brannerite and rutile. The process comprises oxidizing the actinides, milling the oxides to a powder, blending them with ceramic precursors, cold pressing the blend and sintering the pressed material.

  14. Improved method for extracting lanthanides and actinides from acid solutions

    DOEpatents

    Horwitz, E.P.; Kalina, D.G.; Kaplan, L.; Mason, G.W.

    1983-07-26

    A process for the recovery of actinide and lanthanide values from aqueous acidic solutions uses a new series of neutral bi-functional extractants, the alkyl(phenyl)-N,N-dialkylcarbamoylmethylphosphine oxides. The process is suitable for the separation of actinide and lanthanide values from fission product values found together in high-level nuclear reprocessing waste solutions.

  15. Detailed calculations of minor actinide transmutation in a fast reactor

    NASA Astrophysics Data System (ADS)

    Takeda, Toshikazu

    2015-12-01

    The transmutation of minor actinides in a fast reactor is investigated by a new method to investigate the transmutation behavior of individual minor actinides. It is found that Np-237 and Am-241 mainly contributes to the transmutation rate though the transmutation behaviors are very different.

  16. Study of actinide chemistry in saturated potassium fluoride solution

    NASA Technical Reports Server (NTRS)

    Cohen, D.; Thalmayer, C. E.

    1969-01-01

    Study concerning the chemistry of actinides in saturated KF solution included work with neptunium, uranium, and americium. Solubilities, absorption spectra, oxidation-reduction reactions, and solid compounds which can be produced in KF solution were examined. The information is used for preparation of various materials from salts of the actinides.

  17. Hydration rind dates rhyolite flows.

    PubMed

    Friedman, I

    1968-02-23

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago. PMID:17768978

  18. Hydration rind dates rhyolite flows

    USGS Publications Warehouse

    Friedman, I.

    1968-01-01

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago.

  19. Attraction between hydrated hydrophilic surfaces

    NASA Astrophysics Data System (ADS)

    Kanduč, Matej; Schneck, Emanuel; Netz, Roland R.

    2014-08-01

    According to common knowledge, hydrophilic surfaces repel via hydration forces while hydrophobic surfaces attract, but mounting experimental evidence suggests that also hydrophilic surfaces can attract. Using all-atom molecular dynamics simulations at prescribed water chemical potential we study the crossover from hydration repulsion to hydrophobic attraction for planar polar surfaces of varying stiffness and hydrogen-bonding capability. Rescaling the partial charges of the polar surface groups, we cover the complete spectrum from very hydrophobic surfaces (characterized by contact angles θ ≃ 135°) to hydrophilic surfaces exhibiting complete wetting (θ = 0°). Indeed, for a finite range θadh < θ < 90°, we find a regime where hydrophilic surfaces attract at sub-nanometer separation and stably adhere without intervening water. The adhesive contact angle θadh depends on surface type and lies in the range 65° < θadh < 80°, in good agreement with experiments. Analysis of the total number of hydrogen bonds (HBs) formed by water and surface groups rationalizes this crossover between hydration repulsion and hydrophilic attraction in terms of a subtle balance: Highly polar surfaces repel because of strongly bound hydration water, less polar hydrophilic surfaces attract because water-water HBs are preferred over surface-water HBs. Such solvent reorganization forces presumably underlie also other important phenomena, such as selective ion adsorption to interfaces as well as ion pair formation.

  20. Photofission of Actinides with Linearly Polarized Photons

    SciTech Connect

    Dale, D. S.; Cole, P. L.; Conn, A.; Forest, T. A.; Kosinov, O.; Setiniyaz, S.; Shapovlov, R.; Starovoitova, V.; Swanson, J.; Bodily, R.; Kelley, K.

    2010-08-04

    Idaho State University and the Idaho Accelerator Center are developing a polarized photon facility in the 10 MeV region using the off axis bremsstrahlung technique. Initial tests have been performed with the aim of using the high analyzing power of the photodisintegration of the deuteron to measure the beam polarization. A program is currently underway to measure the potential angular asymmetries of neutrons arising from the angular distribution of the fission fragments from photofission with linearly polarized photons. In this paper, we describe the Idaho State University Polarized Photon Facility, present results of commissioning runs, and describe potential application of polarized photofission in detecting actinides for homeland security and safeguards applications.

  1. Actinide management with commercial fast reactors

    NASA Astrophysics Data System (ADS)

    Ohki, Shigeo

    2015-12-01

    The capability of plutonium-breeding and minor-actinide (MA) transmutation in the Japanese commercial sodium-cooled fast reactor offers one of practical solutions for obtaining sustainable energy resources as well as reducing radioactive toxicity and inventory. The reference core design meets the requirement of flexible breeding ratio from 1.03 to 1.2. The MA transmutation amount has been evaluated as 50-100 kg/GWey if the MA content in fresh fuel is 3-5 wt%, where about 30-40% of initial MA can be transmuted in the discharged fuel.

  2. Actinide management with commercial fast reactors

    SciTech Connect

    Ohki, Shigeo

    2015-12-31

    The capability of plutonium-breeding and minor-actinide (MA) transmutation in the Japanese commercial sodium-cooled fast reactor offers one of practical solutions for obtaining sustainable energy resources as well as reducing radioactive toxicity and inventory. The reference core design meets the requirement of flexible breeding ratio from 1.03 to 1.2. The MA transmutation amount has been evaluated as 50-100 kg/GW{sub e}y if the MA content in fresh fuel is 3-5 wt%, where about 30-40% of initial MA can be transmuted in the discharged fuel.

  3. Status of nuclear data for actinides

    SciTech Connect

    Guzhovskii, B.Y.; Gorelov, V.P.; Grebennikov, A.N.

    1995-10-01

    Nuclear data required for transmutation problem include many actinide nuclei. In present paper the analysis of neutron fission, capture, (n,2n) and (n,3n) reaction cross sections at energy region from thermal point to 14 MeV was carried out for Th, Pa, U, Np, Pu, Am and Cm isotops using modern evaluated nuclear data libraries and handbooks of recommended nuclear data. Comparison of these data indicates on substantial discrepancies in different versions of files, that connect with quality and completeness of original experimental data.

  4. {alpha} Decay of Deformed Actinide Nuclei

    SciTech Connect

    Stewart, T.L.; Kermode, M.W.; Beachey, D.J.; Rowley, N.; Grant, I.S.; Kruppa, A.T.

    1996-07-01

    {alpha} decay through a deformed potential barrier produces significant mixing of angular momenta when mapped from the nuclear interior to the outside. Using experimental branching ratios and either semiclassical or coupled-channels transmission matrices, we have found that there is a set of internal amplitudes which is essentially constant for all even-even actinide nuclei. These same amplitudes also give good results for the known anisotropic {alpha}-particle emission of the favored decays of odd nuclei in the same mass region. {copyright} {ital 1996 The American Physical Society.}

  5. Separation of actinides from lanthanides utilizing molten salt electrorefining

    SciTech Connect

    Grimmett, D.L.; Fusselman, S.P.; Roy, J.J.; Gay, R.L.; Krueger, C.L.; Storvick, T.S.; Inoue, T.; Hijikata, T.; Takahashi, N.

    1996-10-01

    TRUMP-S (TRansUranic Management through Pyropartitioning Separation) is a pyrochemical process being developed to separate actinides form fission products in nuclear waste. A key process step involving molten salt electrorefining to separate actinides from lanthanides has been studied on a laboratory scale. Electrorefining of U, Np, Pu, Am, and lanthanide mixtures from molten cadmium at 450 C to a solid cathode utilizing a molten chloride electrolyte resulted in > 99% removal of actinides from the molten cadmium and salt phases. Removal of the last few percent of actinides is accompanied by lowered cathodic current efficiency and some lanthanide codeposition. Actinide/lanthanide separation ratios on the cathode are ordered U > Np > Pu > Am and are consistent with predictions based on equilibrium potentials.

  6. Actinides and Rare Earths Topical Conference (Code AC)

    SciTech Connect

    Tobin, J G

    2009-11-24

    Actinide and the Rare Earth materials exhibit many unique and diverse physical, chemical and magnetic properties, in large part because of the complexity of their f electronic structure. This Topical Conference will focus upon the chemistry, physics and materials science in Lanthanide and Actinide materials, driven by 4f and 5f electronic structure. Particular emphasis will be placed upon 4f/5f magnetic structure, surface science and thin film properties. For the actinides, fundamental actinide science and its role in resolving technical challenges posed by actinide materials will be stressed. Both basic and applied experimental approaches, including synchrotron-radiation-based investigations, as well as theoretical modeling and computational simulations, are planned to be part of the Topical Conference. Of particular importance are the issues related to the potential renaissance in Nuclear Fuels, including synthesis, oxidation, corrosion, intermixing, stability in extreme environments, prediction of properties via benchmarked simulations, separation science, environmental impact and disposal of waste products.

  7. Research in actinide chemistry. Progress report, 1990--1993

    SciTech Connect

    Choppin, G.R.

    1993-04-01

    This research studies the behavior of the actinide elements in aqueous solution. The high radioactivity of the transuranium actinides limits the concentrations which can be studied and, consequently, limits the experimental techniques. However, oxidation state analogs (trivalent lanthanides, tetravalent thorium, and hexavalent uranium) do not suffer from these limitations. Behavior of actinides in the environment are a major USDOE concern, whether in connection with long-term releases from a repository, releases from stored defense wastes or accidental releases in reprocessing, etc. Principal goal of our research was expand the thermodynamic data base on complexation of actinides by natural ligands (e.g., OH{sup {minus}}, CO{sub 3}{sup 2{minus}}, PO{sub 4}{sup 3{minus}}, humates). The research undertakes fundamental studies of actinide complexes which can increase understanding of the environmental behavior of these elements.

  8. Actinide-Aluminate Speciation in Alkaline Radioactive Waste

    SciTech Connect

    Dr. David L. Clark; Dr. Alexander M. Fedosseev

    2001-12-21

    Investigation of behavior of actinides in alkaline media containing AL(III) showed that no aluminate complexes of actinides in oxidation states (IIII-VIII) were formed in alkaline solutions. At alkaline precipitation IPH (10-14) of actinides in presence of AL(III) formation of aluminate compounds is not observed. However, in precipitates contained actinides (IIV)<(VI), and to a lesser degree actinides (III), some interference of components takes place that is reflected in change of solid phase properties in comparison with pure components or their mechanical mixture. The interference decreases with rise of precipitation PH and at PH 14 is exhibited very feebly. In the case of NP(VII) the individual compound with AL(III) is obtained, however it is not aluminate of neptunium(VII), but neptunate of aluminium(III) similar to neptunates of other metals obtained earlier.

  9. Physical activity, hydration and health.

    PubMed

    Marcos, Ascensión; Manonelles, Pedro; Palacios, Nieves; Wärnberg, Julia; Casajús, José A; Pérez, Margarita; Aznar, Susana; Benito, Pedro J; Martínez-Gomez, David; Ortega, Francisco B; Ortega, Eduardo; Urrialde, Rafael

    2014-01-01

    Since the beginning of mankind, man has sought ways to promote and preserve health as well as to prevent disease. Hydration, physical activity and exercise are key factors for enhancing human health. However, either a little dose of them or an excess can be harmful for health maintenance at any age. Water is an essential nutrient for human body and a major key to survival has been to prevent dehydration. However, there is still a general controversy regarding the necessary amount to drink water or other beverages to properly get an adequate level of hydration. In addition, up to now the tools used to measure hydration are controversial. To this end, there are several important groups of variables to take into account such as water balance, hydration biomarkers and total body water. A combination of methods will be the most preferred tool to find out any risk or situation of dehydration at any age range. On the other hand, physical activity and exercise are being demonstrated to promote health, avoiding or reducing health problems, vascular and inflammatory disea ses and helping weight management. Therefore, physical activity is also being used as a pill within a therapy to promote health and reduce risk diseases, but as in the case of drugs, dose, intensity, frequency, duration and precautions have to be evaluated and taken into account in order to get the maximum effectiveness and success of a treatment. On the other hand, sedentariness is the opposite concept to physical activity that has been recently recognized as an important factor of lifestyle involved in the obesogenic environment and consequently in the risk of the non-communicable diseases. In view of the literature consulted and taking into account the expertise of the authors, in this review a Decalogue of global recommendations is included to achieve an adequate hydration and physical activity status to avoid overweight/obesity consequences. PMID:24972459

  10. Mesoscale texture of cement hydrates.

    PubMed

    Ioannidou, Katerina; Krakowiak, Konrad J; Bauchy, Mathieu; Hoover, Christian G; Masoero, Enrico; Yip, Sidney; Ulm, Franz-Josef; Levitz, Pierre; Pellenq, Roland J-M; Del Gado, Emanuela

    2016-02-23

    Strength and other mechanical properties of cement and concrete rely upon the formation of calcium-silicate-hydrates (C-S-H) during cement hydration. Controlling structure and properties of the C-S-H phase is a challenge, due to the complexity of this hydration product and of the mechanisms that drive its precipitation from the ionic solution upon dissolution of cement grains in water. Departing from traditional models mostly focused on length scales above the micrometer, recent research addressed the molecular structure of C-S-H. However, small-angle neutron scattering, electron-microscopy imaging, and nanoindentation experiments suggest that its mesoscale organization, extending over hundreds of nanometers, may be more important. Here we unveil the C-S-H mesoscale texture, a crucial step to connect the fundamental scales to the macroscale of engineering properties. We use simulations that combine information of the nanoscale building units of C-S-H and their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles. We compute small-angle scattering intensities, pore size distributions, specific surface area, local densities, indentation modulus, and hardness of the material, providing quantitative understanding of different experimental investigations. Our results provide insight into how the heterogeneities developed during the early stages of hydration persist in the structure of C-S-H and impact the mechanical performance of the hardened cement paste. Unraveling such links in cement hydrates can be groundbreaking and controlling them can be the key to smarter mix designs of cementitious materials. PMID:26858450

  11. Mesoscale texture of cement hydrates

    PubMed Central

    Ioannidou, Katerina; Krakowiak, Konrad J.; Bauchy, Mathieu; Hoover, Christian G.; Masoero, Enrico; Yip, Sidney; Ulm, Franz-Josef; Levitz, Pierre; Pellenq, Roland J.-M.; Del Gado, Emanuela

    2016-01-01

    Strength and other mechanical properties of cement and concrete rely upon the formation of calcium–silicate–hydrates (C–S–H) during cement hydration. Controlling structure and properties of the C–S–H phase is a challenge, due to the complexity of this hydration product and of the mechanisms that drive its precipitation from the ionic solution upon dissolution of cement grains in water. Departing from traditional models mostly focused on length scales above the micrometer, recent research addressed the molecular structure of C–S–H. However, small-angle neutron scattering, electron-microscopy imaging, and nanoindentation experiments suggest that its mesoscale organization, extending over hundreds of nanometers, may be more important. Here we unveil the C–S–H mesoscale texture, a crucial step to connect the fundamental scales to the macroscale of engineering properties. We use simulations that combine information of the nanoscale building units of C–S–H and their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles. We compute small-angle scattering intensities, pore size distributions, specific surface area, local densities, indentation modulus, and hardness of the material, providing quantitative understanding of different experimental investigations. Our results provide insight into how the heterogeneities developed during the early stages of hydration persist in the structure of C–S–H and impact the mechanical performance of the hardened cement paste. Unraveling such links in cement hydrates can be groundbreaking and controlling them can be the key to smarter mix designs of cementitious materials. PMID:26858450

  12. Actinide Solubility and Speciation in the WIPP

    SciTech Connect

    Reed, Donald T.

    2015-11-02

    The presentation begins with the role and need for nuclear repositories (overall concept, international updates (Sweden, Finland, France, China), US approach and current status), then moves on to the WIPP TRU repository concept (design, current status--safety incidents of February 5 and 14, 2014, path forward), and finally considers the WIPP safety case: dissolved actinide concentrations (overall approach, oxidation state distribution and redox control, solubility of actinides, colloidal contribution and microbial effects). The following conclusions are set forth: (1) International programs are moving forward, but at a very slow and somewhat sporadic pace. (2) In the United States, the Salt repository concept, from the perspective of the long-term safety case, remains a viable option for nuclear waste management despite the current operational issues/concerns. (3) Current model/PA prediction (WIPP example) are built on redundant conservatisms. These conservatisms are being addressed in the ongoing and future research to fill existing data gaps--redox control of plutonium by Fe(0, II), thorium (analog) solubility studies in simulated brine, contribution of intrinsic and biocolloids to the mobile concentration, and clarification of microbial ecology and effects.

  13. Actinide transmutation in a thermal reactor

    SciTech Connect

    Facchini, A.; Sanjust, V.

    1993-12-31

    The long term radiotoxicity of nuclear wastes may be substantially reduced by long irradiation in thermal reactors. Preliminary calculations showed that appreciable quantities of the minor actinides and long lived fission products may be recycled in a power PWR, and that, a few centuries after 20--30 years of irradiation, they reach radiotoxicity levels comparable to those of the uranium quantity required to make the corresponding fuel amount. The purpose of the present work is to investigate the conceptual possibility of reducing the level of the long term radiotoxicity, due to Minor Actinides and Long-Lived Fission Products (MA/LLFP) produced in UO{sub 2} fuel, by long irradiation of them in a power PWR. More precisely the authors pursued the objective of determining what fraction of the MA/LLFP mixture produced in a 1,000 MWe PWR during its whole life, may be burned in a similar power reactor. A waste burning efficiency has been considered satisfactory if the long term radiotoxicity of the MA/LLFP contained in a given quantity of spent fuel reaches, a few centuries after its irradiation, the level corresponding to that of the amount of natural uranium required to produce the same quantity of fresh fuel. This waiting time is in fact necessary in any case for cooling the other fission products to a sufficiently low radioactivity level and is a time span not unreasonable when considering man-made barriers against the radionuclide diffusion into the biosphere.

  14. Fusion-Fission Burner for Transuranic Actinides

    NASA Astrophysics Data System (ADS)

    Choi, Chan

    2013-10-01

    The 14-MeV DT fusion neutron spectrum from mirror confinement fusion can provide a unique capability to transmute the transuranic isotopes from light water reactors (LWR). The transuranic (TRU) actinides, high-level radioactive wastes, from spent LWR fuel pose serious worldwide problem with long-term decay heat and radiotoxicity. However, ``transmuted'' TRU actinides can not only reduce the inventory of the TRU in the spent fuel repository but also generate additional energy. Typical commercial LWR fuel assemblies for BWR (boiling water reactor) and PWR (pressurized water reactor) measure its assembly lengths with 4.470 m and 4.059 m, respectively, while its corresponding fuel rod lengths are 4.064 m and 3.851 m. Mirror-based fusion reactor has inherently simple geometry for transmutation blanket with steady-state reactor operation. Recent development of gas-dynamic mirror configuration has additional attractive feature with reduced size in central plasma chamber, thus providing a unique capability for incorporating the spent fuel assemblies into transmutation blanket designs. The system parameters for the gas-dynamic mirror-based hybrid burner will be discussed.

  15. Evaluation of actinide biosorption by microorganisms

    SciTech Connect

    Happel, A.M.

    1996-06-01

    Conventional methods for removing metals from aqueous solutions include chemical precipitation, chemical oxidation or reduction, ion exchange, reverse osmosis, electrochemical treatment and evaporation. The removal of radionuclides from aqueous waste streams has largely relied on ion exchange methods which can be prohibitively costly given increasingly stringent regulatory effluent limits. The use of microbial cells as biosorbants for heavy metals offers a potential alternative to existing methods for decontamination or recovery of heavy metals from a variety of industrial waste streams and contaminated ground waters. The toxicity and the extreme and variable conditions present in many radionuclide containing waste streams may preclude the use of living microorganisms and favor the use of non-living biomass for the removal of actinides from these waste streams. In the work presented here, we have examined the biosorption of uranium by non-living, non-metabolizing microbial biomass thus avoiding the problems associated with living systems. We are investigating biosorption with the long term goal of developing microbial technologies for the remediation of actinides.

  16. Handbook of gas hydrate properties and occurrence

    SciTech Connect

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

    1983-12-01

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

  17. Thermal conductivity of hydrate-bearing sediments

    USGS Publications Warehouse

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

    2009-01-01

    A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate-saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate-bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces. Copyright 2009 by the American Geophysical Union.

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

    NASA Astrophysics Data System (ADS)

    Mahabadi, Nariman; Zheng, Xianglei; Jang, Jaewon

    2016-05-01

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

  19. Pockmark formation and evolution in deep water Nigeria: Rapid hydrate growth versus slow hydrate dissolution

    NASA Astrophysics Data System (ADS)

    Sultan, N.; Bohrmann, G.; Ruffine, L.; Pape, T.; Riboulot, V.; Colliat, J.-L.; De Prunelé, A.; Dennielou, B.; Garziglia, S.; Himmler, T.; Marsset, T.; Peters, C. A.; Rabiu, A.; Wei, J.

    2014-04-01

    In previous works, it has been suggested that dissolution of gas hydrate can be responsible for pockmark formation and evolution in deep water Nigeria. It was shown that those pockmarks which are at different stages of maturation are characterized by a common internal architecture associated to gas hydrate dynamics. New results obtained by drilling into gas hydrate-bearing sediments with the MeBo seafloor drill rig in concert with geotechnical in situ measurements and pore water analyses indicate that pockmark formation and evolution in the study area are mainly controlled by rapid hydrate growth opposed to slow hydrate dissolution. On one hand, positive temperature anomalies, free gas trapped in shallow microfractures near the seafloor and coexistence of free gas and gas hydrate indicate rapid hydrate growth. On the other hand, slow hydrate dissolution is evident by low methane concentrations and almost constant sulfate values 2 m above the Gas Hydrate Occurrence Zone.

  20. Crystal structure of 4,4′,4′′-(1,3,5-triazine-2,4,6-tri­yl)tripyridinium trichloride 2.5-hydrate

    PubMed Central

    Ling, Bo-Kai; Feng, Xiao-Long; Li, Yang; Luan, Tian-Gang

    2015-01-01

    The asymmetric unit of the title compound, C18H15N6 3+·3Cl−·2.5H2O, contains two independent (1,3,5-triazine-2,4,6-tri­yl)tripyridinium cations. Both cations are approximately planar, the r.m.s. deviations of fitted non-H atoms being 0.045 and 0.051 Å. In the crystal, extensive O—H⋯Cl, O—H⋯O, N—H⋯Cl and N—H⋯O hydrogen bonds and weak C—H⋯Cl and C—H⋯O inter­actions link the organic cations, Cl− anions and water mol­ecules into a three-dimensional supra­molecular architecture. π–π stacking between the pyridine rings of adjacent cations is also observed, the centroid-to-centroid distance being 3.7578 (8) Å. PMID:26594564

  1. On the suitability of lanthanides as actinide analogs

    SciTech Connect

    Raymond, Kenneth; Szigethy, Geza

    2008-07-01

    With the current level of actinide materials used in civilian power generation and the need for safe and efficient methods for the chemical separation of these species from their daughter products and for long-term storage requirements, a detailed understanding of actinide chemistry is of great importance. Due to the unique bonding properties of the f-elements, the lanthanides are commonly used as structural and chemical models for the actinides, but differences in the bonding between these 4f and 5f elements has become a question of immediate applicability to separations technology. This brief overview of actinide coordination chemistry in the Raymond group at UC Berkeley/LBNL examines the validity of using lanthanide analogs as structural models for the actinides, with particular attention paid to single crystal X-ray diffraction structures. Although lanthanides are commonly accepted as reasonable analogs for the actinides, these comparisons suggest the careful study of actinide materials independent of their lanthanide analogs to be of utmost importance to present and future efforts in nuclear industries. (authors)

  2. On the Suitability of Lanthanides as Actinide Analogs

    SciTech Connect

    Szigethy, Geza; Raymond, Kenneth N.

    2008-04-11

    With the current level of actinide materials used in civilian power generation and the need for safe and efficient methods for the chemical separation of these species from their daughter products and for long-term storage requirements, a detailed understanding of actinide chemistry is of great importance. Due to the unique bonding properties of the f-elements, the lanthanides are commonly used as structural and chemical models for the actinides, but differences in the bonding between these 4f and 5f elements has become a question of immediate applicability to separations technology. This brief overview of actinide coordination chemistry in the Raymond group at UC Berkeley/LBNL examines the validity of using lanthanide analogs as structural models for the actinides, with particular attention paid to single crystal X-ray diffraction structures. Although lanthanides are commonly accepted as reasonable analogs for the actinides, these comparisons suggest the careful study of actinide materials independent of their lanthanide analogs to be of utmost importance to present and future efforts in nuclear industries.

  3. End point control of an actinide precipitation reactor

    SciTech Connect

    Muske, K.R.; Palmer, M.J.

    1997-10-01

    The actinide precipitation reactors in the nuclear materials processing facility at Los Alamos National Laboratory are used to remove actinides and other heavy metals from the effluent streams generated during the purification of plutonium. These effluent streams consist of hydrochloric acid solutions, ranging from one to five molar in concentration, in which actinides and other metals are dissolved. The actinides present are plutonium and americium. Typical actinide loadings range from one to five grams per liter. The most prevalent heavy metals are iron, chromium, and nickel that are due to stainless steel. Removal of these metals from solution is accomplished by hydroxide precipitation during the neutralization of the effluent. An end point control algorithm for the semi-batch actinide precipitation reactors at Los Alamos National Laboratory is described. The algorithm is based on an equilibrium solubility model of the chemical species in solution. This model is used to predict the amount of base hydroxide necessary to reach the end point of the actinide precipitation reaction. The model parameters are updated by on-line pH measurements.

  4. Gas core reactors for actinide transmutation. [uranium hexafluoride

    NASA Technical Reports Server (NTRS)

    Clement, J. D.; Rust, J. H.; Wan, P. T.; Chow, S.

    1979-01-01

    The preliminary design of a uranium hexafluoride actinide transmutation reactor to convert long-lived actinide wastes to shorter-lived fission product wastes was analyzed. It is shown that externally moderated gas core reactors are ideal radiators. They provide an abundant supply of thermal neutrons and are insensitive to composition changes in the blanket. For the present reactor, an initial load of 6 metric tons of actinides is loaded. This is equivalent to the quantity produced by 300 LWR-years of operation. At the beginning, the core produces 2000 MWt while the blanket generates only 239 MWt. After four years of irradiation, the actinide mass is reduced to 3.9 metric tonnes. During this time, the blanket is becoming more fissile and its power rapidly approaches 1600 MWt. At the end of four years, continuous refueling of actinides is carried out and the actinide mass is held constant. Equilibrium is essentially achieved at the end of eight years. At equilibrium, the core is producing 1400 MWt and the blanket 1600 MWt. At this power level, the actinide destruction rate is equal to the production rate from 32 LWRs.

  5. Thin extractive membrane for monitoring actinides in aqueous streams.

    PubMed

    Chavan, Vivek; Paul, Sumana; Pandey, Ashok K; Kalsi, P C; Goswami, A

    2013-09-15

    Alpha spectrometry and solid state nuclear track detectors (SSNTDs) are used for monitoring ultra-trace amount of alpha emitting actinides in different aqueous streams. However, these techniques have limitations i.e. alpha spectrometry requires a preconcentration step and SSNTDs are not chemically selective. Therefore, a thin polymer inclusion membrane (PIM) supported on silanized glass was developed for preconcentraion and determination of ultra-trace concentration of actinides by α-spectrometry and SSNTDs. PIMs were formed by spin coating on hydrophobic glass slide or solvent casting to form thin and self-supported membranes, respectively. Sorption experiments indicated that uptakes of actinides in the PIM were highly dependent on acidity of solution i.e. Am(III) sorbed up to 0.1 molL(-1) HNO₃, U(VI) up to 0.5 molL(-1) HNO₃ and Pu(IV) from HNO₃ concentration as high as 4 molL(-1). A scheme was developed for selective sorption of target actinide in the PIM by adjusting acidity and oxidation state of actinide. The actinides sorbed in PIMs were quantified by alpha spectrometry and SSNTDs. For SSNTDs, neutron induced fission-fragment tracks and α-particle tracks were registered in Garware polyester and CR-39 for quantifications of natural uranium and α-emitting actinides ((241)Am/(239)Pu/(233)U), respectively. Finally, the membranes were tested to quantify Pu in 4 molL(-1) HNO3 solutions and synthetic urine samples. PMID:23747462

  6. Separation of actinides from spent nuclear fuel: A review.

    PubMed

    Veliscek-Carolan, Jessica

    2016-11-15

    This review summarises the methods currently available to extract radioactive actinide elements from solutions of spent nuclear fuel. This separation of actinides reduces the hazards associated with spent nuclear fuel, such as its radiotoxicity, volume and the amount of time required for its' radioactivity to return to naturally occurring levels. Separation of actinides from environmental water systems is also briefly discussed. The actinide elements typically found in spent nuclear fuel include uranium, plutonium and the minor actinides (americium, neptunium and curium). Separation methods for uranium and plutonium are reasonably well established. On the other hand separation of the minor actinides from lanthanide fission products also present in spent nuclear fuel is an ongoing challenge and an area of active research. Several separation methods for selective removal of these actinides from spent nuclear fuel will be described. These separation methods include solvent extraction, which is the most commonly used method for radiochemical separations, as well as the less developed but promising use of adsorption and ion-exchange materials. PMID:27427893

  7. Plutonium and ''minor'' actinides: safe sequestration [rapid communication

    NASA Astrophysics Data System (ADS)

    Ewing, Rodney C.

    2005-01-01

    The actinides exhibit a number of unique chemical and nuclear properties. Of particular interest are the man-made actinides (Np, Pu, Cm and Am) that are produced in significant enough quantities that they are a source of energy in fission reactions, a source of fissile material for nuclear weapons and of environmental concern because of their long half-lives and radiotoxicity. During the past 50 yr, over 1400 mT of Pu and substantial quantities of the "minor" actinides, such as Np, Am and Cm, have been generated in nuclear reactors. There are two basic strategies for the disposition of these elements: (1) to "burn" or transmute the actinides using nuclear reactors or accelerators; (2) to "sequester" the actinides in chemically durable, radiation-resistant materials that are suitable for geologic disposal. There has been substantial interest in the use of isometric pyrochlore, A 2B 2O 7 (A=rare earths; B=Ti, Zr, Sn and Hf), for the immobilization of actinides, particularly plutonium. Systematic studies of rare-earth pyrochlores have led to the discovery that certain compositions (B=Zr, Hf) are stable to very high doses of α-decay event damage. The radiation stability of these compositions is closely related to the structural distortions that occur for specific pyrochlore compositions and the electronic structure of the B-site cation. This understanding provides the basis for designing materials for the safe, long-term immobilization and sequestration of actinides.

  8. National workshop on gas hydrates

    NASA Astrophysics Data System (ADS)

    Max, Michael D.; Dillon, William P.; Malone, Rodney D.; Kvenvolden, Keith A.

    The range of present knowledge on the subject of gas hydrates and related federal research programs was the topic of discussion at the National Workshop on Gas Hydrates, April 23-24. The intention of the meeting was to provide the impetus for an expanded and broader-based national research program in both academia and government. Held at the U.S. Geological Survey National Center, Reston, Va., the workshop was organized by Michael D. Max, Naval Research Laboratory, Washington, D.C.; William P. Dillon, USGS, Woods Hole, Mass.; and Rodney D. Malone, U.S. Department of Energy, Morgantown Energy Technology Center, Morgantown, W.Va. The 33 attendees represented academia (33%), federal agencies (58%), and industry (9%).

  9. Dynamics of hydrated starch saccharides

    NASA Astrophysics Data System (ADS)

    Di Bari, M.; Deriu, A.; Albanese, G.; Cavatorta, F.

    2003-08-01

    We report here elastic neutron scattering data on glucose and on two of its polymeric forms: amylose and amylopectin. We have covered the hydration range from the dry state to about 0.6 g water/g dry saccharide. The data indicate, in all the analysed systems, the presence of a dynamic glass-like transition similar to that observed in hydrated proteins. The fact that this feature is observed also in a relatively small molecule like glucose confirms the hypothesis already put forward by other authors, that this transition in biomolecular species is essentially triggered and driven by the interaction of the macromolecule with the network of fluctuating H-bond of the solvent.

  10. Actinide Sub-Actinide Flux Ratio Estimated from NASA Challenger Space Shuttle Borne Passive Detector Experiment

    NASA Astrophysics Data System (ADS)

    Basu, Basudhara; Bhattacharyya, D. P.; Biswas, S.; O'Sullivan, D.; Thompson, A.

    A video trace analysis of 117 ultra heavy cosmic nuclei detected by NASA space shuttle borne lexan detectors has been presented here. The major axes of the elliptical track etch pits in the long hour etched detectors have been measured using a Hund microscope computerized for the measurements using a Pentium. The major axes distribution exhibits the existence of ultra heavy nuclei of charges of Z ranging from 72 to 96 compatible with the expected results from restricted energy loss calculations. The estimated actinide sub-actinide flux ratio has been found to be 0.0636±0.0248 which is comparable to the earlier observations by Fowler et al., Thompson et al. and O'Sullivan.

  11. Uranyl p-toluenesulphonate and its crystal hydrates. Synthesis and dehydration-hydration processes

    NASA Astrophysics Data System (ADS)

    Baluev, A. V.; Mityakhina, V. S.; Bogachev, S. V.; Suglobova, I. G.

    2003-01-01

    Lowest hydrates of uranyl p-toluenesulphonate (UPTS) and anhydrous salt were synthesised. The dehydration-hydration processes were studied by thermal gravimetric analysis. It has been established that the hydrate shell of UPTS has a layered structure. The IR spectra of UPTS and its hydrates were recorded. It was found that the IR spectra of UPTS crystal hydrates of the same composition, produced in dehydration-hydration, noticeably differ in the range of water vibrations and are the same in the range corresponding to vibrations of sulphonate groups.

  12. Gas hydrate cool storage system

    DOEpatents

    Ternes, Mark P.; Kedl, Robert J.

    1985-01-01

    This invention is a process for formation of a gas hydrate to be used as a cool storage medium using a refrigerant in water. Mixing of the immiscible refrigerant and water is effected by addition of a surfactant and agitation. The difficult problem of subcooling during the process is overcome by using the surfactant and agitation and performance of the process significantly improves and approaches ideal.

  13. 5f-electron localization in the actinide metals: thorides, actinides and the Mott transition

    NASA Astrophysics Data System (ADS)

    Lawson, A. C.

    2016-03-01

    For the light actinides Ac-Cm, the numbers of localized and itinerant 5f-electrons are determined by comparing various estimates of the f-electron counts. At least one itinerant f-electron is found for each element, Pa-Cm. These results resolve certain disagreements among electron counts determined by different methods and are consistent with the Mott transition model and with the picture of the 5f-electrons' dual nature.

  14. Separations and Actinide Science -- 2005 Roadmap

    SciTech Connect

    Not Available

    2005-09-01

    The Separations and Actinide Science Roadmap presents a vision to establish a separations and actinide science research (SASR) base composed of people, facilities, and collaborations and provides new and innovative nuclear fuel cycle solutions to nuclear technology issues that preclude nuclear proliferation. This enabling science base will play a key role in ensuring that Idaho National Laboratory (INL) achieves its long-term vision of revitalizing nuclear energy by providing needed technologies to ensure our nation's energy sustainability and security. To that end, this roadmap suggests a 10-year journey to build a strong SASR technical capability with a clear mission to support nuclear technology development. If nuclear technology is to be used to satisfy the expected growth in U.S. electrical energy demand, the once-through fuel cycle currently in use should be reconsidered. Although the once-through fuel cycle is cost-effective and uranium is inexpensive, a once-through fuel cycle requires long-term disposal to protect the environment and public from long-lived radioactive species. The lack of a current disposal option (i.e., a licensed repository) has resulted in accumulation of more than 50,000 metric tons of spent nuclear fuel. The process required to transition the current once-through fuel cycle to full-recycle will require considerable time and significant technical advancement. INL's extensive expertise in aqueous separations will be used to develop advanced separations processes. Computational chemistry will be expanded to support development of future processing options. In the intermediate stage of this transition, reprocessing options will be deployed, waste forms with higher loading densities and greater stability will be developed, and transmutation of long-lived fission products will be explored. SASR will support these activities using its actinide science and aqueous separations expertise. In the final stage, full recycle will be enabled by

  15. Multiple stage multiple filter hydrate store

    DOEpatents

    Bjorkman, H.K. Jr.

    1983-05-31

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

  16. Multiple stage multiple filter hydrate store

    DOEpatents

    Bjorkman, Jr., Harry K.

    1983-05-31

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

  17. The Development Path for Hydrate Natural Gas

    NASA Astrophysics Data System (ADS)

    Johnson, A. H.; Max, M. D.

    2008-12-01

    The question of when gas hydrate will become a commercially viable resource most concerns those nations with the most severe energy deficiencies. With the vast potential attributed to gas hydrate as a new gas play, the interest is understandable. Yet the resource potential of gas hydrate has persistently remained just over the horizon. While technical and economic hurdles have pushed back the timeline for development, considerable progress has been made in the past five years. An important lesson learned is that an analysis of the factors that control the formation of high grade hydrate deposits must be carried out so that both exploration and recovery scenarios can be modeled and engineered. Commercial hydrate development requires high concentrations of hydrate in porous, permeable reservoirs. It is only from such deposits that gas may be recovered in commercial quantities. While it is unrealistic to consider the global potential of gas hydrate to be in the hundreds of thousands of tcfs, there is a strong potential in the hundreds of tcfs or thousands of tcfs. Press releases from several national gas hydrate research programs have reported gas hydrate "discoveries". These are, in fact, hydrate shows that provide proof of the presence of hydrate where it may previously only have been predicted. Except in a few isolated areas, valid resource assessments remain to be accomplished through the identification of suitable hosts for hydrate concentrations such as sandstone reservoirs. A focused exploration effort based on geological and depositional characteristics is needed that addresses hydrate as part of a larger petroleum system. Simply drilling in areas that have identifiable bottom simulating reflectors (BSRs) is unlikely to be a viable exploration tool. It is very likely that with drilling on properly identified targets, commercial development could become a reality in less than a decade.

  18. Gas hydrates: Technology status report

    SciTech Connect

    Not Available

    1987-01-01

    In 1983, the US Department of Energy (DOE) assumed the responsibility for expanding the knowledge base and for developing methods to recover gas from hydrates. These are ice-like mixtures of gas and water where gas molecules are trapped within a framework of water molecules. This research is part of the Unconventional Gas Recovery (UGR) program, a multidisciplinary effort that focuses on developing the technology to produce natural gas from resources that have been classified as unconventional because of their unique geologies and production mechanisms. Current work on gas hydrates emphasizes geological studies; characterization of the resource; and generic research, including modeling of reservoir conditions, production concepts, and predictive strategies for stimulated wells. Complementing this work is research on in situ detection of hydrates and field tests to verify extraction methods. Thus, current research will provide a comprehensive technology base from which estimates of reserve potential can be made, and from which industry can develop recovery strategies. 7 refs., 3 figs., 6 tabs.

  19. Micelle Structure and Hydrophobic Hydration.

    PubMed

    Long, Joshua A; Rankin, Blake M; Ben-Amotz, Dor

    2015-08-26

    Despite the ubiquity and utility of micelles self-assembled from aqueous surfactants, longstanding questions remain regarding their surface structure and interior hydration. Here we combine Raman spectroscopy with multivariate curve resolution (Raman-MCR) to probe the hydrophobic hydration of surfactants with various aliphatic chain lengths, and either anionic (carboxylate) or cationic (trimethylammonium) head groups, both below and above the critical micelle concentration. Our results reveal significant penetration of water into micelle interiors, well beyond the first few carbons adjacent to the headgroup. Moreover, the vibrational C-D frequency shifts of solubilized deuterated n-hexane confirm that it resides in a dry, oil-like environment (while the localization of solubilized benzene is sensitive to headgroup charge). Our findings imply that the hydrophobic core of a micelle is surrounded by a highly corrugated surface containing hydrated non-polar cavities whose depth increases with increasing surfactant chain length, thus bearing a greater resemblance to soluble proteins than previously recognized. PMID:26222042

  20. Energy landscape of clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Desmedt, A.; Bedouret, L.; Pefoute, E.; Pouvreau, M.; Say-Liang-Fat, S.; Alvarez, M.

    2012-11-01

    Clathrate hydrates are nanoporous crystalline materials made of a network of hydrogen-bonded water molecules (forming host cages) that is stabilized by the presence of foreign (generally hydrophobic) guest molecules. The natural existence of large quantities of hydrocarbon hydrates in deep oceans and permafrost is certainly at the origin of numerous applications in the broad areas of energy and environmental sciences and technologies (e.g. gas storage). At a fundamental level, their nanostructuration confers on these materials specific properties (e.g. their "glass-like" thermal conductivity) for which the host-guest interactions play a key role. These interactions occur on broad timescale and thus require the use of multi-technique approach in which neutron scattering brings unvaluable information. This work reviews the dynamical properties of clathrate hydrates, ranging from intramolecular vibrations to Brownian relaxations; it illustrates the contribution of neutron scattering in the understanding of the underlying factors governing chemical-physics properties specific to these nanoporous systems.

  1. Chemistry of tetravalent actinide phosphates-Part I

    SciTech Connect

    Brandel, V. . E-mail: vbrandel@neuf.fr; Dacheux, N. . E-mail: dacheux@ipno.in2p3.fr

    2004-12-01

    The chemistry and crystal structure of phosphates of tetravalent cations, including that of actinides was reviewed several times up to 1985. Later, new compounds were synthesized and characterized. In more recent studies, it was found that some of previously reported phases, especially those of thorium, uranium and neptunium, were wrongly identified. In the light of these new facts an update review and classification of the tetravalent actinide phosphates is proposed in the two parts of this paper. Their crystal structure and some chemical properties are also compared to non-actinide cation phosphates.

  2. Engineering-Scale Distillation of Cadmium for Actinide Recovery

    SciTech Connect

    J.C. Price; D. Vaden; R.W. Benedict

    2007-10-01

    During the recovery of actinide products from spent nuclear fuel, cadmium is separated from the actinide products by a distillation process. Distillation occurs in an induction-heated furnace called a cathode processor capable of processing kilogram quantities of cadmium. Operating parameters have been established for sufficient recovery of the cadmium based on mass balance and product purity. A cadmium distillation rate similar to previous investigators has also been determined. The development of cadmium distillation for spent fuel treatment enhances the capabilities for actinide recovery processes.

  3. Separating the Minor Actinides Through Advances in Selective Coordination Chemistry

    SciTech Connect

    Lumetta, Gregg J.; Braley, Jenifer C.; Sinkov, Sergey I.; Carter, Jennifer C.

    2012-08-22

    This report describes work conducted at the Pacific Northwest National Laboratory (PNNL) in Fiscal Year (FY) 2012 under the auspices of the Sigma Team for Minor Actinide Separation, funded by the U.S. Department of Energy Office of Nuclear Energy. Researchers at PNNL and Argonne National Laboratory (ANL) are investigating a simplified solvent extraction system for providing a single-step process to separate the minor actinide elements from acidic high-level liquid waste (HLW), including separating the minor actinides from the lanthanide fission products.

  4. Process to remove actinides from soil using magnetic separation

    DOEpatents

    Avens, Larry R.; Hill, Dallas D.; Prenger, F. Coyne; Stewart, Walter F.; Tolt, Thomas L.; Worl, Laura A.

    1996-01-01

    A process of separating actinide-containing components from an admixture including forming a slurry including actinide-containing components within an admixture, said slurry including a dispersion-promoting surfactant, adjusting the pH of the slurry to within a desired range, and, passing said slurry through a pretreated matrix material, said matrix material adapted to generate high magnetic field gradients upon the application of a strong magnetic field exceeding about 0.1 Tesla whereupon a portion of said actinide-containing components are separated from said slurry and remain adhered upon said matrix material is provided.

  5. Theoretical atomic volumes of the light actinides

    SciTech Connect

    Jones, M. D.; Boettger, J. C.; Albers, R. C.; Singh, D. J.

    2000-02-15

    The zero-pressure zero-temperature equilibrium volumes and bulk moduli are calculated for the light actinides Th through Pu using two independent all-electron, full-potential, electronic-structure methods: the full-potential linear augmented-plane-wave method and the linear combinations of Gaussian-type orbitals-fitting function method. The results produced by these two distinctly different electronic-structure techniques are in good agreement with each other, but differ significantly from previously published calculations using the full-potential linear muffin-tin-orbital (FP-LMTO) method. The theoretically calculated equilibrium volumes are in some cases nearly 10% larger than the previous FP-LMTO calculations, bringing them much closer to the experimentally observed volumes. We also discuss the anomalous upturn in equilibrium volume seen experimentally for {alpha}-Pu. (c) 2000 The American Physical Society.

  6. Aqueous processing of actinides at Savannah River

    SciTech Connect

    Gray, J.H.

    1990-01-01

    A number of changes affecting the DP-Complex are having an impact on operations at the Savannah River Site (SRS). In order for SRS to continue as a major contributor within the DP-Complex and remain in position to respond to requests based on new initiatives, programs aimed at redirecting the actinide processing activities have been started. One area undergoing process modifications is F-Canyon, where most of the plutonium feedstocks are processed. Programs already underway that are affecting the dissolution of plutonium materials in canyon dissolvers and the purification of aqueous streams in the second plutonium solvent extraction cycle are discussed. Issues influencing program direction involve environmental concerns, waste minimization, health protection, storage limitations, and material recycle. Each of these issues is discussed in relation to operations in F-Canyon and results based on initial development studies are presented.

  7. Electrochemical decontamination of actinide processing gloveboxes

    SciTech Connect

    Lugo, J.L.; Wedman, D.E.; Nelson, T.O.

    1997-12-31

    Electrochemical technology for the decontamination of metallic surfaces has been successfully demonstrated. Highly enriched uranium and stainless steel surfaces are readily decontaminated to Low Level Waste (LLW) criteria using this process. This process is similar to electropolishing and utilizes the anodic dissolution of the substrate material to generate a clean surface. The surface contaminants are thus removed and collected along with the stripped substrate material as a compact precipitate. This separation allows the electrolyte to be recycled indefinitely. Using an alkaline Sodium Sulfate electrolyte solution, we are able to decontaminate to low levels of alpha activity, gloveboxes previously used in Actinide processing. Surfaces with contamination levels > 1,000,000 cpm alpha activity have been decontaminated to levels as low as 7,000. The process is rapid with decontamination occurring at a rate of over 3 square cm/sec.

  8. Aqueous recovery of actinides from aluminum alloys

    SciTech Connect

    Gray, J.H.; Chostner, D.F.; Gray, L.W.

    1989-01-01

    Early in the 1980's, a joint Rocky Flats/Savannah River program was established to recover actinides from scraps and residues generated during Rocky Flats purification operations. The initial program involved pyrochemical treatment of Molten Salt Extraction (MSE) chloride salts and Electrorefining (ER) anode heel metal to form aluminum alloys suitable for aqueous processing at Savannah River. Recently Rocky Flats has expressed interest in expanding the aluminum alloy program to include treatment of chloride salt residues from a modified Molten Salt Extraction process and from the Electrorefining purification operations. Samples of the current aluminum alloy buttons were prepared at Rocky Flats and sent to Savannah River Laboratory for flowsheet development and characterization of the alloys. A summary of the scrub alloy-anode heel alloy program will be presented along with recent results from aqueous dissolution studies of the new aluminum alloys. 2 figs., 4 tabs.

  9. Study of Formation Mechanisms of Gas Hydrate

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  10. Actinide cross section program at ORELA

    SciTech Connect

    Dabbs, J.W.T.

    1980-01-01

    The actinide cross section program at ORELA, the Oak Ridge Electron Linear Accelerator, is aimed at obtaining accurate neutron cross sections (primarily fission, capture, and total) for actinide nuclides which occur in fission reactors. Such cross sections, measured as a function of neutron energy over as wide a range of energies as feasible, comprise a data base that permits calculated predictions of the formation and removal of these nuclides in reactors. The present program is funded by the Division of Basic Energy Sciences of DOE, and has components in several divisions at ORNL. For intensively ..cap alpha..-active nuclides, many of the existing fission cross section data have been provided by underground explosions. New measurement techniques, developed at ORELA, now permit linac measurements on fissionable nuclides with alpha half-lives as short as 28 years. Capture and capture-plus-fission measurements utilize scintillation detectors (of capture ..gamma.. rays and fission neutrons) in which pulse shape discrimination plays an important role. Total cross sections can be measured at ORELA on samples of only a few milligrams. A simultaneous program of chemical and isotopic analyses of samples irradiated in EBR-II is in progress to provide benchmarks for the existing differential measurements. These analyses are being studied with updated versions of ORIGEN and with sensitivity determinations. Calculations of the sensitivity to cross section changes of various aspects of the nuclear fuel cycle are also being made. Even in this relatively mature field, many cross sections still require improvements to provide an adequate data base. Examples of recent techniques and measurements are presented. 12 figures, 3 tables.

  11. Geomechanical Modeling of Gas Hydrate Bearing Sediments

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  12. Fundamentals and applications of gas hydrates.

    PubMed

    Koh, Carolyn A; Sloan, E Dendy; Sum, Amadeu K; Wu, David T

    2011-01-01

    Fundamental understanding of gas hydrate formation and decomposition processes is critical in many energy and environmental areas and has special importance in flow assurance for the oil and gas industry. These areas represent the core of gas hydrate applications, which, albeit widely studied, are still developing as growing fields of research. Discovering the molecular pathways and chemical and physical concepts underlying gas hydrate formation potentially can lead us beyond flowline blockage prevention strategies toward advancing new technological solutions for fuel storage and transportation, safely producing a new energy resource from natural deposits of gas hydrates in oceanic and arctic sediments, and potentially facilitating effective desalination of seawater. The state of the art in gas hydrate research is leading us to new understanding of formation and dissociation phenomena that focuses on measurement and modeling of time-dependent properties of gas hydrates on the basis of their well-established thermodynamic properties. PMID:22432618

  13. Structural characteristics of hydration sites in lysozyme.

    PubMed

    Soda, Kunitsugu; Shimbo, Yudai; Seki, Yasutaka; Taiji, Makoto

    2011-06-01

    A new method is presented for determining the hydration site of proteins, where the effect of structural fluctuations in both protein and hydration water is explicitly considered by using molecular dynamics simulation (MDS). The whole hydration sites (HS) of lysozyme are composed of 195 single HSs and 38 clustered ones (CHS), and divided into 231 external HSs (EHS) and 2 internal ones (IHS). The largest CHSs, 'Hg' and 'Lβ', are the IHSs having 2.54 and 1.35 mean internal hydration waters respectively. The largest EHS, 'Clft', is located in the cleft region. The real hydration structure of a CHS is an ensemble of multiple structures. The transition between two structures occurs through recombinations of some H-bonds. The number of the experimental X-ray crystal waters is nearly the same as that of the estimated MDS hydration waters for 70% of the HSs, but significantly different for the rest of HSs. PMID:21435773

  14. Development of Alaskan gas hydrate resources

    SciTech Connect

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

    1991-06-01

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

  15. Gas hydrates of outer continental margins

    SciTech Connect

    Kvenvolden, K.A. )

    1990-05-01

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

  16. Actinide targets for the synthesis of super-heavy elements

    SciTech Connect

    Roberto, J.; Alexander, Charles W.; Boll, Rose Ann; Ezold, Julie G.; Felker, Leslie Kevin; Rykaczewski, Krzysztof Piotr; Hogle, Susan L.

    2015-06-18

    Since 2000, six new super-heavy elements with atomic numbers 113 through 118 have been synthesized in hot fusion reactions of 48Ca beams on actinide targets. These target materials, including 242Pu, 244Pu, 243Am, 245Cm, 248Cm, 249Cf, and 249Bk, are available in very limited quantities and require specialized production and processing facilities resident in only a few research centers worldwide. This report describes the production and chemical processing of heavy actinide materials for super-heavy element research, current availabilities of these materials, and related target fabrication techniques. The impact of actinide materials in super-heavy element discovery is reviewed, and strategies for enhancing the production of rare actinides including 249Bk, 251Cf, and 254Es are described.

  17. ACTINIDE-ALUMINATE SPECIATION IN ALKALINE RADIOACTIVE WASTE

    EPA Science Inventory

    Highly alkaline radioactive waste tanks contain a number of transuranic species, in particular U, Np, Pu, and Am - the exact forms of which are currently unknown. Knowledge of actinide speciation under highly alkaline conditions is essential towards understanding and predicting ...

  18. Actinide targets for the synthesis of super-heavy elements

    NASA Astrophysics Data System (ADS)

    Roberto, J. B.; Alexander, C. W.; Boll, R. A.; Burns, J. D.; Ezold, J. G.; Felker, L. K.; Hogle, S. L.; Rykaczewski, K. P.

    2015-12-01

    Since 2000, six new super-heavy elements with atomic numbers 113 through 118 have been synthesized in hot fusion reactions of 48Ca beams on actinide targets. These target materials, including 242Pu, 244Pu, 243Am, 245Cm, 248Cm, 249Cf, and 249Bk, are available in very limited quantities and require specialized production and processing facilities resident in only a few research centers worldwide. This report describes the production and chemical processing of heavy actinide materials for super-heavy element research, current availabilities of these materials, and related target fabrication techniques. The impact of actinide materials in super-heavy element discovery is reviewed, and strategies for enhancing the production of rare actinides including 249Bk, 251Cf, and 254Es are described.

  19. In-situ mineralization of actinides with phytic acid

    SciTech Connect

    Nash, K.L.; Jensen, M.P.; Morss, L.R.; Appelman, E.H.

    1997-12-31

    A new approach to the remediation of actinide contamination is described. A hydrolytically unstable organophosphorus compound, phytic acid, is introduced into the contaminated environment. In the short term (up to several hundred years), phytate acts as a cation exchanger to absorb mobile actinide ions from ground waters. Ultimately, phytate decomposes to release phosphate and promote the formation of insoluble phosphate mineral phases, considered an ideal medium to immobilize actinides, as it forms compounds with the lowest solubility of any candidate mineral species. This overview will discuss the rate of hydrolysis of phytic acid, the formation of lanthanide/actinide phosphate mineral forms, the cation exchange behavior of insoluble phytate, and results from laboratory demonstration of the application to soils from the Fernald site.

  20. Separation of Minor Actinides from Lanthanides by Dithiophosphinic Acid Extractants

    SciTech Connect

    D. R. Peterman; M. R. Greenhalgh; R. D. Tillotson; J. R. Klaehn; M. K. Harrup; T. A. Luther; J. D. Law; L. M. Daniels

    2008-09-01

    The selective extraction of the minor actinides (Am(III) and Cm(III)) from the lanthanides is an important part of advanced reprocessing of spent nuclear fuel. This separation would allow the Am/Cm to be fabricated into targets and recycled to a reactor and the lanthanides to be dispositioned. This separation is difficult to accomplish due to the similarities in the chemical properties of the trivalent actinides and lanthanides. Research efforts at the Idaho National Laboratory have identified an innovative synthetic pathway yielding new regiospecific dithiophosphinic acid (DPAH) extractants. The synthesis provides DPAH derivatives that can address the issues concerning minor actinide separation and extractant stability. For this work, two new symmetric DPAH extractants have been prepared. The use of these extractants for the separation of minor actinides from lanthanides will be discussed.

  1. Actinide targets for the synthesis of super-heavy elements

    DOE PAGESBeta

    Roberto, J.; Alexander, Charles W.; Boll, Rose Ann; Ezold, Julie G.; Felker, Leslie Kevin; Rykaczewski, Krzysztof Piotr; Hogle, Susan L.

    2015-06-18

    Since 2000, six new super-heavy elements with atomic numbers 113 through 118 have been synthesized in hot fusion reactions of 48Ca beams on actinide targets. These target materials, including 242Pu, 244Pu, 243Am, 245Cm, 248Cm, 249Cf, and 249Bk, are available in very limited quantities and require specialized production and processing facilities resident in only a few research centers worldwide. This report describes the production and chemical processing of heavy actinide materials for super-heavy element research, current availabilities of these materials, and related target fabrication techniques. The impact of actinide materials in super-heavy element discovery is reviewed, and strategies for enhancing themore » production of rare actinides including 249Bk, 251Cf, and 254Es are described.« less

  2. Physical Properties of Gas Hydrates: A Review

    DOE PAGESBeta

    Gabitto, Jorge F.; Tsouris, Costas

    2010-01-01

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

  3. Physical Properties of Gas Hydrates: A Review

    SciTech Connect

    Gabitto, Jorge; Tsouris, Costas

    2010-01-01

    Methane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 1016?m3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.

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

    SciTech Connect

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

    2008-01-01

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

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

    ERIC Educational Resources Information Center

    Barlag, Rebecca; Nyasulu, Frazier

    2011-01-01

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

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

    USGS Publications Warehouse

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

    2007-01-01

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

  7. Actinide Source Term Program, position paper. Revision 1

    SciTech Connect

    Novak, C.F.; Papenguth, H.W.; Crafts, C.C.; Dhooge, N.J.

    1994-11-15

    The Actinide Source Term represents the quantity of actinides that could be mobilized within WIPP brines and could migrate with the brines away from the disposal room vicinity. This document presents the various proposed methods for estimating this source term, with a particular focus on defining these methods and evaluating the defensibility of the models for mobile actinide concentrations. The conclusions reached in this document are: the 92 PA {open_quotes}expert panel{close_quotes} model for mobile actinide concentrations is not defensible; and, although it is extremely conservative, the {open_quotes}inventory limits{close_quotes} model is the only existing defensible model for the actinide source term. The model effort in progress, {open_quotes}chemical modeling of mobile actinide concentrations{close_quotes}, supported by a laboratory effort that is also in progress, is designed to provide a reasonable description of the system and be scientifically realistic and supplant the {open_quotes}Inventory limits{close_quotes} model.

  8. Analysis of the Gas Core Actinide Transmutation Reactor (GCATR)

    NASA Technical Reports Server (NTRS)

    Clement, J. D.; Rust, J. H.

    1977-01-01

    Design power plant studies were carried out for two applications of the plasma core reactor: (1) As a breeder reactor, (2) As a reactor able to transmute actinides effectively. In addition to the above applications the reactor produced electrical power with a high efficiency. A reactor subsystem was designed for each of the two applications. For the breeder reactor, neutronics calculations were carried out for a U-233 plasma core with a molten salt breeding blanket. A reactor was designed with a low critical mass (less than a few hundred kilograms U-233) and a breeding ratio of 1.01. The plasma core actinide transmutation reactor was designed to transmute the nuclear waste from conventional LWR's. The spent fuel is reprocessed during which 100% of Np, Am, Cm, and higher actinides are separated from the other components. These actinides are then manufactured as oxides into zirconium clad fuel rods and charged as fuel assemblies in the reflector region of the plasma core actinide transmutation reactor. In the equilibrium cycle, about 7% of the actinides are directly fissioned away, while about 31% are removed by reprocessing.

  9. Comparative studies of actinide and sub-actinide fission cross section calculation from MCNP6 and TALYS

    SciTech Connect

    Perkasa, Y. S.; Waris, A. Kurniadi, R. Su'ud, Z.

    2014-09-30

    Comparative studies of actinide and sub-actinide fission cross section calculation from MCNP6 and TALYS have been conducted. In this work, fission cross section resulted from MCNP6 prediction will be compared with result from TALYS calculation. MCNP6 with its event generator CEM03.03 and LAQGSM03.03 have been validated and verified for several intermediate and heavy nuclides fission reaction data and also has a good agreement with experimental data for fission reaction that induced by photons, pions, and nucleons at energy from several ten of MeV to about 1 TeV. The calculation that induced within TALYS will be focused mainly to several hundred MeV for actinide and sub-actinide nuclides and will be compared with MCNP6 code and several experimental data from other evaluator.

  10. Methane hydrate research at NETL: Research to make methane production from hydrates a reality

    SciTech Connect

    Taylor, C.E.; Link, D.D.; English, N.

    2007-03-01

    Research is underway at NETL to understand the physical properties of methane hydrates. Five key areas of research that need further investigation have been identified. These five areas, i.e. thermal properties of hydrates in sediments, kinetics of natural hydrate dissociation, hysteresis effects, permeability of sediments to gas flow and capillary pressures within sediments, and hydrate distribution at porous scale, are important to the production models that will be used for producing methane from hydrate deposits. NETL is using both laboratory experiments and computational modeling to address these five key areas. The laboratory and computational research reinforce each other by providing feedback. The laboratory results are used in the computational models and the results from the computational modeling is used to help direct future laboratory research. The data generated at NETL will be used to help fulfill The National Methane Hydrate R&D Program of a “long-term supply of natural gas by developing the knowledge and technology base to allow commercial production of methane from domestic hydrate deposits by the year 2015” as outlined on the NETL Website [NETL Website, 2005. http://www.netl.doe.gov/scngo/Natural%20Gas/hydrates/index.html]. Laboratory research is accomplished in one of the numerous high-pressure hydrate cells available ranging in size from 0.15 mL to 15 L in volume. A dedicated high-pressure view cell within the Raman spectrometer allows for monitoring the formation and dissociation of hydrates. Thermal conductivity of hydrates (synthetic and natural) at a certain temperature and pressure is performed in a NETL-designed cell. Computational modeling studies are investigating the kinetics of hydrate formation and dissociation, modeling methane hydrate reservoirs, molecular dynamics simulations of hydrate formation, dissociation, and thermal properties, and Monte Carlo simulations of hydrate formation and dissociation.

  11. First structural characterization of Pa(iv) in aqueous solution and quantum chemical investigations of the tetravalent actinides up to Bk(IV): the evidence of a curium break.

    PubMed

    Banik, Nidhu lal; Vallet, Valérie; Réal, Florent; Belmecheri, Réda Mohamed; Schimmelpfennig, Bernd; Rothe, Jörg; Marsac, Rémi; Lindqvist-Reis, Patric; Walther, Clemens; Denecke, Melissa A; Marquardt, Christian M

    2016-01-14

    More than a century after its discovery the structure of the Pa(4+) ion in acidic aqueous solution has been investigated for the first time experimentally and by quantum chemistry. The combined results of EXAFS data and quantum chemically optimized structures suggest that the Pa(4+) aqua ion has an average of nine water molecules in its first hydration sphere at a mean Pa-O distance of 2.43 Å. The data available for the early tetravalent actinide (An) elements from Th(4+) to Bk(4+) show that the An-O bonds have a pronounced electrostatic character, with bond distances following the same monotonic decreasing trend as the An(4+) ionic radii, with a decrease of the hydration number from nine to eight for the heaviest ions Cm(4+) and Bk(4+). Being the first open-shell tetravalent actinide, Pa(4+) features a coordination chemistry very similar to its successors. The electronic configuration of all open-shell systems corresponds to occupation of the valence 5f orbitals, without contribution from the 6d orbitals. Our results thus demonstrate that Pa(iv) resembles its early actinide neighbors. PMID:26465740

  12. A Heterogeneous Sodium Fast Reactor Designed to Transmute Minor Actinide Actinide Waste Isotopes into Plutonium Fuel

    SciTech Connect

    Samuel E. Bays

    2011-02-01

    An axial heterogeneous sodium fast reactor design is developed for converting minor actinide waste isotopes into plutonium fuel. The reactor design incorporates zirconium hydride moderating rods in an axial blanket above the active core. The blanket design traps the active core’s axial leakage for the purpose of transmuting Am-241 into Pu-238. This Pu-238 is then co-recycled with the spent driver fuel to make new driver fuel. Because Pu-238 is significantly more fissile than Am-241 in a fast neutron spectrum, the fissile worth of the initial minor actinide material is upgraded by its preconditioning via transmutation in the axial targets. Because, the Am-241 neutron capture worth is significantly stronger in a moderated epithermal spectrum than the fast spectrum, the axial targets serve as a neutron trap which recovers the axial leakage lost by the active core. The sodium fast reactor proposed by this work is designed as an overall transuranic burner. Therefore, a low transuranic conversion ratio is achieved by a degree of core flattening which increases axial leakage. Unlike a traditional “pancake” design, neutron leakage is recovered by the axial target/blanket system. This heterogeneous core design is constrained to have sodium void and Doppler reactivity worth similar to that of an equivalent homogeneous design. Because minor actinides are irradiated only once in the axial target region; elemental partitioning is not required. This fact enables the use of metal targets with electrochemical reprocessing. Therefore, the irradiation environment of both drivers and targets was constrained to ensure applicability of the established experience database for metal alloy sodium fast reactor fuels.

  13. Vibrational lifetimes of hydrated phospholipids

    NASA Astrophysics Data System (ADS)

    Jadidi, Tayebeh; Anvari, Mehrnaz; Mashaghi, Alireza; Sahimi, Muhammad; Rahimi Tabar, M. Reza

    2013-04-01

    Large-scale ab initio molecular-dynamics simulations have been carried out to compute, at human-body temperature, the vibrational modes and lifetimes of pure and hydrated dipalmitoylphosphatidylcholine (DPPC) lipids. The projected atomic vibrations calculated from the spectral energy density are used to compute the vibrational modes and the lifetimes. All the normal modes of the pure and hydrated DPPC and their frequencies are identified. The computed lifetimes incorporate the full anharmonicity of the atomic interactions. The vibrational modes of the water molecules close to the head group of DPPC are active (possess large projected spectrum amplitudes) in the frequency range 0.5-55 THz, with a peak at 2.80 THz in the energy spectrum. The computed lifetimes for the high-frequency modes agree well with the recent data measured at room temperature where high-order phonon scattering is not negligible. The computed lifetimes of the low-frequency modes can be tested using the current experimental capabilities. Moreover, the approach may be applied to other lipids and biomolecules, in order to predict their vibrational dispersion relations, and to study the dynamics of vibrational energy transfer.

  14. Gas hydrates in the ocean environment

    USGS Publications Warehouse

    Dillon, William P.

    2002-01-01

    A GAS HYDRATE, also known as a gas clathrate, is a gas-bearing, icelike material. It occurs in abundance in marine sediments and stores immense amounts of methane, with major implications for future energy resources and global climate change. Furthermore, gas hydrate controls some of the physical properties of sedimentary deposits and thereby influences seafloor stability.

  15. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Donn McGuire; Steve Runyon; Richard Sigal; Bill Liddell; Thomas Williams; George Moridis

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. Hot Ice No. 1 was planned to test the Ugnu and West Sak sequences for gas hydrates and a concomitant free gas accumulation on Anadarko's 100% working interest acreage in section 30 of Township 9N, Range 8E of the Harrison Bay quadrangle of the North Slope of Alaska. The Ugnu and West Sak intervals are favorably positioned in the hydrate-stability zone over an area extending from Anadarko's acreage westward to the vicinity of the aforementioned gas-hydrate occurrences. This suggests that a large, north-to-south trending gas-hydrate accumulation may exist in that area. The presence of gas shows in the Ugnu and West Sak reservoirs in wells situated eastward and down dip of the Hot Ice location indicate that a free-gas accumulation may be trapped by gas hydrates. The Hot Ice No. 1 well was designed to core from the surface to the base of the West Sak interval using the revolutionary and new

  16. Natural Gas Hydrates: Occurrence, Distribution, and Detection

    NASA Astrophysics Data System (ADS)

    Paull, Charles K.; Dillon, William P.

    We publish this volume at a time when there is a growing interest in gas hydrates and major expansion in international research efforts. The first recognition of natural gas hydrate on land in Arctic conditions was in the mid-1960s (by I. Makogon) and in the seabed environment only in the early 1970s, after natural seafloor gas hydrate was drilled on the Blake Ridge during Deep Sea Drilling Project Leg 11. Initial scientific investigations were slow to develop because the study of natural gas hydrates is unusually challenging. Gas hydrate exists in nature in conditions of temperature and pressure where human beings cannot survive, and if gas hydrate is transported from its region of stability to normal Earth-surface conditions, it dissociates. Thus, in contrast to most minerals, we cannot depend on drilled samples to provide accurate estimates of the amount of gas hydrate present. Even the heat and changes in chemistry (methane saturation, salinity, etc.) introduced by the drilling process affect the gas hydrate, independent of the changes brought about by moving a sample to the surface. Gas hydrate has been identified in nature generally by inference from indirect evidence in drilling data or by using remotely sensed indications, mostly from seismic data. Obviously, the established techniques ofgeologic analysis, which require direct observation and sampling, do not apply to gas hydrate studies, and controversy has surrounded many interpretations. Pressure/temperature conditions appropriate for the existence of gas hydrate occur over the greater part of the shallow subsurface of the Earth beneath the ocean at water depths exceeding about 500 m (shallower beneath colder Arctic seas) and on land beneath high-latitude permafrost. Gas hydrate actually will be present in such conditions, however, only where methane is present at high concentrations. In the Arctic, these methane concentrations are often associated with petroleum deposits, whereas at continental margins

  17. Hydration forces at solid and fluid biointerfaces.

    PubMed

    Shrestha, Buddha Ratna; Banquy, Xavier

    2016-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

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

  19. Microbial transformations of actinides in the environment

    NASA Astrophysics Data System (ADS)

    Livens, F. R.; Al-Bokari, M.; Fomina, M.; Gadd, G. M.; Geissler, A.; Lloyd, J. R.; Renshaw, J. C.; Vaughan, D. J.

    2010-03-01

    The diversity of microorganisms is still far from understood, although many examples of the microbial biotransformation of stable, pollutant and radioactive elements, involving Bacteria, Archaea and Fungi, are known. In estuarine sediments from the Irish Sea basin, which have been labelled by low level effluent discharges, there is evidence of an annual cycle in Pu solubility, and microcosm experiments have demonstrated both shifts in the bacterial community and changes in Pu solubility as a result of changes in redox conditions. In the laboratory, redox transformation of both U and Pu by Geobacter sulfurreducens has been demonstrated and EXAFS spectroscopy has been used to understand the inability of G. sufurreducens to reduce Np(V). Fungi promote corrosion of metallic U alloy through production of a range of carboxylic acid metabolites, and are capable of translocating the dissolved U before precipitating it externally to the hyphae, as U(VI) phosphate phases. These examples illustrate the far-reaching but complex effects which microorganisms can have on actinide behaviour.

  20. Synthesis of crystalline ceramics for actinide immobilisation

    SciTech Connect

    Burakov, B.; Gribova, V.; Kitsay, A.; Ojovan, M.; Hyatt, N.C.; Stennett, M.C.

    2007-07-01

    Methods for the synthesis of ceramic wasteforms for the immobilization of actinides are common to those for non-radioactive ceramics: hot uniaxial pressing (HUP); hot isostatic pressing (HIP); cold pressing followed by sintering; melting (for some specific ceramics, such as garnet/perovskite composites). Synthesis of ceramics doped with radionuclides is characterized with some important considerations: all the radionuclides should be incorporated into crystalline structure of durable host-phases in the form of solid solutions and no separate phases of radionuclides should be present in the matrix of final ceramic wasteform; all procedures of starting precursor preparation and ceramic synthesis should follow safety requirements of nuclear industry. Synthesis methods that avoid the use of very high temperatures and pressures and are easily accomplished within the environment of a glove-box or hot cell are preferable. Knowledge transfer between the V. G. Khlopin Radium Institute (KRI, Russia) and Immobilisation Science Laboratory (ISL, UK) was facilitated in the framework of a joint project supported by UK Royal Society. In order to introduce methods of precursor preparation and ceramic synthesis we selected well-known procedures readily deployable in radiochemical processing plants. We accounted that training should include main types of ceramic wasteforms which are currently discussed for industrial applications. (authors)

  1. Actinides AMS at CIRCE in Caserta (Italy)

    NASA Astrophysics Data System (ADS)

    De Cesare, M.; Gialanella, L.; Rogalla, D.; Petraglia, A.; Guan, Y.; De Cesare, N.; D'Onofrio, A.; Quinto, F.; Roca, V.; Sabbarese, C.; Terrasi, F.

    2010-04-01

    The operation of Nuclear Power Plants and atmospheric tests of nuclear weapons performed in the past, together with production, transport and reprocessing of nuclear fuel, lead to the release into the environment of a wide range of radioactive nuclides, such as uranium, plutonium, fission and activation products. These nuclides are present in the environment at ultra trace levels. Their detection requires sensitive techniques like AMS (Accelerator Mass Spectrometry). In order to perform isotopic ratio measurements of the longer-lived actinides, e.g., of 236U relative to the primary 238U and various Pu isotopes relative to 239Pu, an upgrade of the CIRCE accelerator (Center for Isotopic Research on Cultural and Environmental Heritage) in Caserta, Italy, is underway. In this paper we report on the results of simulations aiming to define the best ion optics and to understand the origin of possible measurement background. The design of a high resolution TOF- E (Time of Flight-Energy) detector system is described, which will be used to identify the rare isotopes among interfering background signals.

  2. Electrochemical decontamination system for actinide processing gloveboxes

    SciTech Connect

    Wedman, D.E.; Lugo, J.L.; Ford, D.K.; Nelson, T.O.; Trujillo, V.L.; Martinez, H.E.

    1998-03-01

    An electrolytic decontamination technology has been developed and successfully demonstrated at Los Alamos National Laboratory (LANL) for the decontamination of actinide processing gloveboxes. The technique decontaminates the interior surfaces of stainless steel gloveboxes utilizing a process similar to electropolishing. The decontamination device is compact and transportable allowing it to be placed entirely within the glovebox line. In this way, decontamination does not require the operator to wear any additional personal protective equipment and there is no need for additional air handling or containment systems. Decontamination prior to glovebox decommissioning reduces the potential for worker exposure and environmental releases during the decommissioning, transport, and size reduction procedures which follow. The goal of this effort is to reduce contamination levels of alpha emitting nuclides for a resultant reduction in waste level category from High Level Transuranic (TRU) to low Specific Activity (LSA, less than or equal 100 nCi/g). This reduction in category results in a 95% reduction in disposal and disposition costs for the decontaminated gloveboxes. The resulting contamination levels following decontamination by this method are generally five orders of magnitude below the LSA specification. Additionally, the sodium sulfate based electrolyte utilized in the process is fully recyclable which results in the minimum of secondary waste. The process bas been implemented on seven gloveboxes within LANL`s Plutonium Facility at Technical Area 55. Of these gloveboxes, two have been discarded as low level waste items and the remaining five have been reused.

  3. Correlation and relativistic effects in actinide ions

    SciTech Connect

    Safronova, U. I.; Safronova, M. S.

    2011-11-15

    Wavelengths, line strengths, and transition rates are calculated for the multipole (E1, M1, E2, M2, E3, and M3) transitions between the excited 6s{sup 2}6p{sup 5}nl and 6s6p{sup 6}nl states and the ground 6s{sup 2}6p{sup 6} state in Ac{sup 3+}, Th{sup 4+}, and U{sup 6+} Rn-like ions. Relativistic many-body perturbation theory (RMBPT), including the Breit interaction, is used to evaluate energies and transition rates for multipole transitions in these hole-particle systems. The RMBPT method agrees with multiconfigurational Dirac-Fock (MCDF) calculations in lowest order, includes all second-order correlation corrections, and includes corrections from negative-energy states. The calculations start from a [Xe]4f{sup 14}5d{sup 10}6s{sup 2}6p{sup 6} Dirac-Fock potential. First-order perturbation theory is used to obtain intermediate-coupling coefficients, and second-order RMBPT is used to determine the matrix elements. Evaluated multipole matrix elements for transitions from excited states to the ground states are used to determine the line strengths, transition rates, and multipole polarizabilities. This work provides a number of yet unmeasured properties of these actinide ions for various applications and for benchmark tests of theory and experiment.

  4. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-07-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope drilled and cored a well The HOT ICE No.1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report.

  5. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Bill Liddell

    2005-03-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Oil-field engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in Arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored the HOT ICE No. 1 on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was designed, constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. Unfortunately, no gas hydrates were encountered in this well; however, a wealth of information was generated and is

  6. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-06-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the final stages of a cost shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope drilled and cored a well The HOT ICE No.1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report.

  7. Overview on Hydrate Coring, Handling and Analysis

    SciTech Connect

    Jon Burger; Deepak Gupta; Patrick Jacobs; John Shillinglaw

    2003-06-30

    Gas hydrates are crystalline, ice-like compounds of gas and water molecules that are formed under certain thermodynamic conditions. Hydrate deposits occur naturally within ocean sediments just below the sea floor at temperatures and pressures existing below about 500 meters water depth. Gas hydrate is also stable in conjunction with the permafrost in the Arctic. Most marine gas hydrate is formed of microbially generated gas. It binds huge amounts of methane into the sediments. Worldwide, gas hydrate is estimated to hold about 1016 kg of organic carbon in the form of methane (Kvenvolden et al., 1993). Gas hydrate is one of the fossil fuel resources that is yet untapped, but may play a major role in meeting the energy challenge of this century. In June 2002, Westport Technology Center was requested by the Department of Energy (DOE) to prepare a ''Best Practices Manual on Gas Hydrate Coring, Handling and Analysis'' under Award No. DE-FC26-02NT41327. The scope of the task was specifically targeted for coring sediments with hydrates in Alaska, the Gulf of Mexico (GOM) and from the present Ocean Drilling Program (ODP) drillship. The specific subjects under this scope were defined in 3 stages as follows: Stage 1: Collect information on coring sediments with hydrates, core handling, core preservation, sample transportation, analysis of the core, and long term preservation. Stage 2: Provide copies of the first draft to a list of experts and stakeholders designated by DOE. Stage 3: Produce a second draft of the manual with benefit of input from external review for delivery. The manual provides an overview of existing information available in the published literature and reports on coring, analysis, preservation and transport of gas hydrates for laboratory analysis as of June 2003. The manual was delivered as draft version 3 to the DOE Project Manager for distribution in July 2003. This Final Report is provided for records purposes.

  8. Identification of hexanuclear Actinide(IV) carboxylates with Thorium, Uranium and Neptunium by EXAFS spectroscopy

    NASA Astrophysics Data System (ADS)

    Hennig, Christoph; Takao, Shinobu; Takao, Koichiro; Weiss, Stephan; Kraus, Werner; Emmerling, Franziska; Meyer, Michel; Scheinost, Andreas C.

    2013-04-01

    Hydrated actinide(IV) ions undergo hydrolysis and further polymerization and precipitation with increasing pH. The resulting amorphous and partly crystalline oxydydroxides AnOn(OH)4-2n·xH2O can usually be observed as colloids above the An(IV) solubility limit. The aging process of such colloids results in crystalline AnO2. The presence of carboxylates in the solution prevents the occurrence of such colloids by formation of polynuclear complexes through a competing reaction between hydrolysis and ligation. The majority of recently described carboxylates reveals a hexanuclear core of [An6(μ3-O)4(μ3-OH)4]12+ terminated by 12 carboxylate ligands. We found that the An(IV) carboxylate solution species remain often preserved in crystalline state. The An(IV) carboxylates show An-An distances which are ~ 0.03 Å shorter than the An-An distances in AnO2 like colloids. The difference in the distances could be used to identify such species in solution.

  9. Experimental Work Conducted on MgO Inundated Hydration in WIPP-Relevant Brines

    NASA Astrophysics Data System (ADS)

    Deng, H.; Xiong, Y.; Nemer, M. B.; Johnsen, S.

    2009-12-01

    Magnesium oxide (MgO) is being emplaced in the Waste Isolation Pilot Plant (WIPP) as an engineered barrier to mitigate the effect of microbial CO2 generation on actinide mobility in a postclosure repository environment. MgO will sequester CO2 and consume water in brine or water vapor in the gaseous phase. Martin Marietta (MM) MgO is currently being emplaced in the WIPP. A fractional-factorial experiment has been performed to study the inundated-hydration of MM MgO as a function of its particle size, solid-to-liquid ratio, and brine type. MgO hydration experiments have been carried out with three MgO particle sizes and two solid-to-liquid ratios in three WIPP-related brines: ERDA-6, GWB and simplified GWB. ERDA-6 is a synthetic NaCl-rich brine typical of a Castile brine reservoir below the repository. GWB is a synthetic MgCl2- and NaCl-rich brine representative of intergranular brines from the Salado Formation at or near the stratigraphic horizon of the repository. Simplified GWB contains amounts of Mg, Na, and Cl similar to those in GWB without other minor constituents. The hydration products include brucite (Mg(OH)2) and phase 5 (Mg3(OH)5Cl4H2O). In addition to phase 5, MgO hydration in GWB or simplified GWB produces brucite, whereas MgO hydrated in ERDA-6 only produces brucite. The MgO particle size has had a significant effect on the formation of hydration products: small MgO particles have hydrated before the large particles. MgO has hydrated faster in simplified GWB than in the other two brines. In ERDA-6, the solid-to-liquid ratio has affected the brine pH due to the presence of CaO (~1 wt %) as an impurity in MM MgO. GWB has sufficient dissolved Mg to buffer pH despite small amounts of CaO. Both our results and thermodynamic modeling indicate that phase-5 is the stable Mg-OH-Cl phase in Mg-Na-Cl-dominated brines with ionic strengths and chemical compositions similar to that of GWB. In contrast, phase-3 (Mg2(OH)3Cl4H2O) is the stable phase in the MgCl2

  10. Methane Recovery from Hydrate-bearing Sediments

    SciTech Connect

    J. Carlos Santamarina; Costas Tsouris

    2011-04-30

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

  11. Clathrate hydrate tuning for technological purposes

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

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

  12. Gas Hydrate Storage of Natural Gas

    SciTech Connect

    Rudy Rogers; John Etheridge

    2006-03-31

    Environmental and economic benefits could accrue from a safe, above-ground, natural-gas storage process allowing electric power plants to utilize natural gas for peak load demands; numerous other applications of a gas storage process exist. A laboratory study conducted in 1999 to determine the feasibility of a gas-hydrates storage process looked promising. The subsequent scale-up of the process was designed to preserve important features of the laboratory apparatus: (1) symmetry of hydrate accumulation, (2) favorable surface area to volume ratio, (3) heat exchanger surfaces serving as hydrate adsorption surfaces, (4) refrigeration system to remove heat liberated from bulk hydrate formation, (5) rapid hydrate formation in a non-stirred system, (6) hydrate self-packing, and (7) heat-exchanger/adsorption plates serving dual purposes to add or extract energy for hydrate formation or decomposition. The hydrate formation/storage/decomposition Proof-of-Concept (POC) pressure vessel and supporting equipment were designed, constructed, and tested. This final report details the design of the scaled POC gas-hydrate storage process, some comments on its fabrication and installation, checkout of the equipment, procedures for conducting the experimental tests, and the test results. The design, construction, and installation of the equipment were on budget target, as was the tests that were subsequently conducted. The budget proposed was met. The primary goal of storing 5000-scf of natural gas in the gas hydrates was exceeded in the final test, as 5289-scf of gas storage was achieved in 54.33 hours. After this 54.33-hour period, as pressure in the formation vessel declined, additional gas went into the hydrates until equilibrium pressure/temperature was reached, so that ultimately more than the 5289-scf storage was achieved. The time required to store the 5000-scf (48.1 hours of operating time) was longer than designed. The lower gas hydrate formation rate is attributed to a

  13. Rapid determination of alpha emitters using Actinide resin.

    PubMed

    Navarro, N; Rodriguez, L; Alvarez, A; Sancho, C

    2004-01-01

    The European Commission has recently published the recommended radiological protection criteria for the clearance of building and building rubble from the dismantling of nuclear installations. Radionuclide specific clearance levels for actinides are very low (between 0.1 and 1 Bq g(-1)). The prevalence of natural radionuclides in rubble materials makes the verification of these levels by direct alpha counting impossible. The capability of Actinide resin (Eichrom Industries, Inc.) for extracting plutonium and americium from rubble samples has been tested in this work. Besides a strong affinity for actinides in the tri, tetra and hexavalent oxidation states, this extraction chromatographic resin presents an easy recovery of absorbed radionuclides. The retention capability was evaluated on rubble samples spiked with certified radionuclide standards (239Pu and 241Am). Samples were leached with nitric acid, passed through a chromatographic column containing the resin and the elution fraction was measured by LSC. Actinide retention varies from 60% to 80%. Based on these results, a rapid method for the verification of clearance levels for actinides in rubble samples is proposed. PMID:15177360

  14. Crystal growth methods dedicated to low solubility actinide oxalates

    NASA Astrophysics Data System (ADS)

    Tamain, C.; Arab-Chapelet, B.; Rivenet, M.; Grandjean, S.; Abraham, F.

    2016-04-01

    Two novel crystal growth syntheses dedicated to low solubility actinide-oxalate systems and adapted to glove box handling are described. These methods based on the use of precursors of either actinide metal or oxalic acid have been optimized on lanthanide systems (analogue of actinides(III)) and then assessed on real actinide systems. They allow the synthesis of several actinide oxalate single crystals, Am2(C2O4)3(H2O)3·xH2O, Th(C2O4)2·6H2O, M2+x[PuIV2-xPuIIIx(C2O4)5]·nH2O and M1-x[PuIII1-xPuIVx(C2O4)2·H2O]·nH2O. It is the first time that these well-known compounds are formed by crystal growth methods, thus enabling direct structural studies on transuranic element systems and acquisition of basic data beyond deductions from isomorphic (or not) lanthanide compounds. Characterizations by X-ray diffraction, UV-visible solid spectroscopy, demonstrate the potentialities of these two crystal growth methods to obtain oxalate compounds.

  15. Siderocalin-mediated recognition, sensitization, and cellular uptake of actinides.

    PubMed

    Allred, Benjamin E; Rupert, Peter B; Gauny, Stacey S; An, Dahlia D; Ralston, Corie Y; Sturzbecher-Hoehne, Manuel; Strong, Roland K; Abergel, Rebecca J

    2015-08-18

    Synthetic radionuclides, such as the transuranic actinides plutonium, americium, and curium, present severe health threats as contaminants, and understanding the scope of the biochemical interactions involved in actinide transport is instrumental in managing human contamination. Here we show that siderocalin, a mammalian siderophore-binding protein from the lipocalin family, specifically binds lanthanide and actinide complexes through molecular recognition of the ligands chelating the metal ions. Using crystallography, we structurally characterized the resulting siderocalin-transuranic actinide complexes, providing unprecedented insights into the biological coordination of heavy radioelements. In controlled in vitro assays, we found that intracellular plutonium uptake can occur through siderocalin-mediated endocytosis. We also demonstrated that siderocalin can act as a synergistic antenna to sensitize the luminescence of trivalent lanthanide and actinide ions in ternary protein-ligand complexes, dramatically increasing the brightness and efficiency of intramolecular energy transfer processes that give rise to metal luminescence. Our results identify siderocalin as a potential player in the biological trafficking of f elements, but through a secondary ligand-based metal sequestration mechanism. Beyond elucidating contamination pathways, this work is a starting point for the design of two-stage biomimetic platforms for photoluminescence, separation, and transport applications. PMID:26240330

  16. Laboratory studies of actinide metal-silicate fractionation

    NASA Technical Reports Server (NTRS)

    Jones, J. H.; Burnett, D. S.

    1980-01-01

    Actinide and Sm partition coefficients between silicate melt and several metallic phases have been measured. Under reducing conditions Si, Th, U and Pu can be reduced to metals from silicate melts and alloyed with a platinum-gold alloy. U and Pu enter a molten Pt-Si alloy with roughly equal affinity but U strongly partitions into the solid Pt. Th behaves qualitatively the same as Pu but is much less readily reduced than U, and Sm appears to remain unreduced. Experiments with Fe metal have shown that the partition coefficients of the actinides between Fe and silicate liquid are extremely low, suggesting a very low actinide concentration in planetary cores. Experiments show that platinum metals can efficiently fractionate actinides and fractionate actinides from lanthanides and this process may be relevant to the condensation behavior of these elements from the solar nebula. Pt-metal grains in Allende Ca-Al-rich inclusions appear to be U-poor, although the sub-class of Zr-bearing Pt metals may have high U contents.

  17. Gas core reactors for actinide transmutation and breeder applications

    NASA Technical Reports Server (NTRS)

    Clement, J. D.; Rust, J. H.

    1978-01-01

    This work consists of design power plant studies for four types of reactor systems: uranium plasma core breeder, uranium plasma core actinide transmuter, UF6 breeder and UF6 actinide transmuter. The plasma core systems can be coupled to MHD generators to obtain high efficiency electrical power generation. A 1074 MWt UF6 breeder reactor was designed with a breeding ratio of 1.002 to guard against diversion of fuel. Using molten salt technology and a superheated steam cycle, an efficiency of 39.2% was obtained for the plant and the U233 inventory in the core and heat exchangers was limited to 105 Kg. It was found that the UF6 reactor can produce high fluxes (10 to the 14th power n/sq cm-sec) necessary for efficient burnup of actinide. However, the buildup of fissile isotopes posed severe heat transfer problems. Therefore, the flux in the actinide region must be decreased with time. Consequently, only beginning-of-life conditions were considered for the power plant design. A 577 MWt UF6 actinide transmutation reactor power plant was designed to operate with 39.3% efficiency and 102 Kg of U233 in the core and heat exchanger for beginning-of-life conditions.

  18. Siderocalin-mediated recognition, sensitization, and cellular uptake of actinides

    PubMed Central

    Allred, Benjamin E.; Rupert, Peter B.; Gauny, Stacey S.; An, Dahlia D.; Ralston, Corie Y.; Sturzbecher-Hoehne, Manuel; Strong, Roland K.; Abergel, Rebecca J.

    2015-01-01

    Synthetic radionuclides, such as the transuranic actinides plutonium, americium, and curium, present severe health threats as contaminants, and understanding the scope of the biochemical interactions involved in actinide transport is instrumental in managing human contamination. Here we show that siderocalin, a mammalian siderophore-binding protein from the lipocalin family, specifically binds lanthanide and actinide complexes through molecular recognition of the ligands chelating the metal ions. Using crystallography, we structurally characterized the resulting siderocalin–transuranic actinide complexes, providing unprecedented insights into the biological coordination of heavy radioelements. In controlled in vitro assays, we found that intracellular plutonium uptake can occur through siderocalin-mediated endocytosis. We also demonstrated that siderocalin can act as a synergistic antenna to sensitize the luminescence of trivalent lanthanide and actinide ions in ternary protein–ligand complexes, dramatically increasing the brightness and efficiency of intramolecular energy transfer processes that give rise to metal luminescence. Our results identify siderocalin as a potential player in the biological trafficking of f elements, but through a secondary ligand-based metal sequestration mechanism. Beyond elucidating contamination pathways, this work is a starting point for the design of two-stage biomimetic platforms for photoluminescence, separation, and transport applications. PMID:26240330

  19. Diffusion of CO2 During Hydrate Formation and Dissolution

    SciTech Connect

    Franklin M. Orr, Jr.

    2002-08-20

    Experiments were performed to measure the rate of diffusion of CO2 through hydrate films. Hydrate films were created in a capillary tube, and the growth of the hydrate film was measured. Difficulties were encountered in creating hydrate repeatedly, and some non-uniform growth of the films was observed. Sufficient observations were obtained to demonstrate that hydrate growth occurs preferentially on the hydrate/water side of the interface, rather than at the hydrate/CO2 interface. Diffusion coefficients were estimated from observations of the rate of growth of the hydrate film along with estimates of the solubility of CO2 in water and of the concentration gradient across the hydrate layer. The experimental observations indicate that hydrate formation occurs much more rapidly at the hydrate water interface than at the hydrate/CO2 interface. Any growth of hydrate at the CO2/hydrate interface was too slow to be observed at the time scale of the experiments. That observation is consistent with the idea that CO2 can move more easily through the hydrate, presumably by hopping between hydrate cages, than water can move through the hydrate, presumably by lattice hopping. Estimated diffusion coefficients were in the range 1-3E-06 cm2/sec. Those values are about an order of magnitude lower than the diffusion coefficient for CO2 in liquid water, but four orders of magnitude larger than the value for diffusion of CO2 in a solid. The rate of diffusion through the hydrate controls both the creation of new hydrate at the hydrate/water interface and the rate at which CO2 dissolves in the liquid water and diffuses away from the hydrate layer. Formation of a hydrate layer reduces the rate at which CO2 dissolves in liquid water.

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

    USGS Publications Warehouse

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

    2013-01-01

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

  1. Detection and Production of Methane Hydrate

    SciTech Connect

    George Hirasaki; Walter Chapman; Gerald Dickens; Colin Zelt; Brandon Dugan; Kishore Mohanty; Priyank Jaiswal

    2011-12-31

    This project seeks to understand regional differences in gas hydrate systems from the perspective of as an energy resource, geohazard, and long-term climate influence. Specifically, the effort will: (1) collect data and conceptual models that targets causes of gas hydrate variance, (2) construct numerical models that explain and predict regional-scale gas hydrate differences in 2-dimensions with minimal 'free parameters', (3) simulate hydrocarbon production from various gas hydrate systems to establish promising resource characteristics, (4) perturb different gas hydrate systems to assess potential impacts of hot fluids on seafloor stability and well stability, and (5) develop geophysical approaches that enable remote quantification of gas hydrate heterogeneities so that they can be characterized with minimal costly drilling. Our integrated program takes advantage of the fact that we have a close working team comprised of experts in distinct disciplines. The expected outcomes of this project are improved exploration and production technology for production of natural gas from methane hydrates and improved safety through understanding of seafloor and well bore stability in the presence of hydrates. The scope of this project was to more fully characterize, understand, and appreciate fundamental differences in the amount and distribution of gas hydrate and how this would affect the production potential of a hydrate accumulation in the marine environment. The effort combines existing information from locations in the ocean that are dominated by low permeability sediments with small amounts of high permeability sediments, one permafrost location where extensive hydrates exist in reservoir quality rocks and other locations deemed by mutual agreement of DOE and Rice to be appropriate. The initial ocean locations were Blake Ridge, Hydrate Ridge, Peru Margin and GOM. The permafrost location was Mallik. Although the ultimate goal of the project was to understand processes

  2. Surface topography dependence of biomolecular hydrophobic hydration

    NASA Astrophysics Data System (ADS)

    Cheng, Yuen-Kit; Rossky, Peter J.

    1998-04-01

    Many biomolecules are characterized by surfaces containing extended nonpolar regions, and the aggregation and subsequent removal of such surfaces from water is believed to play a critical role in the biomolecular assembly in cells. A better understanding of the hydrophobic hydration of biomolecules may therefore yield new insights into intracellular assembly. Conventional views hold that the hydration shell of small hydrophobic solutes is clathrate-like, characterized by local cage-like hydrogen-bonding structures and a distinct loss in entropy. The hydration of extended nonpolar planar surfaces, however, appears to involve structures that are orientationally inverted relative to clathrate-like hydration shells,, with unsatisfied hydrogen bonds that are directed towards the hydrophobic surface. Here we present computer simulations of the interaction between the polypeptide melittin and water that demonstrate that the two different hydration structures also exist near a biomolecular surface. We find that the two structures are distinguished by a substantial difference in the water-water interaction enthalpy, and that their relative contributions depend strongly on the surface topography of the melittin molecule: clathrate-like structures dominate near convex surface patches, whereas the hydration shell near flat surfaces fluctuates between clathrate-like and less-ordered or inverted structures. The strong influence of surface topography on the structure and free energy of hydrophobic hydration is likely to hold in general, and will be particularly important for the many biomolecules whose surfaces contain convex patches, deep or shallow concave grooves and roughly planar areas.

  3. Gas Hydrates Research Programs: An International Review

    SciTech Connect

    Jorge Gabitto; Maria Barrufet

    2009-12-09

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

  4. Electrical properties of methane hydrate + sediment mixtures

    USGS Publications Warehouse

    Du Frane, Wyatt L.; Stern, Laura A.; Weitemeyer, Karen A.; Constable, Steven; Roberts, Jeffery J.

    2011-01-01

    As part of our DOE-funded proposal to characterize gas hydrate in the Gulf of Mexico using marine electromagnetic methods, a collaboration between SIO, LLNL, and USGS with the goal of measuring the electrical properties of lab-created methane (CH4) hydrate and sediment mixtures was formed. We examined samples with known characteristics to better relate electrical properties measured in the field to specific gas hydrate concentration and distribution patterns. Here we discuss first-ever electrical conductivity (σ) measurements on unmixed CH4 hydrate (Du Frane et al., 2011): 6 x 10-5 S/m at 5 °C, which is ~5 orders of magnitude lower than seawater. This difference allows electromagnetic (EM) techniques to distinguish highly resistive gas hydrate deposits from conductive water saturated sediments in EM field surveys. More recently, we performed measurements on CH4 hydrate mixed with sediment and we also discuss those initial findings here. Our results on samples free of liquid water are important for predicting conductivity of sediments with pores highly saturated with gas hydrate, and are an essential starting point for comprehensive mixing models.

  5. Ab Initio Studies of Calcium Carbonate Hydration.

    PubMed

    Lopez-Berganza, Josue A; Diao, Yijue; Pamidighantam, Sudhakar; Espinosa-Marzal, Rosa M

    2015-11-25

    Ab initio simulations of large hydrated calcium carbonate clusters are challenging due to the existence of multiple local energy minima. Extensive conformational searches around hydrated calcium carbonate clusters (CaCO3·nH2O for n = 1-18) were performed to find low-energy hydration structures using an efficient combination of Monte Carlo searches, density-functional tight binding (DFTB+) method, and density-functional theory (DFT) at the B3LYP level, or Møller-Plesset perturbation theory at the MP2 level. This multilevel optimization yields several low-energy structures for hydrated calcium carbonate. Structural and energetics analysis of the hydration of these clusters revealed a first hydration shell composed of 12 water molecules. Bond-length and charge densities were also determined for different cluster sizes. The solvation of calcium carbonate in bulk water was investigated by placing the explicitly solvated CaCO3·nH2O clusters in a polarizable continuum model (PCM). The findings of this study provide new insights into the energetics and structure of hydrated calcium carbonate and contribute to the understanding of mechanisms where calcium carbonate formation or dissolution is of relevance. PMID:26505205

  6. Mechanisms for thermal conduction in hydrogen hydrate

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

    Extensive equilibrium molecular dynamics simulations have been performed to investigate thermal conduction mechanisms via the Green-Kubo approach for (type II) hydrogen hydrate, at 0.05 kbar and between 30 and 250 K, for both lightly filled H2 hydrates (1s4l) and for more densely filled H2 systems (2s4l), in which four H2 molecules are present in the large cavities, with respective single- and double-occupation of the small cages. The TIP4P water model was used in conjunction with a fully atomistic hydrogen potential along with long-range Ewald electrostatics. It was found that substantially less damping in guest-host energy transfer is present in hydrogen hydrate as is observed in common type I clathrates (e.g., methane hydrate), but more akin in to previous results for type II and H methane hydrate polymorphs. This gives rise to larger thermal conductivities relative to common type I hydrates, and also larger than type II and H methane hydrate polymorphs, and a more crystal-like temperature dependence of the thermal conductivity.

  7. Prospecting for marine gas hydrate resources

    USGS Publications Warehouse

    Boswell, Ray; Shipp, Craig; Reichel, Thomas; Shelander, Dianna; Saeki, Tetsuo; Frye, Matthew; Shedd, William; Collett, Timothy S.; McConnell, Daniel R.

    2016-01-01

    As gas hydrate energy assessment matures worldwide, emphasis has evolved away from confirmation of the mere presence of gas hydrate to the more complex issue of prospecting for those specific accumulations that are viable resource targets. Gas hydrate exploration now integrates the unique pressure and temperature preconditions for gas hydrate occurrence with those concepts and practices that are the basis for conventional oil and gas exploration. We have aimed to assimilate the lessons learned to date in global gas hydrate exploration to outline a generalized prospecting approach as follows: (1) use existing well and geophysical data to delineate the gas hydrate stability zone (GHSZ), (2) identify and evaluate potential direct indications of hydrate occurrence through evaluation of interval of elevated acoustic velocity and/or seismic events of prospective amplitude and polarity, (3) mitigate geologic risk via regional seismic and stratigraphic facies analysis as well as seismic mapping of amplitude distribution along prospective horizons, and (4) mitigate further prospect risk through assessment of the evidence of gas presence and migration into the GHSZ. Although a wide range of occurrence types might ultimately become viable energy supply options, this approach, which has been tested in only a small number of locations worldwide, has directed prospect evaluation toward those sand-hosted, high-saturation occurrences that were presently considered to have the greatest future commercial potential.

  8. Prompt Fission Neutron Spectra of Actinides

    SciTech Connect

    Capote, R; Chen, Y J; Hambsch, F J; Kornilov, N V; Lestone, J P; Litaize, O; Morillon, B; Neudecker, D; Oberstedt, S; Ohsawa, T; Smith, D. L.

    2016-01-01

    The energy spectrum of prompt neutrons emitted in fission (PFNS) plays a very important role in nuclear science and technology. A Coordinated Research Project (CRP) “Evaluation of Prompt Fission Neutron Spectra of Actinides”was established by the IAEA Nuclear Data Section in 2009, with the major goal to produce new PFNS evaluations with uncertainties for actinide nuclei. The following technical areas were addressed: (i) experiments and uncertainty quantification (UQ): New data for neutron-induced fission of 233U, 235U, 238U, and 239Pu have been measured, and older data have been compiled and reassessed. There is evidence from the experimental work of this CRP that a very small percentage of neutrons emitted in fission are actually scission neutrons; (ii) modeling: The Los Alamos model (LAM) continues to be the workhorse for PFNS evaluations. Monte Carlo models have been developed that describe the fission phenomena microscopically, but further development is needed to produce PFNS evaluations meeting the uncertainty targets; (iii) evaluation methodologies: PFNS evaluations rely on the use of the least-squares techniques for merging experimental and model data. Considerable insight was achieved on how to deal with the problem of too small uncertainties in PFNS evaluations. The importance of considering that all experimental PFNS data are “shape” data was stressed; (iv) PFNS evaluations: New evaluations, including covariance data, were generated for major actinides including 1) non-model GMA evaluations of the 235U(nth,f), 239Pu(nth,f), and 233U(nth,f) PFNS based exclusively on experimental data (0.02 ≤ E ≤ 10 MeV), which resulted in PFNS average energies E of 2.00±0.01, 2.073±0.010, and 2.030±0.013 MeV, respectively; 2) LAM evaluations of neutron-induced fission spectra on uranium and plutonium targets with improved UQ for incident energies from thermal up to 30 MeV; and 3) Point-by-Point calculations for 232Th, 234U and 237Np targets; and (v) data

  9. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2003-12-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the US have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the second year of a three-year endeavor being sponsored by maurer Technology, noble, and Anadarko Petroleum, in partnership with the DOE. The purpose of the project is to build on previous and ongoing R and D in the area of onshore hydrate deposition. They plan to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. They also plan to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope is to drill and core a well on Anadarko leases in FY 2003 and 2004. They are also using an on-site core analysis laboratory to determine some of the physical characteristics of the hydrates and surrounding rock. The well is being drilled from a new Anadarko Arctic Platform that will have minimal footprint and environmental impact. They hope to correlate geology, geophysics, logs, and drilling and production data to allow reservoir models to be calibrated. Ultimately, the goal is to form an objective technical and economic evaluation of reservoir potential in Alaska.

  10. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Buddy King

    2004-03-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is in the second year of a three-year endeavor being sponsored by Maurer Technology, Noble, and Anadarko Petroleum, in partnership with the DOE. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition. We plan to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. We also plan to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope is to drill and core a well on Anadarko leases in FY 2003 and 2004. We are also using an on-site core analysis laboratory to determine some of the physical characteristics of the hydrates and surrounding rock. The well is being drilled from a new Anadarko Arctic Platform that will have minimal footprint and environmental impact. We hope to correlate geology, geophysics, logs, and drilling and production data to allow reservoir models to be calibrated. Ultimately, our goal is to form an objective technical and economic evaluation of reservoir potential in Alaska.

  11. Electrical properties of methane hydrate + sediment mixtures

    NASA Astrophysics Data System (ADS)

    Du Frane, Wyatt L.; Stern, Laura A.; Constable, Steven; Weitemeyer, Karen A.; Smith, Megan M.; Roberts, Jeffery J.

    2015-07-01

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

  12. Modeling actinide chemistry with ASPEN PLUS

    SciTech Connect

    Grigsby, C.O.

    1995-12-31

    When chemical engineers think of chemical processing, they often do not include the US government or the national laboratories as significant participants. Compared to the scale of chemical processing in the chemical process, petrochemical and pharmaceutical industries, the government contribution to chemical processing is not large. However, for the past fifty years, the US government has been, heavily involved in chemical processing of some very specialized materials, in particular, uranium and plutonium for nuclear weapons. Individuals and corporations have paid taxes that, in part have been used to construct and to maintain a series of very expensive laboratories and production facilities throughout the country. Even ignoring the ongoing R & D costs, the price per pound of enriched uranium or of plutonium exceeds that of platinum by a wide margin. Now, with the end of the cold war, the government is decommissioning large numbers of nuclear weapons and cleaning up the legacy of radioactive wastes generated over the last fifty years. It is likely that the costs associated with the build-down and clean-up of the nuclear weapons complex will exceed the investment of the past fifty years of production. Los Alamos National Laboratory occupies a special place in the history of nuclear weapons. The first weapons were designed and assembled at Los Alamos using uranium produced in Oak Ridge, Tennessee or plutonium produced in Richland, Washington. Many of the thermophysical and metallurgical properties of actinide elements have been investigated at Los Alamos. The only plutonium processing facility currently operating in the US is in Los Alamos, and the Laboratory is striving to capture and maintain the uranium processing technology applicable to the post-cold war era. Laboratory researchers are actively involved in developing methods for cleaning up the wastes associated with production of nuclear weapons throughout the US.

  13. Actinide consumption: Nuclear resource conservation without breeding

    SciTech Connect

    Hannum, W.H.; Battles, J.E.; Johnson, T.R.; McPheeters, C.C.

    1991-01-01

    A new approach to the nuclear power issue based on a metallic fast reactor fuel and pyrometallurgical processing of spent fuel is showing great potential and is approaching a critical demonstration phase. If successful, this approach will complement and validate the LWR reactor systems and the attendant infrastructure (including repository development) and will alleviate the dominant concerns over the acceptability of nuclear power. The Integral Fast Reactor (IFR) concept is a metal-fueled, sodium-cooled pool-type fast reactor supported by a pyrometallurgical reprocessing system. The concept of a sodium cooled fast reactor is broadly demonstrated by the EBR-II and FFTF in the US; DFR and PFR in the UK; Phenix and SuperPhenix in France; BOR-60, BN-350, BN-600 in the USSR; and JOYO in Japan. The metallic fuel is an evolution from early EBR-II fuels. This fuel, a ternary U-Pu-Zr alloy, has been demonstrated to be highly reliable and fault tolerant even at very high burnup (160-180,000 MWd/MT). The fuel, coupled with the pool type reactor configuration, has been shown to have outstanding safety characteristics: even with all active safety systems disabled, such a reactor can survive a loss of coolant flow, a loss of heat sink, or other major accidents. Design studies based on a small modular approach show not only its impressive safety characteristics, but are projected to be economically competitive. The program to explore the feasibility of actinide recovery from spent LWR fuel is in its initial phase, but it is expected that technical feasibility could be demonstrated by about 1995; DOE has not yet committed funds to achieve this objective. 27 refs.

  14. In pursuit of homoleptic actinide alkyl complexes.

    PubMed

    Seaman, Lani A; Walensky, Justin R; Wu, Guang; Hayton, Trevor W

    2013-04-01

    This Forum Article describes the pursuit of isolable homoleptic actinide alkyl complexes, starting with the pioneering work of Gilman during the Manhattan project. The initial reports in this area suggested that homoleptic uranium alkyls were too unstable to be isolated, but Wilkinson demonstrated that tractable uranium alkyls could be generated by purposeful "ate" complex formation, which serves to saturate the uranium coordination sphere and provide the complexes with greater kinetic stability. More recently, we reported the solid-state molecular structures of several homoleptic uranium alkyl complexes, including [Li(THF)4][U(CH2(t)Bu)5], [Li(TMEDA)]2[UMe6], [K(THF)]3[K(THF)2][U(CH2Ph)6]2, and [Li(THF)4][U(CH2SiMe3)6], by employing Wilkinson's strategy. Herein, we describe our attempts to extend this chemistry to thorium. The treatment of ThCl4(DME)2 with 5 equiv of LiCH2(t)Bu or LiCH2SiMe3 at -25 °C in THF affords [Th(CH2(t)Bu)5] (1) and [Li(DME)2][Th(CH2SiMe3)5 (2), respectively, in moderate yields. Similarly, the treatment of ThCl4(DME)2 with 6 equiv of K(CH2Ph) produces [K(THF)]2[Th(CH2Ph)6] (3), in good yield. Complexes 1-3 have been fully characterized, while the structures of 1 and 3 were confirmed by X-ray crystallography. Additionally, the electronic properties of 1 and 3 were explored by density functional theory. PMID:22716022

  15. Clathrate hydrates in cometary nuclei and porosity

    NASA Technical Reports Server (NTRS)

    Smoluchowski, R.

    1988-01-01

    Possible mechanisms of formation and decomposition of CO2-clathrate hydrate in cometary nuclei are discussed. As far as it is known, this is the only clathrate hydrate which is unstable at low temperatures. Calculation shows that, in accord with other evidence, neither volume nor grain boundary diffusion in the clathrate lattice can be responsible for the rate of these reactions and that a surface mechanism with the attendant sensitivity to pressure must play a crucial role. Density changes accompanying CO2-clathrate decomposition and formation can lead to microporosity and enhanced brittleness or even to fracture of cometary nuclei at low temperatures. Other clathrate hydrates and mixed clathrates are also discussed.

  16. Carbon dioxide hydrate and floods on Mars

    NASA Technical Reports Server (NTRS)

    Milton, D. J.

    1974-01-01

    Ground ice on Mars probably consists largely of carbon dioxide hydrate. This hydrate dissociates upon release of pressure at temperatures between 0 and 10 C. The heat capacity of the ground would be sufficient to produce up to 4% (by volume) of water at a rate equal to that at which it can be drained away. Catastrophic dissociation of carbon dioxide hydrate during some past epoch when the near-surface temperature was in this range would have produced chaotic terrain and flood channels.

  17. Dissociation of Natural and Artificial Methane Hydrate

    NASA Astrophysics Data System (ADS)

    Misyura, S. Y.

    2016-02-01

    Present work deals with natural and artificial methane hydrate dissociation. The heating of the powder produced due to the temperature difference between the external air and the powder. The dissociation rate was determined by gravimetric method. The range of the partial self-preservation for the natural hydrate is significantly longer than for the artificial one and moved to higher temperatures. The destruction of the natural sample is slower than the artificial one. The time-averaged dissociation rate for the artificial sample is equal to 1,25 %/s and for the natural hydrate corresponds to 0,59 %/s.

  18. Advancing the scientific basis of trivalent actinide-lanthanide separations

    SciTech Connect

    Nash, K.L.

    2013-07-01

    For advanced fuel cycles designed to support transmutation of transplutonium actinides, several options have been demonstrated for process-scale aqueous separations for U, Np, Pu management and for partitioning of trivalent actinides and fission product lanthanides away from other fission products. The more difficult mutual separation of Am/Cm from La-Tb remains the subject of considerable fundamental and applied research. The chemical separations literature teaches that the most productive alternatives to pursue are those based on ligand donor atoms less electronegative than O, specifically N- and S-containing complexants and chloride ion (Cl{sup -}). These 'soft-donor' atoms have exhibited usable selectivity in their bonding interactions with trivalent actinides relative to lanthanides. In this report, selected features of soft donor reagent design, characterization and application development will be discussed. The roles of thiocyanate, aminopoly-carboxylic acids and lactate in separation processes are detailed. (authors)

  19. Actinide chemistry in Allende Ca-Al-rich inclusions

    NASA Astrophysics Data System (ADS)

    Murrell, M. T.; Burnett, D. S.

    1987-04-01

    Fission track radiography is used to investigate the U and Th microscale distribution in a set of Allende-meteorite Ca-Al-rich inclusions. In the Type B inclusions, the major phases melilite and fassaite are important actinide host phases, and on the rims of Type B inclusions and throughout all other inclusions studied, perovskite is the dominant actinide host phase. Results suggest that neither alteration nor loss or gain of an actinide-rich phase appears to have been an important Th/U fractionation mechanism, and that volatility differences may be the dominant factor. Th/U and rare earth element abundance patterns for the spinel and perovskite rim suggest rim formation by volatilization of interior material, and within the constraints of the brief time scale required for this heating, several mechanisms for spinel-perovskite rim formation are possible.

  20. Systematic view of optical absorption spectra in the actinide series

    SciTech Connect

    Carnall, W.T.

    1985-01-01

    In recent years sufficient new spectra of actinides in their numerous valence states have been measured to encourage a broader scale analysis effort than was attempted in the past. Theoretical modelling in terms of effective operators has also undergone development. Well established electronic structure parameters for the trivalent actinides are being used as a basis for estimating parameters in other valence states and relationships to atomic spectra are being extended. Recent contributions to our understanding of the spectra of 4+ actinides have been particularly revealing and supportive of a developing general effort to progress beyond a preoccupation with modelling structure to consideration of the much broader area of structure-bonding relationships. We summarize here both the developments in modelling electronic structure and the interpretation of apparent trends in bonding. 60 refs., 9 figs., 1 tab.

  1. Assessment of the Thermochemical Properties of Actinides in Molten Chlorides

    NASA Astrophysics Data System (ADS)

    Masset, Patrick I.; Apostolidis, Christos; Malmbeck, Rikard; Rebizant, Jean; Serp, Jérôme; Glatz, Jean-Paul

    2008-02-01

    The electrochemical properties of the chlorides of the actinides U, Pu, Np and Am (AnCl3) were investigated by transient electrochemical techniques in the LiCl-KCl eutectic at 400 - 550 °C. The diffusion coefficients of the cations and the apparent standard potentials of the redox systems on an inert W electrode were measured. The Gibbs energy of dilute solutions of AnCl3 as well as the activity coefficients were derived from electrochemical measurements. In addition, the electrochemical behaviour of the actinides on an Al electrode was investigated. They formed AnAl4 alloys, the formation potentials of which allowed a quantitative recovery of the actinides and their separation from fission products and especially from lanthanides. In addition, the thermochemical properties of the AnAl4 alloys were determined by electrochemical measurements.

  2. Advances in actinide solid-state and coordination chemistry

    SciTech Connect

    Burns, Peter C; Ikeda, Y.; Czerwinski, K.

    2011-01-31

    Actinide solid-state and coordination chemistry has advanced through unexpected results that have further revealed the complex nature of the 5f elements. Nanoscale control of actinide materials is emerging, as shown by the creation of a considerable range of cluster and tubular topologies. Departures from established structural trends for actinyl ions are provided by cation-cation interactions in which an O atom of one actinyl ion is an equatorial ligand of a bipyramid of another actinyl ion. The solid-state structural complexity of actinide materials has been further demonstrated by open framework materials with interesting properties. The U(VI) tetraoxide core has been added to this cation's repertoire of coordination possibilities. The emergence of pentavalent uranium solid-state and coordination chemistry has resulted from the prudent selection of ligands. Finally, analogues of the uranyl ion have challenged our understanding of this normally unreactive functional group.

  3. Actinide chemistry in Allende Ca-Al-rich inclusions

    NASA Technical Reports Server (NTRS)

    Murrell, M. T.; Burnett, D. S.

    1987-01-01

    Fission track radiography is used to investigate the U and Th microscale distribution in a set of Allende-meteorite Ca-Al-rich inclusions. In the Type B inclusions, the major phases melilite and fassaite are important actinide host phases, and on the rims of Type B inclusions and throughout all other inclusions studied, perovskite is the dominant actinide host phase. Results suggest that neither alteration nor loss or gain of an actinide-rich phase appears to have been an important Th/U fractionation mechanism, and that volatility differences may be the dominant factor. Th/U and rare earth element abundance patterns for the spinel and perovskite rim suggest rim formation by volatilization of interior material, and within the constraints of the brief time scale required for this heating, several mechanisms for spinel-perovskite rim formation are possible.

  4. Actinide (III) solubility in WIPP Brine: data summary and recommendations

    SciTech Connect

    Borkowski, Marian; Lucchini, Jean-Francois; Richmann, Michael K.; Reed, Donald T.

    2009-09-01

    The solubility of actinides in the +3 oxidation state is an important input into the Waste Isolation Pilot Plant (WIPP) performance assessment (PA) models that calculate potential actinide release from the WIPP repository. In this context, the solubility of neodymium(III) was determined as a function of pH, carbonate concentration, and WIPP brine composition. Additionally, we conducted a literature review on the solubility of +3 actinides under WIPP-related conditions. Neodymium(III) was used as a redox-invariant analog for the +3 oxidation state of americium and plutonium, which is the oxidation state that accounts for over 90% of the potential release from the WIPP through the dissolved brine release (DBR) mechanism, based on current WIPP performance assessment assumptions. These solubility data extend past studies to brine compositions that are more WIPP-relevant and cover a broader range of experimental conditions than past studies.

  5. FY2010 Annual Report for the Actinide Isomer Detection Project

    SciTech Connect

    Warren, Glen A.; Francy, Christopher J.; Ressler, Jennifer J.; Erikson, Luke E.; Miller, Erin A.; Hatarik, R.

    2011-01-01

    This project seeks to identify a new signature for actinide element detection in active interrogation. This technique works by exciting and identifying long-lived nuclear excited states (isomers) in the actinide isotopes and/or primary fission products. Observation of isomers in the fission products will provide a signature for fissile material. For the actinide isomers, the decay time and energy of the isomeric state is unique to a particular isotope, providing an unambiguous signature for Special Nuclear Materials (SNM). Future work will include a follow-up measurement scheduled for December 2010 at LBNL. Lessons learned from the July 2010 measurements will be incorporated into these new measurements. Analysis of both the July and December experiments will be completed in a few months. A research paper to be submitted to a peer-reviewed journal will be drafted if the conclusions from the measurements warrant publication.

  6. Removal of actinides from nuclear fuel reprocessing wastes using an organophosphorous extractant. [DHDECMP

    SciTech Connect

    Chamberlain, D.B.; Maxey, H.R.; McIsaac, L.D.; McManus, G.J.

    1980-01-01

    By removing actinides from nuclear fuel reprocessing wastes, long term waste storage hazards are reduced. A solvent extraction process to remove actinides has been demonstrated in miniature mixer-settlers and in simulated columns using actinide feeds. Nonradioactive pilot plant results have established the feasibility of using pulse columns for the process.

  7. Glass powder blended cement hydration modelling

    NASA Astrophysics Data System (ADS)

    Saeed, Huda

    The use of waste materials in construction is among the most attractive options to consume these materials without affecting the environment. Glass is among these types of potential waste materials. In this research, waste glass in powder form, i.e. glass powder (GP) is examined for potential use in enhancing the characteristics of concrete on the basis that it is a pozzolanic material. The experimental and the theoretical components of the work are carried out primarily to prove that glass powder belongs to the "family" of the pozzolanic materials. The chemical and physical properties of the hydrated activated glass powder and the hydrated glass powder cement on the microstructure level have been studied experimentally and theoretically. The work presented in this thesis consists of two main phases. The first phase contains experimental investigations of the reaction of glass powder with calcium hydroxide (CH) and water. In addition, it includes experiments that are aimed at determining the consumption of water and CH with time. The reactivity, degree of hydration, and nature of the pore solution of the glass powder-blended cement pastes and the effect of adding different ratios of glass powder on cement hydration is also investigated. The experiments proved that glass powder has a pozzolanic effect on cement hydration; hence it enhances the chemical and physical properties of cement paste. Based on the experimental test results, it is recommended to use a glass powder-to-cement ratio (GP/C) of 10% as an optimum ratio to achieve the best hydration and best properties of the paste. Two different chemical formulas for the produced GP C-S-H gel due to the pure GP and GP-CH pozzolanic reaction hydration are proposed. For the pure GP hydration, the produced GP C-S-H gel has a calcium-to-silica ratio (C/S) of 0.164, water-to-silica ratio (H/S) of 1.3 and sodium/silica ratio (N/S) of 0.18. However, for the GP-CH hydration, the produced GP C-S-H gel has a C/S ratio of 1

  8. Crystal structure of tris­(trans-1,2-di­amino­cyclo­hexane-κ2 N,N′)cobalt(III) trichloride monohydrate

    PubMed Central

    Gallagher, Megan K.; Oliver, Allen G.; Lappin, A. Graham

    2016-01-01

    The synthesis of the title hydrated complex salt, [Co(C6H14N2)3]Cl3·H2O, from racemic trans-1,2-di­amino­cyclo­hexane and [CoCl(NH3)5]Cl2 and its structural characterization are presented in this paper. The product was synthesized in the inter­est of understanding the hydrogen-bonding patterns of coordination complexes. Previous characterizations of the product in the I-42d space group have not yielded coordinates; thus, this paper provides the first coordinates for this complex in this space group. The octahedrally coordinated cation adopts twofold rotation symmetry, with outer-sphere chloride counter-ions and solvent water mol­ecules forming a hydrogen-bonded network with amine H atoms. PMID:26870583

  9. Crystal structure of tris-(trans-1,2-di-amino-cyclo-hexane-κ(2) N,N')cobalt(III) trichloride monohydrate.

    PubMed

    Gallagher, Megan K; Oliver, Allen G; Lappin, A Graham

    2016-01-01

    The synthesis of the title hydrated complex salt, [Co(C6H14N2)3]Cl3·H2O, from racemic trans-1,2-di-amino-cyclo-hexane and [CoCl(NH3)5]Cl2 and its structural characterization are presented in this paper. The product was synthesized in the inter-est of understanding the hydrogen-bonding patterns of coordination complexes. Previous characterizations of the product in the I-42d space group have not yielded coordinates; thus, this paper provides the first coordinates for this complex in this space group. The octahedrally coordinated cation adopts twofold rotation symmetry, with outer-sphere chloride counter-ions and solvent water mol-ecules forming a hydrogen-bonded network with amine H atoms. PMID:26870583

  10. Grouped actinide separation in advanced nuclear fuel cycles

    SciTech Connect

    Glatz, J.P.; Malmbeck, R.; Ougier, M.; Soucek, P.; Murakamin, T.; Tsukada, T.; Koyama, T.

    2013-07-01

    Aiming at cleaner waste streams (containing only the short-lived fission products) a partitioning and transmutation (P-T) scheme can significantly reduce the quantities of long-lived radionuclides consigned to waste. Many issues and options are being discussed and studied at present in view of selecting the optimal route. The choice is between individual treatment of the relevant elements and a grouped treatment of all actinides together. In the European Collaborative Project ACSEPT (Actinide recycling by Separation and Transmutation), grouped separation options derived from an aqueous extraction or from a dry pyroprocessing route were extensively investigated. Successful demonstration tests for both systems have been carried out in the frame of this project. The aqueous process called GANEX (Grouped Actinide Extraction) is composed of 2 cycles, a first one to recover the major part of U followed by a co-extraction of Np, Pu, Am, and Cm altogether. The pyro-reprocessing primarily applicable to metallic fuels such as the U-Pu-Zr alloy originally developed by the Argonne National Laboratory (US) in the mid 1980s, has also been applied to the METAPHIX fuels containing up to 5% of minor actinides and 5% of lanthanides (e.g. U{sub 60}Pu{sub 20}-Zr{sub 10}Am{sub 2}Nd{sub 3.5}Y{sub 0.5}Ce{sub 0.5}Gd{sub 0.5}). A grouped actinide separation has been successfully carried out by electrorefining on solid Al cathodes. At present the recovery of the actinides from the alloy formed with Al upon electrodeposition is under investigation, because an efficient P-T cycle requires multiple re-fabrication and re-irradiation. (authors)

  11. Selection of actinide chemical analogues for WIPP tests

    SciTech Connect

    Villarreal, R.; Spall, D.

    1995-07-05

    The Department of Energy must demonstrate the effectiveness of the Waste Isolation Pilot Plant (WIPP) as a permanent repository for the disposal of transuranic (TRU) waste. Performance assessments of the WIPP require that estimates of the transportability and outcome of the radionuclides (actinides) be determined from disposal rooms that may become either partially or completely filled with brine. Federal regulations limit the amount of radioactivity that may be unintentionally released to the accessible environment by any mechanism during the post closure phase up to 10,000 years. Thermodynamic models have been developed to predict the concentrations of actinides in the WIPP disposal rooms under various situations and chemical conditions. These models are based on empirical and theoretical projections of the chemistry that might be present in and around the disposal room zone for both near and long-term periods. The actinides that are known to be present in the TRU wastes (and are included in the model) are Th, U, Np, Pu, and Am. Knowledge of the chemistry that might occur in the disposal rooms when the waste comes in contact with brine is important in understanding the range of oxidation states that might be present under different conditions. There is a need to establish the mechanisms and resultant rate of transport, migration, or effective retardation of actinides beyond the disposal rooms to the boundary of the accessible environment. The influence of the bulk salt rock, clay sediments and other geologic matrices on the transport behavior of actinides must be determined to establish the overall performance and capability of the WIPP in isolating waste from the environment. Tests to determine the capabilities of the WIPP geologic formations in retarding actinide species in several projected oxidation states would provide a means to demonstrate the effectiveness of the WIPP in retaining TRU wastes.

  12. Measurement of Actinides in Molybdenum-99 Solution Analytical Procedure

    SciTech Connect

    Soderquist, Chuck Z.; Weaver, Jamie L.

    2015-11-01

    This document is a companion report to a previous report, PNNL 24519, Measurement of Actinides in Molybdenum-99 Solution, A Brief Review of the Literature, August 2015. In this companion report, we report a fast, accurate, newly developed analytical method for measurement of trace alpha-emitting actinide elements in commercial high-activity molybdenum-99 solution. Molybdenum-99 is widely used to produce 99mTc for medical imaging. Because it is used as a radiopharmaceutical, its purity must be proven to be extremely high, particularly for the alpha emitting actinides. The sample of 99Mo solution is measured into a vessel (such as a polyethylene centrifuge tube) and acidified with dilute nitric acid. A gadolinium carrier is added (50 µg). Tracers and spikes are added as necessary. Then the solution is made strongly basic with ammonium hydroxide, which causes the gadolinium carrier to precipitate as hydrous Gd(OH)3. The precipitate of Gd(OH)3 carries all of the actinide elements. The suspension of gadolinium hydroxide is then passed through a membrane filter to make a counting mount suitable for direct alpha spectrometry. The high-activity 99Mo and 99mTc pass through the membrane filter and are separated from the alpha emitters. The gadolinium hydroxide, carrying any trace actinide elements that might be present in the sample, forms a thin, uniform cake on the surface of the membrane filter. The filter cake is first washed with dilute ammonium hydroxide to push the last traces of molybdate through, then with water. The filter is then mounted on a stainless steel counting disk. Finally, the alpha emitting actinide elements are measured by alpha spectrometry.

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

    USGS Publications Warehouse

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

    2004-01-01

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

  14. MINING INTEGRAL ACTINIDES CROSS SECTIONS FROM REACTOR DATA

    SciTech Connect

    PUIGH RJ

    2009-09-11

    The conclusions of this paper are: (1) mining of actinide cross-sections from reactor data is a viable and inexpensive approach to confirm burn-up codes; (2) extensive data for actinides in Hanford test data ({approx} 200 radiochemical analyses); (3) not only cross-section values and reaction rates can be established but also possible benchmark like data can be constructed to test and validate reactor and criticality safety codes such as SCALE/KENO or MCNPX; and (4) analysis along multiple transmutation paths can be evaluated to show consistency.

  15. New cubic structure compounds as actinide host phases

    NASA Astrophysics Data System (ADS)

    Stefanovsky, S. V.; Yudintsev, S. V.; Livshits, T. S.

    2010-03-01

    Various compounds with fluorite (cubic zirconia) and fluorite-derived (pyrochlore, zirconolite) structures are considered as promising actinide host phases at immobilization of actinide-bearing nuclear wastes. Recently some new cubic compounds — stannate and stannate-zirconate pyrochlores, murataite and related phases, and actinide-bearing garnet structure compounds were proposed as perspective matrices for complex actinide wastes. Zirconate pyrochlore (ideally Gd2Zr2O7) has excellent radiation resistance and high chemical durability but requires high temperatures (at least 1500 °C) to be produced by hot-pressing from sol-gel derived precursor. Partial Sn4+ substitution for Zr4+ reduces production temperature and the compounds REE2ZrSnO7 may be hot-pressed or cold pressed and sintered at ~1400 °C. Pyrochlore, A2B2O7-x (two-fold elementary fluorite unit cell), and murataite, A3B6C2O20-y (three-fold fluorite unit cell), are end-members of the polysomatic series consisting of the phases whose structures are built from alternating pyrochlore and murataite blocks (nano-sized modules) with seven- (2C/3C/2C), five- (2C/3C), eight- (3C/2C/3C) and three-fold (3C — murataite) fluorite unit cells. Actinide content in this series reduces in the row: 2C (pyrochlore) > 7C > 5C > 8C > 3C (murataite). Due to congruent melting murataite-based ceramics may be produced by melting and the firstly segregated phase at melt crystallization is that with the highest fraction of the pyrochlore modules in its structure. The melts containing up to 10 wt. % AnO2 (An = Th, U, Np, Pu) or REE/An fraction of HLW form at crystallization zoned grains composed sequentially of the 5C → 8C → 3C phases with the highest actinide concentration in the core and the lowest — in the rim of the grains. Radiation resistance of the "murataite" is comparable to titanate pyrochlores. One more promising actinide hosts are ferrites with garnet structure. The matrices containing sometime complex fluorite

  16. SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES

    DOEpatents

    Hildebrandt, R.A.; Hyman, H.H.; Vogler, S.

    1962-08-14

    A process of countercurrently extracting an aqueous mineral acid feed solution for the separation of actinides from lanthanides dissolved therern is described. The feed solution is made acid-defrcient with alkali metal hydroxide prior to.contact with acid extractant; during extraction, however, acid is transferred from organic to aqueous solution and the aqueous solution gradually becomes acid. The acid-deficient phase ' of the process promotes the extraction of the actinides, while the latter acid phase'' of the process improves retention of the lanthanides in the aqueous solution. This provides for an improved separation. (AEC)

  17. Thermally unstable complexants/phosphate mineralization of actinides

    SciTech Connect

    Nash, K.

    1996-10-01

    In situ immobilization is an approach to isolation of radionuclides from the hydrosphere that is receiving increasing attention. Rather than removing the actinides from contaminated soils, this approach transforms the actinides into intrinsically insoluble mineral phases resistant to leaching by groundwater. The principal advangates of this concept are the low cost and low risk of operator exposure and/or dispersion of the radionuclides to the wider environment. The challenge of this approach is toe accomplish the immobilization without causing collateral damage to the environment (the cure shouldn`t be worse than the disease) and verification of system performance.

  18. Method for extracting lanthanides and actinides from acid solutions

    DOEpatents

    Horwitz, E. Philip; Kalina, Dale G.; Kaplan, Louis; Mason, George W.

    1985-01-01

    A process for the recovery of actinide and lanthanide values from aqueous acidic solutions with an organic extractant having the formula: ##STR1## where .phi. is phenyl, R.sup.1 is a straight or branched alkyl or alkoxyalkyl containing from 6 to 12 carbon atoms and R.sup.2 is an alkyl containing from 3 to 6 carbon atoms. The process is suitable for the separation of actinide and lanthanide values from fission product values found together in high level nuclear reprocessing waste solutions.

  19. Physics studies of higher actinide consumption in an LMR

    SciTech Connect

    Hill, R.N.; Wade, D.C.; Fujita, E.K.; Khalil, H.S.

    1990-01-01

    The core physics aspects of the transuranic burning potential of the Integral Fast Reactor (IFR) are assessed. The actinide behavior in fissile self-sufficient IFR closed cycles of 1200 MWt size is characterized, and the transuranic isotopics and risk potential of the working inventory are compared to those from a once-through LWR. The core neutronic performance effects of rare-earth impurities present in the recycled fuel are addressed. Fuel cycle strategies for burning transuranics from an external source are discussed, and specialized actinide burner designs are described. 4 refs., 4 figs., 3 tabs.

  20. Production of heavy actinides in incomplete fusion reactions

    NASA Astrophysics Data System (ADS)

    Antonenko, N. V.; Cherepanov, E. A.; Iljinov, A. S.; Mebel, M. V.

    1994-10-01

    We present preliminary results of calculations by the phenomenological model of the estimated yield of some heavy actinide isotopes. It is assumed that these isotopes are produced as a result of multinucleon transfers followed by neutrons and charged particle emission A.S. Iljinov and E.A. Cherepanov (1980). The yield P(sub Z, N)(E*) of primary excited actinides is found using the model of N.V. Antonenko and R.V. Jolos (1991). Absolute cross-sections for different binary reaction channels are obtained by summing the cross-sections for all subchannels with an appreciable yield according to J. Wilczynski et al. (1980).

  1. Analogue Study of Actinide Transport at Sites in Russia

    SciTech Connect

    Novikov, A P; Simmons, A M; Halsey, W G

    2003-02-12

    The U. S. Department of Energy (DOE) and the Russian Academy of Sciences (RAS) are engaged in a three-year cooperative study to observe the behavior of actinides in the natural environment at selected disposal sites and/or contamination sites in Russia. The purpose is to develop experimental data and models for actinide speciation, mobilization and transport processes in support of geologic repository design, safety and performance analyses. Currently at the mid-point of the study, the accomplishments to date include: evaluation of existing data and data needs, site screening and selection, initial data acquisition, and development of preliminary conceptual models.

  2. Observation of Large Scissors Resonance Strength in Actinides

    NASA Astrophysics Data System (ADS)

    Guttormsen, M.; Bernstein, L. A.; Bürger, A.; Görgen, A.; Gunsing, F.; Hagen, T. W.; Larsen, A. C.; Renstrøm, T.; Siem, S.; Wiedeking, M.; Wilson, J. N.

    2012-10-01

    The orbital M1 scissors resonance has been measured for the first time in the quasicontinuum of actinides. Particle-γ coincidences are recorded with deuteron and He3-induced reactions on Th232. The residual nuclei Th231,232,233 and 232,233Pa show an unexpectedly strong integrated strength of BM1=11-15μn2 in the Eγ=1.0-3.5MeV region. The increased γ-decay probability in actinides due to scissors resonance is important for cross-section calculations for future fuel cycles of fast nuclear reactors and may also have an impact on stellar nucleosynthesis.

  3. Novel complexing agents for the efficient separation of actinides and remediation of actinide-contaminated sites

    SciTech Connect

    Baisden, P.; Kadkhodayan, B.

    1996-03-15

    Research into the coordination chemistry of transactinide elements should provide us with new fundamental knowledge about structure, geometry, and stability of these metal complexes. Our approach involves the design, synthesis, and characterization of {open_quotes}expanded porphyrin{close_quotes} macrocyclic ligands which coordinate the actinide metal cations with high thermodynamic affinity and kinetic stability. We can use the knowledge from understanding the fundamental coordination chemistry of these elements as a stepping stone to heavy metal detoxification, radioactive waste cleanup, and possibly radioactive isotope separation. The critical components of this research endeavor, along with the viability of metal complex formation, will be correlated to ring size and core geometry of the ligand and, the atomic radius, oxidation state, coordination geometry and coordination number of the transactinium metal ion. These chelating agents may have certain applications to the solution of some radioactive waste problems if they can be attached to polymer supports and used to chemically separate the radioactive components in waste.

  4. Understanding effect of structure and stability on transformation of CH4 hydrate to CO2 hydrate

    NASA Astrophysics Data System (ADS)

    Liu, Jinxiang; Yan, Yujie; Liu, Haiying; Xu, Jiafang; Zhang, Jun; Chen, Gang

    2016-03-01

    Understanding the transformation process of CH4 hydrate to CO2 hydrate is crucial to develop the CH4sbnd CO2 replacement technique for CH4 production and CO2 sequestration. Ab initio calculations show that the transformation will slightly distort the host lattice and decrease the binding strength of guest molecules, but it is a thermodynamically spontaneous process dominated by the entropic contribution. Moreover, ab initio molecular dynamics simulations suggest that the dynamics of the host lattice is independent on the guest molecules, while CO2 in hydrate exhibits slower translational and rotational motion than CH4 in hydrate.

  5. Hydrate Control for Gas Storage Operations

    SciTech Connect

    Jeffrey Savidge

    2008-10-31

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

  6. Polyethylene oxide hydration in grafted layers

    NASA Astrophysics Data System (ADS)

    Dormidontova, Elena; Wang, Zilu

    Hydration of water soluble polymers is one of the key-factors defining their conformation and properties, similar to biopolymers. Polyethylene oxide (PEO) is one of the most important biomedical-applications polymers and is known for its reverse temperature solubility due to hydrogen bonding with water. As in many practical applications PEO chains are grafted to surfaces, e.g. of nanoparticles or planar surfaces, it is important to understand PEO hydration in such grafted layers. Using atomistic molecular dynamic simulations we investigate the details of molecular conformation and hydration of PEO end-grafted to gold surfaces. We analyze polymer and water density distribution as a function of distance from the surface for different grafting densities. Based on a detailed analysis of hydrogen bonding between polymer and water in grafted PEO layers, we will discuss the extent of PEO hydration and its implication for polymer conformation, mobility and layer properties. This research is supported by NSF (DMR-1410928).

  7. Infrared Spectroscopy of Hydrated Nitromethane Anions

    NASA Astrophysics Data System (ADS)

    Marcum, Jesse C.; Weber, J. Mathias

    2009-06-01

    The hydration of molecular anions is still not as thoroughly explored as for atomic anions. We present IR spectra and quantum chemical calculations of hydrated nitromethane anions. In the monohydrate, the nitro group of the ion interacts with the water molecule via two hydrogen bonds, one from each O atom. This motif is partially conserved in the dihydrate. Adding the third water molecule results in a ring-like structure of the water ligands, each of which forms one H bond to one of the O atoms of the nitro group and another to a neighboring water ligand, reminiscent of the hydration motif of the heavier halides. Interestingly, while the methyl group is not directly involved in the interaction with the water ligands, its infrared signature is strongly affected by the changes in the intramolecular charge distribution through hydration.

  8. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Donn McGuire; Thomas Williams; Bjorn Paulsson; Alexander Goertz

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a drilling hazard by the oil and gas industry for years. Drilling engineers working in Russia, Canada and the USA have documented numerous problems, including drilling kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrates as a potential energy source agree that the resource potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained from physical samples taken from actual hydrate-bearing rocks. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The project team drilled and continuously cored the Hot Ice No. 1 well on Anadarko-leased acreage beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and used for determining physical characteristics of hydrates and surrounding rock. After the well was logged, a 3D vertical seismic profile (VSP) was recorded to calibrate the shallow geologic section with seismic data and to investigate techniques to better resolve lateral subsurface variations of potential hydrate-bearing strata. Paulsson Geophysical Services, Inc. deployed their 80 level 3C clamped borehole seismic receiver array in the wellbore to record samples every 25 ft. Seismic vibrators were successively positioned at 1185 different surface positions in a circular pattern around the wellbore. This technique generated a 3D image of the subsurface. Correlations were

  9. Hydration states of AFm cement phases

    SciTech Connect

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

    2015-07-15

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

  10. Overview: Gas hydrate geology and geography

    SciTech Connect

    Malone, R.D.

    1993-01-01

    Several geological factors which are directly responsible for the presence or absence of gas hydrates have been reviewed and are: tectonic position of the region; sedimentary environments; structural deformation; shale diapirism; hydrocarbon generation and migration; thermal regime in the hydrate formation zone (HFZ); pressure conditions; and hydrocarbon gas supply to the HFZ. Work on gas hydrate formation in the geological environment has made significant advances, but there is still much to be learned. Work is continuing in the deeper offshore areas through the Ocean Drilling Program, Government Agencies, and Industry. The pressure/temperature conditions necessary for formation has been identified for various compositions of natural gas through laboratory investigations and conditions for formation are being advanced through drilling in areas where gas hydrates exist.

  11. ConocoPhillips Gas Hydrate Production Test

    SciTech Connect

    Schoderbek, David; Farrell, Helen; Howard, James; Raterman, Kevin; Silpngarmlert, Suntichai; Martin, Kenneth; Smith, Bruce; Klein, Perry

    2013-06-30

    Work began on the ConocoPhillips Gas Hydrates Production Test (DOE award number DE-NT0006553) on October 1, 2008. This final report summarizes the entire project from January 1, 2011 to June 30, 2013.

  12. Indian National Gas Hydrate Program Expedition 01 report

    USGS Publications Warehouse

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

    2015-01-01

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

  13. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Ali Kadaster; Bill Liddell; Tommy Thompson; Thomas Williams; Michael Niedermayr

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project was a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope included drilling and coring a well (Hot Ice No. 1) on Anadarko leases beginning in FY 2003 and completed in 2004. During the first drilling season, operations were conducted at the site between January 28, 2003 to April 30, 2003. The well was spudded and drilled to a depth of 1403 ft. Due to the onset of warmer weather, work was then suspended for the season. Operations at the site were continued after the tundra was re-opened the following season. Between January 12, 2004 and March 19, 2004, the well was drilled and cored to a final depth of 2300 ft. An on-site core analysis laboratory was built and implemented for determining physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. Final efforts of the project are to correlate geology, geophysics, logs, and drilling and

  14. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Bill Liddell

    2004-11-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored a well (the Hot Ice No. 1) on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in the

  15. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Steve Runyon; Mike Globe; Kent Newsham; Robert Kleinberg; Doug Griffin

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project was a cost-shared partnership between Maurer Technology, Noble Corporation, Anadarko Petroleum, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. The work scope included drilling and coring a well (Hot Ice No. 1) on Anadarko leases beginning in FY 2003 and completed in 2004. During the first drilling season, operations were conducted at the site between January 28, 2003 to April 30, 2003. The well was spudded and drilled to a depth of 1403 ft. Due to the onset of warmer weather, work was then suspended for the season. Operations at the site were continued after the tundra was re-opened the following season. Between January 12, 2004 and March 19, 2004, the well was drilled and cored to a final depth of 2300 ft. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and

  16. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Thomas E. Williams; Keith Millheim; Bill Liddell

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. This gas-hydrate project is a cost-shared partnership between Maurer Technology, Anadarko Petroleum, Noble Corporation, and the U.S. Department of Energy's Methane Hydrate R&D program. The purpose of the project is to build on previous and ongoing R&D in the area of onshore hydrate deposition to help identify, quantify and predict production potential for hydrates located on the North Slope of Alaska. As part of the project work scope, team members drilled and cored a well (the Hot Ice No. 1) on Anadarko leases beginning in January 2003 and completed in March 2004. Due to scheduling constraints imposed by the Arctic drilling season, operations at the site were suspended between April 21, 2003 and January 30, 2004. An on-site core analysis laboratory was constructed and used for determining physical characteristics of frozen core immediately after it was retrieved from the well. The well was drilled from a new and innovative Anadarko Arctic Platform that has a greatly reduced footprint and environmental impact. Final efforts of the project were to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists for future hydrate operations. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in the

  17. Spectroscopic methods in gas hydrate research.

    PubMed

    Rauh, Florian; Mizaikoff, Boris

    2012-01-01

    Gas hydrates are crystalline structures comprising a guest molecule surrounded by a water cage, and are particularly relevant due to their natural occurrence in the deep sea and in permafrost areas. Low molecular weight molecules such as methane and carbon dioxide can be sequestered into that cage at suitable temperatures and pressures, facilitating the transition to the solid phase. While the composition and structure of gas hydrates appear to be well understood, their formation and dissociation mechanisms, along with the dynamics and kinetics associated with those processes, remain ambiguous. In order to take advantage of gas hydrates as an energy resource (e.g., methane hydrate), as a sequestration matrix in (for example) CO(2) storage, or for chemical energy conservation/storage, a more detailed molecular level understanding of their formation and dissociation processes, as well as the chemical, physical, and biological parameters that affect these processes, is required. Spectroscopic techniques appear to be most suitable for analyzing the structures of gas hydrates (sometimes in situ), thus providing access to such information across the electromagnetic spectrum. A variety of spectroscopic methods are currently used in gas hydrate research to determine the composition, structure, cage occupancy, guest molecule position, and binding/formation/dissociation mechanisms of the hydrate. To date, the most commonly applied techniques are Raman spectroscopy and solid-state nuclear magnetic resonance (NMR) spectroscopy. Diffraction methods such as neutron and X-ray diffraction are used to determine gas hydrate structures, and to study lattice expansions. Furthermore, UV-vis spectroscopic techniques and scanning electron microscopy (SEM) have assisted in structural studies of gas hydrates. Most recently, waveguide-coupled mid-infrared spectroscopy in the 3-20 μm spectral range has demonstrated its value for in situ studies on the formation and dissociation of gas

  18. Exploitation of subsea gas hydrate reservoirs

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  19. Experimental Dissociation of Methane Hydrates Through Depressurization

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  20. Preservation of methane hydrate at 1 atm

    USGS Publications Warehouse

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

    2001-01-01

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

  1. Methyltrihydroborate complexes of the lanthanides and actinides

    SciTech Connect

    Shinomoto, R.S.

    1984-11-01

    Reaction of MC1/sub 4/ (M = Zr, Hf, U, Th, Np) with LiBH/sub 3/CH/sub 3/ in chlorobenzene produces volatile, hexane-soluble M(BH/sub 3/CH/sub 3/)/sub 4/. Crystal structures are monomeric, tetrahedral species. Lewis base adducts prepared include U(BH/sub 3/CH/sub 3/)/sub 4/.THT, Th(BH/sub 3/CH/sub 3/)/sub 4/.L (L = THF (tetrahydrofuran), THT (tetrahydrothiophene), SMe/sub 2/, OMe/sub 2/), U(BH/sub 3/CH/sub 3/)/sub 4/.2L (L = THF, pyridine, NH/sub 3/), Th(BH/sub 3/CH/sub 3/)/sub 4/.2L (L = THF, THT, py, NH/sub 3/), M(BH/sub 3/CH/sub 3/)/sub 4/.L-L (M = U, Th; L-L = dme (1,2-dimethoxyethane), bmte (bis(1,2-methylthio)ethane), tmed (N,N,N',N'-tetramethylethylenediamine), dmpe (1,2-dimethylphosphinoethane)) and Th(BH/sub 3/CH/sub 3/)/sub 4/.1/2 OEt/sub 2/. Reaction of MC1/sub 3/ (M = Ho, Yb, Lu) with LiBH/sub 3/CH/sub 3/ in diethyl ether produces volatile, toluene-soluble M(BH/sub 3/CH/sub 3/)/sub 3/.OEt/sub 2/. Other Lewis base adducts prepared from M(BH/sub 3/CH/sub 3/)/sub 3/.OEt/sub 2/ include Ho(BH/sub 3/CH/sub 3/)/sub 3/.L (L = THT, THF, py), Ho(BH/sub 3/CH/sub 3/)/sub 3/.2L (L = THT, THF, py), Ho(BH/sub 3/CH/sub 3/)/sub 3/.tmed, Ho(BH/sub 3/CH/sub 3/)/sub 3/.3/2 L-L (L-L = dmpe, bmte), Yb(BH/sub 3/CH/sub 3/)/sub 3/.3/2 dmpe, Yb(BH/sub 3/Ch/sub 3/).L (L = THF, dme), Yb(BH/sub 3/CH/sub 3/)/sub 3/.2THF, and Lu(BH/sub 3/CH/sub 3/)/sub 3/.THF. By structural criteria, the bonding in actinide and lanthanide methyltrihydroborate complexes is primarily ionic in character even though they display covalent-like physical properties. Spectroscopic measurements indicate that there is some degree of covalent bonding in U(BH/sub 3/CH/sub 3/)/sub 4/.

  2. Selective Permeability of Uranyl Peroxide Nanocages to Different Alkali Ions: Influences from Surface Pores and Hydration Shells

    NASA Astrophysics Data System (ADS)

    Gao, Yunyi; Szymanowski, Jennifer; Burns, Peter; Liu, Tianbo

    The precise guidance to different ions across the biological channels is essential for many biological processes. An artificial nanopore system will facilitate the study of ion transport mechanism through nanosized channels and offer new views for designing nanodevices. Here we reveal that a 2.5-nm-size, fullerene-shaped molecular cluster Li48+mK12(OH)m[UO2(O2) (OH)]60-(H2O)n (m ~20 and n ~310) (U60) shows selective permeability to different alkali ions. The sub-nanometer pores on the water-ligand-rich surface of U60 are able to block Rb+ and Cs+ ions from passing through, while allow Na+ and K+ ions, which possess larger hydrated sizes, to enter the interior space of U60. An interestingly high entropy gain during the binding process between U60 and alkali ions suggest that the hydration shells of Na+i/K+ and U60 are damaged during the interaction. The ion selectivity of U60 is greatly influenced by both the morphologies of surface nanopores and the dynamics of the hydration shells. This material is based upon work supported as part of the Materials Science of Actinides Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001089.

  3. Measurement of clathrate hydrates via Raman spectroscopy

    USGS Publications Warehouse

    Sum, A.K.; Burruss, R.C.; Sloan, E.D., Jr.

    1997-01-01

    Raman spectra of clathrate hydrate guest molecules are presented for three known structures (I (sI), II (sII), and H (sH)) in the following systems: CH4 (sI), CO2 (sI), C3H8 (sII), CH4 + CO2 (sI), CD4 + C3H8 (sII), CH4 + N2 (sI), CH4 + THF-d8 (sII), and CH4 + C7D14 (sH). Relative occupancy of CH4 in the large and small cavities of sI were determined by deconvoluting the ??1 symmetric bands, resulting in hydration numbers of 6.04 ?? 0.03. The frequency of the ??1 bands for CH4 in structures I, II, and H differ statistically, so that Raman spectroscopy is a potential tool to identify hydrate crystal structure. Hydrate guest compositions were also measured for two vapor compositions of the CH4 + CO2 system, and they compared favorably with predictions. 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. Hydration numbers from 7.27 to 7.45 were calculated for the mixed hydrate.

  4. Fe-containing phases in hydrated cements

    SciTech Connect

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

    2014-04-01

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

  5. Electrical properties of polycrystalline methane hydrate

    USGS Publications Warehouse

    Du Frane, W. L.; Stern, L.A.; Weitemeyer, K.A.; Constable, S.; Pinkston, J.C.; Roberts, J.J.

    2011-01-01

    Electromagnetic (EM) remote-sensing techniques are demonstrated to be sensitive to gas hydrate concentration and distribution and complement other resource assessment techniques, particularly seismic methods. To fully utilize EM results requires knowledge of the electrical properties of individual phases and mixing relations, yet little is known about the electrical properties of gas hydrates. We developed a pressure cell to synthesize gas hydrate while simultaneously measuring in situ frequency-dependent electrical conductivity (σ). Synthesis of methane (CH4) hydrate was verified by thermal monitoring and by post run cryogenic scanning electron microscope imaging. Impedance spectra (20 Hz to 2 MHz) were collected before and after synthesis of polycrystalline CH4 hydrate from polycrystalline ice and used to calculate σ. We determined the σ of CH4 hydrate to be 5 × 10−5 S/m at 0°C with activation energy (Ea) of 30.6 kJ/mol (−15 to 15°C). After dissociation back into ice, σ measurements of samples increased by a factor of ~4 and Ea increased by ~50%, similar to the starting ice samples.

  6. Clathrate hydrates in the solar system

    NASA Technical Reports Server (NTRS)

    Miller, S. L.

    1985-01-01

    Clathrate hydrates are crystalline compounds in which an expanded ice lattice forms cages that contain gas molecules. There are two principal hydrate structures. Structure I, with a 12 A cubic unit cell, contains 46 water molecules and 8 cages of two types, giving an ideal formula (for CH4) of CH4.5.75H2O. The actual formula contains somewhat more water as the cages are not completely filled. Other examples that form Structure I hydrates are C2H6, C2H4, C2H2, CO2, SO2, OCS, Xe, H2S. Structure II, with a 17 A cubic unit cell, contains 136 water molecules, and 8 large and 16 small cages. The ideal formula for CHCl3 is CHCL3.17H2O. Other examples of Structure II hydrates include C3H8, C2H5Cl, acetone, and tetrahydrofuran. Small molecules such as Ar, Kr and probably N2 and O2 also form a Structure II hydrate. The small molecules occupy both the large and small cages, giving an ideal formula of Ar.5.67H2O. The conditions of pressure and temperature for hydrate formation are discussed.

  7. [Preoperative oral hydration for pregnant women].

    PubMed

    Okutomi, Toshiyuki; Kato, Rie

    2011-07-01

    Preoperative oral hydration is an important component of "enhanced recovery after surgery" strategies. This was originally developed for patients undergoing colon surgery. The Obstetric Anesthesia Practice Guideline issued by American Society of Anesthesiologists states that intake of minimum amount of clear fluid 2 hours prior to surgery may be safe. However, anesthesiologists have to consider physiological changes that parturients undergo during pregnancy, such as increased risk of aspiration and impaired glucose tolerance. We also have to consider the potential effect of glucose loading on neonates. Mothers are more likely to develop ketosis by glucose loading. It also stimulates insulin release in the fetus, which can result in neonatal hypoglycemia. In addition, sodium overloading may deteriorate intra-vascular dehydration and cause lung edema to mothers. On the other hand, oral hydration can alleviate a sense of thirst and increase maternal satisfaction. Our data showed that maternal urinal ketone body at delivery tended to decrease with oral hydration during labor. Moreover, some articles suggest that oral hydration may improve utero-placental perfusion. Therefore, we have to balance risks and benefits of oral hydration in parturients. Further investigations are needed among this specific subgroup of patients in order to establish the safe application of preoperative oral hydration. PMID:21800658

  8. Literature review of intrinsic actinide colloids related to spent fuel waste package release rates

    SciTech Connect

    Zhao, P.; Steward, S.A.

    1997-01-01

    Existence of actinide colloids provides an important mechanism in the migration of radionuclides and will be important in performance of a geologic repository for high-level nuclear waste. Actinide colloids have been formed during long-term unsaturated dissolution of spent fuel by groundwater. This article summarizes a literature search of actinide colloids. This report emphasizes the formation of intrinsic actinide colloids, because they would have the opportunity to form soon after groundwater contact with the spent fuel and before actinide-bearing groundwater reaches the surrounding geologic formations.

  9. Hydration during intense exercise training.

    PubMed

    Maughan, R J; Meyer, N L

    2013-01-01

    Hydration status has profound effects on both physical and mental performance, and sports performance is thus critically affected. Both overhydration and underhydration - if sufficiently severe - will impair performance and pose a risk to health. Athletes may begin exercise in a hypohydrated state as a result of incomplete recovery from water loss induced in order to achieve a specific body mass target or due to incomplete recovery from a previous competition or training session. Dehydration will also develop in endurance exercise where fluid intake does not match water loss. The focus has generally been on training rather than on competition, but sweat loss and fluid replacement in training may have important implications. Hypohydration may impair training quality and may also increase stress levels. It is unclear whether this will have negative effects (reduced training quality, impaired immunity) or whether it will promote a greater adaptive response. Hypohydration and the consequent hyperthermia, however, can enhance the effectiveness of a heat acclimation program, resulting in improved endurance performance in warm and temperate environments. Drinking in training may be important in enhancing tolerance of the gut when athletes plan to drink in competition. The distribution of water between body water compartments may also be important in the initiation and promotion of cellular adaptations to the training stimulus. PMID:23899752

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

    NASA Astrophysics Data System (ADS)

    Xu, W.

    2003-12-01

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

  11. Method for recovery of actinides from actinide-bearing scrap and waste nuclear material using O/sub 2/F/sub 2/

    DOEpatents

    Asprey, L.B.; Eller, P.G.

    1984-09-12

    Method for recovery of actinides from nuclear waste material containing sintered and other oxides thereof and from scrap materials containing the metal actinides using O/sub 2/F/sub 2/ to generate the hexafluorides of the actinides present therein. The fluorinating agent, O/sub 2/F/sub 2/, has been observed to perform the above-described tasks at sufficiently low temperatures that there is virtually no damage to the containment vessels. Moreover, the resulting actinide hexafluorides are not detroyed by high temperature reactions with the walls of the reaction vessel. Dioxygen difluoride is readily prepared, stored and transferred to the place of reaction.

  12. Experimental Evaluation of Actinide Transport in a Fractured Granodiorite

    SciTech Connect

    Dittrich, Timothy M.; Reimus, Paul W.

    2015-03-16

    The objective of this study was to demonstrate and evaluate new experimental methods for quantifying the potential for actinide transport in deep fractured crystalline rock formations. We selected a fractured granodiorite at the Grimsel Test Site (GTS) in Switzerland as a model system because field experiments have already been conducted with uranium and additional field experiments using other actinides are planned at the site. Thus, working on this system provides a unique opportunity to compare lab experiment results with fieldscale observations. Rock cores drilled from the GTS were shipped to Los Alamos National Laboratory, characterized by x-ray diffraction and microscopy, and used in batch sorption and column breakthrough experiments. Solutions with pH 6.8 and 8.8 were tested. Solutions were switched to radionuclide-free synthetic Grimsel groundwater after near-steady actinide/colloid breakthrough occurred in column experiments. We are currently evaluating actinide adsorption/desorption rates as a function of water chemistry (initial focus on pH), with future testing planned to evaluate the influence of carbonate concentrations, flow rates, and mineralogy in solutions and suspensions with bentonite colloids. (auth)

  13. Electronic structure and ionicity of actinide oxides from first principles

    NASA Astrophysics Data System (ADS)

    Petit, L.; Svane, A.; Szotek, Z.; Temmerman, W. M.; Stocks, G. M.

    2010-01-01

    The ground-state electronic structures of the actinide oxides AO , A2O3 , and AO2 ( A=U , Np, Pu, Am, Cm, Bk, and Cf) are determined from first-principles calculations, using the self-interaction corrected local spin-density approximation. Emphasis is put on the degree of f -electron localization, which for AO2 and A2O3 is found to follow the stoichiometry, namely, corresponding to A4+ ions in the dioxide and A3+ ions in the sesquioxides. In contrast, the A2+ ionic configuration is not favorable in the monoxides, which therefore become metallic. The energetics of the oxidation and reduction in the actinide dioxides is discussed, and it is found that the dioxide is the most stable oxide for the actinides from Np onward. Our study reveals a strong link between preferred oxidation number and degree of localization which is confirmed by comparing to the ground-state configurations of the corresponding lanthanide oxides. The ionic nature of the actinide oxides emerges from the fact that only those compounds will form where the calculated ground-state valency agrees with the nominal valency expected from a simple charge counting.

  14. Citrate based ``TALSPEAK`` lanthanide-actinide separation process

    SciTech Connect

    Del Cul, G.D.; Bond, W.D.; Toth, L.M.; Davis, G.D.; Dai, S.; Metcalf, D.H.

    1994-09-01

    The potential hazard posed to future generations by long-lived radionuclides such as the transuranic elements (TRU) is perceived as a major problem associated with the use of nuclear power. TRU wastes have to remain isolated from the environment for ``geological`` periods of time. The costs of building, maintaining, and operating a ``geological TRU repository`` can be very high. Therefore, there are significant economical advantages in segregating the relatively low volume of TRU wastes from other nuclear wastes. The chemical behavior of lanthanides and actinides, 4f and 5f elements respectively, is rather similar. As a consequence, the separation of these two groups is difficult. The ``TALSPEAK`` process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Complexes) is one of the few means available to separate the trivalent actinides from the lanthanides. The method is based on the preferential complexation of the trivalent actinides by an aminopolyacetic acid. Cold experiments showed that by using citric acid the deleterious effects produced by impurities such as zirconium are greatly reduced.

  15. Molecular solids of actinide hexacyanoferrate: Structure and bonding

    NASA Astrophysics Data System (ADS)

    Dupouy, G.; Dumas, T.; Fillaux, C.; Guillaumont, D.; Moisy, P.; Den Auwer, C.; Le Naour, C.; Simoni, E.; Fuster, E. G.; Papalardo, R.; Sanchez Marcos, E.; Hennig, C.; Scheinost, A.; Conradson, S. D.; Shuh, D. K.; Tyliszczak, T.

    2010-03-01

    The hexacyanometallate family is well known in transition metal chemistry because the remarkable electronic delocalization along the metal-cyano-metal bond can be tuned in order to design systems that undergo a reversible and controlled change of their physical properties. We have been working for few years on the description of the molecular and electronic structure of materials formed with [Fe(CN)6]n- building blocks and actinide ions (An = Th, U, Np, Pu, Am) and have compared these new materials to those obtained with lanthanide cations at oxidation state +III. In order to evaluate the influence of the actinide coordination polyhedron on the three-dimensional molecular structure, both atomic number and formal oxidation state have been varied : oxidation states +III, +IV. EXAFS at both iron K edge and actinide LIII edge is the dedicated structural probe to obtain structural information on these systems. Data at both edges have been combined to obtain a three-dimensional model. In addition, qualitative electronic information has been gathered with two spectroscopic tools : UV-Near IR spectrophotometry and low energy XANES data that can probe each atom of the structural unit : Fe, C, N and An. Coupling these spectroscopic tools to theoretical calculations will lead in the future to a better description of bonding in these molecular solids. Of primary interest is the actinide cation ability to form ionic — covalent bonding as 5f orbitals are being filled by modification of oxidation state and/or atomic number.

  16. Actinide Targets for Neutron Cross Section Measurements (C)

    SciTech Connect

    J. D. Baker; C. A. McGrath

    2006-04-01

    The Advanced Fuel Cycle Initiative (AFCI) and the Generation IV Reactor Initiative have demonstrated a lack of detailed neutron cross-sections for certain "minor" actinides, those other than the most common (235U, 238U, and 239Pu). For some closed-fuel-cycle reactor designs more than 50% of reactivity will, at some point, be derived from “minor” actinides that currently have poorly known (n,g) and (n,f) cross sections. A program of measurements under AFCI has begun to correct this. One of the initial hurdles has been to produce well-characterized, highly isotopically enriched, and chemically pure actinide targets on thin backings. Using a combination of resurrected techniques and new developments, we have made a series of targets including highly enriched 240Pu, and 242Pu. Thus far, we have electrodeposited these actinide targets. In the future, we plan to study reductive distillation to achieve homogeneous, adherent targets on thin metal foils and polymer backings. As we move forward, separated isotopes become scarcer, and safety concerns become greater. The chemical purification and electodeposition techniques will be described.

  17. ACTINIDE-SPECIFIC INTERFACIAL CHEMISTRY OF MONOLAYER COATED MESOPOROUS CERAMICS

    EPA Science Inventory

    The need exists in the management of Hanford's high level wastes (HLW) to be able to selectively and completely remove the actinides so that HLW volume can be minimized and the non-radioactive components can be segregated and disposed of as low level waste. In addition, the short...

  18. ACTINIDE BIOCOLLOID FORMATION IN BRINE BY HALOPHILIC BACTERIA

    SciTech Connect

    GILLOW,J.B.; FRANCIS,A.J.; DODGE,C.J.; HARRIS,R.; BEVERIDGE,T.J.; BRADY,P.B.; PAPENGUTH,H.W.

    1998-11-09

    The authors examined the ability of a halophilic bacterium (WIPP 1A) isolated from the Waste Isolation Pilot Plant (WIPP) site to accumulate uranium in order to determine the potential for biocolloid facilitated actinide transport. The bacterial cell surface functional groups involved in the complexation of the actinide were determined by titration. Uranium, added as uranyl nitrate, was removed from solution at pH 5 by cells but at pH 7 and 9 very little uranium was removed due to its limited solubility. Although present as soluble species, uranyl citrate at pH 5, 7, and 9, and uranyl carbonate at pH 9 were not removed by the bacterium because they were not bioavailable due to their neutral or negative charge. Addition of uranyl EDTA to brine at pH 5, 7, and 9 resulted in the immediate precipitation of U. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) analysis revealed that uranium was not only associated with the cell surface but also accumulated intracellularly as uranium-enriched granules. Extended X-ray absorption fine structure (EXAFS) analysis of the bacterial cells indicated the bulk sample contained more than one uranium phase. Nevertheless these results show the potential for the formation of actinide bearing bacterial biocolloids that are strictly regulated by the speciation and bioavailability of the actinide.

  19. Actinide Biocolloid Formation in Brine by Halophilic Bacteria

    SciTech Connect

    Gillow, J.B.; Francis, A.J.; Dodge, C.J.; Harris, R.; Beveridge, T.J.; Brady, P.V.; Papenguth, H.W.

    1999-07-28

    We examined the ability of a halophilic bacterium (WFP 1A) isolated from the Waste Isolation Pilot Plant (WIPP) site to accumulate uranium in order to determine the potential for biocolloid facilitated actinide transport. The bacterial cell Surface functional groups involved in the complexation of the actinide were determined by titration. Uranium, added as uranyl nitrate, was removed from solution at pH 5 by cells but at pH 7 and 9 very little uranium was removed due to its limited volubility. Although present as soluble species, uranyl citrate at pH 5, 7, and 9, and uranyl carbonate at pH 9 were not removed by the bacterium because they were not bioavailable due to their neutral or negative charge. Addition of uranyl EDTA to brine at pH 5, 7, and 9 resulted in the immediate precipitation of U. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) analysis revealed that uranium was not only associated with the cell surface but also accumulated intracellulary as uranium-enriched granules. Extended X-ray absorption fine structure (EXAFS) analysis, of the bacterial cells indicated the bulk sample contained more than one uranium phase. Nevertheless these results show the potential for the formation of actinide bearing bacterial biocolloids that are strictly regulated by the speciation and bioavailability of the actinide.

  20. Actinide biocolloid formation in brine by halophilic bacteria

    SciTech Connect

    Gillow, J.B.; Francis, A.J.; Dodge, C.J.; Harris, R.; Beveridge, T.J.; Brady, P.V.; Papenguth, H.W.

    1998-12-31

    The authors examined the ability of a halophilic bacterium (WIPP 1A) isolated from the Waste Isolation Pilot Plant (WIPP) site to accumulate uranium in order to determine the potential for biocolloid facilitated actinide transport. The bacterial cell surface functional groups involved in the complexation of the actinide were determined by titration. Uranium, added as uranyl nitrate, was removed from solution at pH 5 by cells but at pH 7 and 9 very little uranium was removed due to its limited solubility. Although present as soluble species, uranyl citrate at pH 5, 7, and 9, and uranyl carbonate at pH 9 were not removed by the bacterium because they were not bioavailable due to their neutral or negative charge. Addition of uranyl EDTA to brine at pH 5, 7, and 9 resulted in the immediate precipitation of U. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) analysis revealed that uranium was not only associated with the cell surface but also accumulated intracellularly as uranium-enriched granules. Extended X-ray absorption fine structure (EXAFS) analysis of the bacterial cells indicated the bulk sample contained more than one uranium phase. Nevertheless these results show the potential for the formation of actinide bearing bacterial biocolloids that are strictly regulated by the speciation and bioavailability of the actinide.

  1. RAPID SEPARATION OF ACTINIDES AND RADIOSTRONTIUM IN VEGETATION SAMPLES

    SciTech Connect

    Maxwell, S.

    2010-06-01

    A new rapid method for the determination of actinides and radiostrontium in vegetation samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used in emergency response situations or for routine analysis. The actinides in vegetation method utilizes a rapid sodium hydroxide fusion method, a lanthanum fluoride matrix removal step, and a streamlined column separation process with stacked TEVA, TRU and DGA Resin cartridges. Lanthanum was separated rapidly and effectively from Am and Cm on DGA Resin. Alpha emitters are prepared using rare earth microprecipitation for counting by alpha spectrometry. The purified {sup 90}Sr fractions are mounted directly on planchets and counted by gas flow proportional counting. The method showed high chemical recoveries and effective removal of interferences. The actinide and {sup 90}Sr in vegetation sample analysis can be performed in less than 8 h with excellent quality for emergency samples. The rapid fusion technique is a rugged sample digestion method that ensures that any refractory actinide particles or vegetation residue after furnace heating is effectively digested.

  2. Placental transfer of the actinides and related heavy elements

    SciTech Connect

    Sikov, M.R.

    1986-11-01

    A selective literature review dealing with prenatal exposure of animals and humans to actinides and related heavy elements, comparative aspects of placental transfer and fetoplacental distribution are considered. General patterns have been derived from typical quantitative values, and used to compare similarities and dissimilarities, and to examine factors responsible for observed differences. 37 refs., 2 tabs.

  3. ANNUAL REPORT. ACTINIDE-ALUMINATE SPECIATION IN ALKALINE RADIOACTIVE WASTE

    EPA Science Inventory

    Highly alkaline radioactive waste tanks contain a number of transuranic species, in particular U, Np, Pu, and Am-the exact forms of which are currently unknown. Knowledge of actinide speciation under highly alkaline conditions is essential towards understanding and predicting the...

  4. Hydrate pingoes at Nyegga: some characteristic features

    NASA Astrophysics Data System (ADS)

    Hovland, M.

    2009-04-01

    Hydrate pingoes were observed on the seafloor during two different remotely operated vehicle (ROV)-dives, conducted by Statoil at complex-pockmark G11, at Nyegga, off Mid-Norway. Confirmation that these structures actually represent hydrate ice-cored sediment mounds (pingoes), was done by other investigators (Ivanov et al., 2006). Because it is expected that hydrate pingoes represent relatively dynamic seafloor topographic structures and that their shape and size most probably will change over relatively short time, it is important to know how to recognise them visually. Hovland and Svensen (2006) highlighted five different characteristic aspects that define hydrate pingoes on the sea floor: 1) They are dome- or disc-shaped features, which may attain any size from ~0.5 m in height and upwards. Inside pockmark G11, they were up to 1 m high. 2) They are circular or oval in plan view and may attain lateral sizes on the seafloor ranging upwards from ~0.5 m. Inside G11 they had lengths of several metres and widths of up to 4 m. 3) They have dense communities of organisms growing on their surfaces. At G11, they were overgrown with small pogonophoran tube-worms. 4) They have patches of white or grey bacterial mats growing on their surface, indicating advection (seepage) of reduced pore-waters. 5) They have small pits and patches of fluidized sediments on their surface, indicating pit corrosion of the sub-surface gas hydrate. Because gas hydrates often form in high-porosity, near-surface sediments, where water is readily available, it is thought that they will build up at locations where gases are actively migrating upwards from depth. However, gas hydrates are not stable in the presence of ambient seawater, as seawater is deficient in guest molecule gases (normally methane). Therefore, they tend to build up below surface above conduits for gas flow from depth. But, the near-surface hydrate ice-lenses will continually be corroded by seawater circulating into the sediments

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

    PubMed

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

    2009-06-01

    Magnetic resonance imaging was used to monitor and quantify methane hydrate formation and exchange in porous media. Conversion of methane hydrate to carbon dioxide hydrate, when exposed to liquid carbon dioxide at 8.27 MPa and approximately 4 degrees C, was experimentally demonstrated with MRI data and verified by mass balance calculations of consumed volumes of gases and liquids. No detectable dissociation of the hydrate was measured during the exchange process. PMID:19168304

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

    PubMed

    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

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

    PubMed

    Rayne, Sierra; Forest, Kaya

    2016-01-01

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

  8. Controls on Gas Hydrate Formation and Dissociation

    SciTech Connect

    Miriam Kastner; Ian MacDonald

    2006-03-03

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

  9. The INE-Beamline for actinide science at ANKA

    NASA Astrophysics Data System (ADS)

    Rothe, J.; Butorin, S.; Dardenne, K.; Denecke, M. A.; Kienzler, B.; Löble, M.; Metz, V.; Seibert, A.; Steppert, M.; Vitova, T.; Walther, C.; Geckeis, H.

    2012-04-01

    Since its inauguration in 2005, the INE-Beamline for actinide research at the synchrotron source ANKA (KIT North Campus) provides dedicated instrumentation for x-ray spectroscopic characterization of actinide samples and other radioactive materials. R&D work at the beamline focuses on various aspects of nuclear waste disposal within INE's mission to provide the scientific basis for assessing long-term safety of a final nuclear waste repository. The INE-Beamline is accessible for the actinide and radiochemistry community through the ANKA proposal system and the European Union Integrated Infrastructure Initiative ACTINET-I3. Experiments with activities up to 1 × 10+6 times the European exemption limit are feasible within a safe but flexible containment concept. Measurements with monochromatic radiation are performed at photon energies varying between ˜2.1 keV (P K-edge) and ˜25 keV (Pd K-edge), including the lanthanide L-edges and the actinide M- and L3-edges up to Cf. The close proximity of the INE-Beamline to INE controlled area labs offers infrastructure unique in Europe for the spectroscopic and microscopic characterization of actinide samples. The modular beamline design enables sufficient flexibility to adapt sample environments and detection systems to many scientific questions. The well-established bulk techniques x-ray absorption fine structure (XAFS) spectroscopy in transmission and fluorescence mode have been augmented by advanced methods using a microfocused beam, including (confocal) XAFS/x-ray fluorescence detection and a combination of (micro-)XAFS and (micro-)x-ray diffraction. Additional instrumentation for high energy-resolution x-ray emission spectroscopy has been successfully developed and tested.

  10. Lauriston S. Taylor Lecture: the quest for therapeutic actinide chelators.

    PubMed

    Durbin, Patricia W

    2008-11-01

    All of the actinides are radioactive. Taken into the body, they damage and induce cancer in bone and liver, and in the lungs if inhaled, and U(VI) is a chemical kidney poison. Containment of radionuclides is fundamental to radiation protection, but if it is breached accidentally or deliberately, decontamination of exposed persons is needed to reduce the consequences of radionuclide intake. The only known way to reduce the health risks of internally deposited actinides is to accelerate their excretion with chelating agents. Ethylendiaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) were introduced in the 1950's. DTPA is now clinically accepted, but its oral activity is low, it must be injected as a Ca(II) or Zn(II) chelate to avoid toxicity, and it is structurally unsuitable for chelating U(VI) or Np(V). Actinide penetration into the mammalian iron transport and storage systems suggested that actinide ions would form stable complexes with the Fe(III)-binding units found in potent selective natural iron chelators (siderophores). Testing of that biomimetic approach began in the late 1970's with the design, production, and assessment for in vivo Pu(IV) chelation of synthetic multidentate ligands based on the backbone structures and Fe(III)-binding groups of siderophores. New efficacious actinide chelators have emerged from that program, in particular, octadentate 3,4,3-LI(1,2-HOPO) and tetradentate 5-LIO(Me-3,2-HOPO) have potential for clinical acceptance. Both are much more effective than CaNa3-DTPA for decorporation of Pu(IV), Am(III), U(VI), and Np(IV,V), they are orally active, and toxicity is acceptably low at effective dosage. PMID:18849679

  11. Actinide Speciation and Solubility in a Salt Repository (Invited)

    NASA Astrophysics Data System (ADS)

    Reed, D.; Borkowski, M.; Richmann, M.; Lucchini, J.; Khaing, H.; Swanson, J.

    2009-12-01

    The use of bedded salt deposits for the permanent disposal of nuclear waste continues to receive much attention in the United States and internationally. This is largely based on the highly successful Waste Isolation Pilot Plant (WIPP) transuranic waste repository that was opened in 1999 in Southeastern New Mexico. A bedded salt formation, such as the one in which the WIPP is located, has many advantages that make it an ideal geology for permanent disposal of nuclear waste. This includes well established mining techniques, self-sealing that lead to a naturally-induced geologic isolation, a relatively dry environment, and a favorable chemistry. Herein we report on recent progress in our investigations, as part of ongoing recertification effort for the operating WIPP repository, to establish the redox distribution and overall solubility of actinides in brine. The overall ranking of actinides, from the perspective of potential contribution to release from the WIPP, is: Pu ~ Am >>U > Th >> Np, Cm. Our recent research emphasis has centered on the redox chemistry of multivalent actinides (e.g., U, Pu and Np) with the use of oxidation-state-invariant analogs (Th and Nd) to establish the solubilities. Under a wide range of conditions investigated, the predominant oxidation states established are Pu(III) and Pu(IV) for plutonium, U(IV) and U(VI) for uranium, and Am (III) for americium. Reduction pathways for plutonium include reaction with organics, reaction with reduced iron, and bioreduction by halophiles under anaerobic conditions. Uranium(VI) can also be reduced to U(IV) by reduced iron and microbial processes. Solubility data for neodymium (+3 analog), Uranium (+6 analog) and thorium (+4 analog) in brine are also reported. These data extend our past understanding of WIPP-specific actinide chemistry and show the WIPP, and salt-based repositories in general, to be a robust repository design from the perspective of actinide containment and immobilization.

  12. Actinide partitioning-transmutation program final report. I. Overall assessment

    SciTech Connect

    Croff, A.G.; Blomeke, J.O.; Finney, B.C.

    1980-06-01

    This report is concerned with an overall assessment of the feasibility of and incentives for partitioning (recovering) long-lived nuclides from fuel reprocessing and fuel refabrication plant radioactive wastes and transmuting them to shorter-lived or stable nuclides by neutron irradiation. The principal class of nuclides considered is the actinides, although a brief analysis is given of the partitioning and transmutation (P-T) of /sup 99/Tc and /sup 129/I. The results obtained in this program permit us to make a comparison of the impacts of waste management with and without actinide recovery and transmutation. Three major conclusions concerning technical feasibility can be drawn from the assessment: (1) actinide P-T is feasible, subject to the acceptability of fuels containing recycle actinides; (2) technetium P-T is feasible if satisfactory partitioning processes can be developed and satisfactory fuels identified (no studies have been made in this area); and (3) iodine P-T is marginally feasible at best because of the low transmutation rates, the high volatility, and the corrosiveness of iodine and iodine compounds. It was concluded on the basis of a very conservative repository risk analysis that there are no safety or cost incentives for actinide P-T. In fact, if nonradiological risks are included, the short-term risks of P-T exceed the long-term benefits integrated over a period of 1 million years. Incentives for technetium and iodine P-T exist only if extremely conservative long-term risk analyses are used. Further RD and D in support of P-T is not warranted.

  13. Actinide partitioning processes for fuel reprocessing and refabrication plant wastes

    SciTech Connect

    Finney, B.C.; Tedder, D.W.

    1980-01-01

    Chemical processing methods have been developed on a laboratory scale to partition the actinides from the liquid and solid fuel reprocessing plant (FRP) and refabrication plant (FFP) wastes. It was envisioned that these processes would be incorporated into separate waste treatment facilities (WTFs) that are adjacent to, but not integrated with, the fuel reprocessing and refabrication plants. Engineering equipment and material balance flowsheets have been developed for WTFs in support of a 2000-MTHM/year FRP and a 660-MTHM/year MOX-FFP. The processing subsystems incorporated in the FRP-WTF are: High-Level Solid Waste Treatment, High-Level Liquid Waste Treatment, Solid Alpha Waste Treatment, Cation Exchange Chromatography, Salt Waste Treatment, Actinide Recovery, Solvent Cleanup and recycle, Off-Gas Treatment, Actinide Product Concentration, and Acid and Water Recycle. The WTF supporting a fuel refabrication facility, although similar, does not contain subsystems (1) and (2). Based on the results of the laboratory and hot-cell experimental work, we believe that the processes and flowsheets offer the potential to reduce the total unrecovered actinides in FRP and FFP wastes to less than or equal to 0.25%. The actinide partitioning processes and the WTF concept represent advanced technology that would require substantial work before commercialization. It is estimated that an orderly development program would require 15 to 20 years to complete and would cost about 700 million 1979 dollars. It is estimated that the capital cost and annual operating cost, in mid-1979 dollars, for the FRP-WTF are $1035 million and $71.5 million/year, and for the FFP-WTF are $436 million and $25.6 million/year, respectively.

  14. Sequestering agents for the removal of actinides from waste streams

    SciTech Connect

    Raymond, K.N.; White, D.J.; Xu, Jide; Mohs, T.R.

    1997-10-01

    The goal of this project is to take a biomimetic approach toward developing new separation technologies for the removal of radioactive elements from contaminated DOE sites. To achieve this objective, the authors are investigating the fundamental chemistry of naturally occurring, highly specific metal ion sequestering agents and developing them into liquid/liquid and solid supported actinide extraction agents. Nature produces sideophores (e.g., Enterobactin and Desferrioxamine B) to selectivity sequester Lewis acidic metal ions, in particular Fe(III), from its surroundings. These chelating agents typically use multiple catechols or hydroxamic acids to form polydentate ligands that chelate the metal ion forming very stable complexes. The authors are investigating and developing analogous molecules into selective chelators targeting actinide(IV) ions, which display similar properties to Fe(III). By taking advantage of differences in charge, preferred coordination number, and pH stability range, the transition from nature to actinide sequestering agents has been applied to the development of new and highly selective actinide extraction technologies. Additionally, the authors have shown that these chelating ligands are versatile ligands for chelating U(VI). In particular, they have been studying their coordination chemistry and fundamental interactions with the uranyl ion [UO{sub 2}]{sup 2+}, the dominant form of uranium found in aqueous media. With an understanding of this chemistry, and results obtained from in vivo uranium sequestration studies, it should be possible to apply these actinide(IV) extraction technologies to the development of new extraction agents for the removal of uranium from waste streams.

  15. The INE-Beamline for actinide science at ANKA

    SciTech Connect

    Rothe, J.; Dardenne, K.; Denecke, M. A.; Kienzler, B.; Loeble, M.; Metz, V.; Steppert, M.; Vitova, T.; Geckeis, H.; Butorin, S.; Seibert, A.; Walther, C.

    2012-04-15

    Since its inauguration in 2005, the INE-Beamline for actinide research at the synchrotron source ANKA (KIT North Campus) provides dedicated instrumentation for x-ray spectroscopic characterization of actinide samples and other radioactive materials. R and D work at the beamline focuses on various aspects of nuclear waste disposal within INE's mission to provide the scientific basis for assessing long-term safety of a final nuclear waste repository. The INE-Beamline is accessible for the actinide and radiochemistry community through the ANKA proposal system and the European Union Integrated Infrastructure Initiative ACTINET-I3. Experiments with activities up to 1 x 10{sup +6} times the European exemption limit are feasible within a safe but flexible containment concept. Measurements with monochromatic radiation are performed at photon energies varying between {approx}2.1 keV (P K-edge) and {approx}25 keV (Pd K-edge), including the lanthanide L-edges and the actinide M- and L3-edges up to Cf. The close proximity of the INE-Beamline to INE controlled area labs offers infrastructure unique in Europe for the spectroscopic and microscopic characterization of actinide samples. The modular beamline design enables sufficient flexibility to adapt sample environments and detection systems to many scientific questions. The well-established bulk techniques x-ray absorption fine structure (XAFS) spectroscopy in transmission and fluorescence mode have been augmented by advanced methods using a microfocused beam, including (confocal) XAFS/x-ray fluorescence detection and a combination of (micro-)XAFS and (micro-)x-ray diffraction. Additional instrumentation for high energy-resolution x-ray emission spectroscopy has been successfully developed and tested.

  16. Properties of equilibrium carbon dioxide hydrate in porous medium

    NASA Astrophysics Data System (ADS)

    Voronov, V. P.; Gorodetskii, E. E.; Podnek, V. E.; Grigoriev, B. A.

    2016-09-01

    Specific heat capacity, dissociation heat and hydration number of carbon dioxide hydrate in porous medium are determined by adiabatic calorimetry method. The measurements were carried out in the temperature range 250-290 K and in pressure range 1-5 MPa. The measured specific heat of the hydrate is approximately 2.7 J/(g K), which is significantly larger than the specific heat of methane hydrate. In particular, at heating, larger value of the specific heat of carbon dioxide hydrate is a result of gas emission from the hydrate. The hydration number at the hydrate-gas coexistence changes from 6.2 to 6.9. The dissociation heat of carbon dioxide hydrate varies from the 55 kJ/mol near the upper quadruple point to the 57 kJ/mol near the lower quadruple point.

  17. Depressurization and electrical heating of hydrate sediment for gas production

    NASA Astrophysics Data System (ADS)

    Minagawa, H.

    2015-12-01

    As a part of a Japanese National hydrate research program (MH21, funded by METI), we performed a study on electrical heating of the hydrate core combined with depressurization for gas production. In-situ dissociation of natural gas hydrate is necessary for commercial recovery of natural gas from natural gas hydrate sediment. Thermal stimulation is an effective dissociation method, along with depressurization.To simulate methane gas production from methane hydrate layer, we investigated electrical heating of methane hydrate sediment. A decrease in core temperature due to the endothermic reaction of methane hydrate dissociation was suppressed and the core temperature increased between 1oC and 4oC above the control temperature with electric heating. A current density of 10A/m2 with depressurization would effectively dissociate hydrate. Therefore, depressurization and additional electrode heating of hydrate sediment saturated with electrolyte solution was confirmed to enable higher gas production from sediment with less electric power.

  18. High-Altitude Hydration System

    NASA Technical Reports Server (NTRS)

    Parazynski, Scott E.; Orndoff, Evelyne; Bue, Grant C.; Schaefbauer, Mark E.; Urban, Kase

    2010-01-01

    Three methods are being developed for keeping water from freezing during high-altitude climbs so that mountaineers can remain hydrated. Three strategies have been developed. At the time of this reporting two needed to be tested in the field and one was conceptual. The first method is Passive Thermal Control Using Aerogels. This involves mounting the fluid reservoir of the climber s canteen to an inner layer of clothing for better heat retention. For the field test, bottles were mounted to the inner fleece layer of clothing, and then aerogel insulation was placed on the outside of the bottle, and circumferentially around the drink straw. When climbers need to drink, they can pull up the insulated straw from underneath the down suit, take a sip, and then put it back into the relative warmth of the suit. For the field test, a data logger assessed the temperatures of the water reservoir, as well as near the tip of the drink straw. The second method is Passive Thermal Control with Copper-Shielded Drink Straw and Aerogels, also mounted to inner layers of clothing for better heat retention. Braided wire emanates from the inside of the fleece jacket layer, and continues up and around the drink straw in order to use body heat to keep the system-critical drink straw warm enough to keep water in the liquid state. For the field test, a data logger will be used to compare this with the above concept. The third, and still conceptual, method is Active Thermal Control with Microcontroller. If the above methods do not work, microcontrollers and tape heaters have been identified that could keep the drink straw warm even under extremely cold conditions. Power requirements are not yet determined because the thermal environment inside the down suit relative to the external environment has not been established. A data logger will be used to track both the external and internal temperatures of the suit on a summit day.

  19. Study on propane-butane gas storage by hydrate technology

    NASA Astrophysics Data System (ADS)

    Hamidi, Nurkholis; Wijayanti, Widya; Widhiyanuriyawan, Denny

    2016-03-01

    Different technology has been applied to store and transport gas fuel. In this work the storage of gas mixture of propane-butane by hydrate technology was studied. The investigation was done on the effect of crystallizer rotation speed on the formation of propane-butane hydrate. The hydrates were formed using crystallizer with rotation speed of 100, 200, and 300 rpm. The formation of gas hydrates was done at initial pressure of 3 bar and temperature of 274K. The results indicated that the higher rotation speed was found to increase the formation rate of propane-butane hydrate and improve the hydrates stability.

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

    DOEpatents

    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.

  1. Hydrate problems in pipelines: A study from Norwegian continental waters

    SciTech Connect

    Lysne, D.; Larsen, R.; Lund, A.; Thomsen, A.K.

    1995-12-31

    This study was undertaken by the Norwegian Petroleum Directorate and SINTEF to identify hydrate problems occurring in pipelines on the Norwegian continental shelf. A brief review of hydrate dissociation theory is given. Three major techniques for hydrate removal are discussed, as well as hazards related to hydrate plug removal. Questionnaire answers from 15 companies operating in Norwegian waters show three specific occurrences of hydrate plugs in the North Sea. Problems from other geographical areas are also discussed. Hydrate problems are reported for a wide variety of pipe lengths, diameters, profiles, insulations characteristics and fluids. Most problems occur during normal operation.

  2. Gas storage through impermeation of porous media by hydrate formation

    SciTech Connect

    Hatzikiriakos, S.G.; Englezos, P.

    1994-12-31

    A mathematical model was developed for the simulation of the methane hydrate formation in a homocline. The rate of hydrate growth was computed by calculating the movement of the hydrate-water interface. This movement was found to be very slow (less than 0.01 mm/hr) and strongly dependent on the value of the effective diffusivity of the gas in the hydrate zone. The temperature at the hydrate-water interface was found to remain practically constant. Finally, the simulations indicate that the development of a hydrate barrier in the permeable formation creates favorable gas storage conditions in the homocline.

  3. Nucleation and Growth of Gas Hydrate in Natural Seawater

    NASA Astrophysics Data System (ADS)

    Holman, S. A.; Osegovic, J. P.; Young, J. C.; Max, M. D.; Ames, A. L.

    2003-12-01

    Large-scale nucleation of gas hydrate takes place when hydrate-forming gas and seawater are brought together under suitable pressure-temperature conditions or where dissolved hydrate-forming gas in saturated or near-saturated seawater is chilled or brought to higher pressures. Profuse formation of hydrate shells on gas bubbles and nucleation of at least five different forms of gas hydrate have been achieved in fresh natural seawater. Growth of masses of solid gas hydrate takes place when hydrate-forming gas reactant dissolved in seawater is brought into the vicinity of the hydrate. The gas concentration of the enriched water in the vicinity of hydrate is higher than the hydrate equilibrium gas concentration. Hydrate growth under these conditions is accelerated due to the chemical potential difference between the enriched water and the hydrate crystals, which induces mass flux of dissolved hydrate forming gas into new hydrate crystals. As long as water enriched in the hydrate-forming gas is circulated into the vicinity of the hydrate, growth proceeds into the water space. Experimental approaches for growth of examples of solid masses of hydrate are presented. Results of these experiments provide an insight into the growth of gas hydrate under natural conditions where interstitial water in marine sediments is captured by burial from open seawater, and where solid gas hydrate forms on the seafloor. By using fresh natural seawater, which is a chemically and materially complex fluid, our experiments in pressurized, refrigerated reactors should closely track the growth history of solid hydrate in the natural environment. In our model for hydrate growth in sediments, nearly complete pore fill by diagenetic hydrate can best be accomplished by nucleation of hydrate at a point source within the pore water or at a particular point on sediment particulate, with growth outward into the water space that is refreshed with ground water having high concentrations of hydrate

  4. Development of hydrate risk quantification in oil and gas production

    NASA Astrophysics Data System (ADS)

    Chaudhari, Piyush N.

    Subsea flowlines that transport hydrocarbons from wellhead to the processing facility face issues from solid deposits such as hydrates, waxes, asphaltenes, etc. The solid deposits not only affect the production but also pose a safety concern; thus, flow assurance is significantly important in designing and operating subsea oil and gas production. In most subsea oil and gas operations, gas hydrates form at high pressure and low temperature conditions, causing the risk of plugging flowlines, with a undesirable impact on production. Over the years, the oil and gas industry has shifted their perspective from hydrate avoidance to hydrate management given several parameters such as production facility, production chemistry, economic and environmental concerns. Thus, understanding the level of hydrate risk associated with subsea flowlines is an important in developing efficient hydrate management techniques. In the past, hydrate formation models were developed for various flow-systems (e.g., oil dominated, water dominated, and gas dominated) present in the oil and gas production. The objective of this research is to extend the application of the present hydrate prediction models for assessing the hydrate risk associated with subsea flowlines that are prone to hydrate formation. It involves a novel approach for developing quantitative hydrate risk models based on the conceptual models built from the qualitative knowledge obtained from experimental studies. A comprehensive hydrate risk model, that ranks the hydrate risk associated with the subsea production system as a function of time, hydrates, and several other parameters, which account for inertial, viscous, interfacial forces acting on the flow-system, is developed for oil dominated and condensate systems. The hydrate plugging risk for water dominated systems is successfully modeled using The Colorado School of Mines Hydrate Flow Assurance Tool (CSMHyFAST). It is found that CSMHyFAST can be used as a screening tool in

  5. METHANE HYDRATE PRODUCTION FROM ALASKAN PERMAFROST

    SciTech Connect

    Richard Sigal; Kent Newsham; Thomas Williams; Barry Freifeld; Timothy Kneafsey; Carl Sondergeld; Shandra Rai; Jonathan Kwan; Stephen Kirby; Robert Kleinberg; Doug Griffin

    2005-02-01

    Natural-gas hydrates have been encountered beneath the permafrost and considered a nuisance by the oil and gas industry for years. Engineers working in Russia, Canada and the USA have documented numerous drilling problems, including kicks and uncontrolled gas releases, in arctic regions. Information has been generated in laboratory studies pertaining to the extent, volume, chemistry and phase behavior of gas hydrates. Scientists studying hydrate potential agree that the potential is great--on the North Slope of Alaska alone, it has been estimated at 590 TCF. However, little information has been obtained on physical samples taken from actual rock containing hydrates. The work scope drilled and cored a well The Hot Ice No. 1 on Anadarko leases beginning in FY 2003 and completed in 2004. An on-site core analysis laboratory was built and utilized for determining the physical characteristics of the hydrates and surrounding rock. The well was drilled from a new Anadarko Arctic Platform that has a minimal footprint and environmental impact. The final efforts of the project are to correlate geology, geophysics, logs, and drilling and production data and provide this information to scientists developing reservoir models. No gas hydrates were encountered in this well; however, a wealth of information was generated and is contained in this report. The Hot Ice No. 1 well was drilled from the surface to a measured depth of 2300 ft. There was almost 100% core recovery from the bottom of surface casing at 107 ft to total depth. Based on the best estimate of the bottom of the methane hydrate stability zone (which used new data obtained from Hot Ice No. 1 and new analysis of data from adjacent wells), core was recovered over its complete range. Approximately 580 ft of porous, mostly frozen, sandstone and 155 of conglomerate were recovered in the Ugnu Formation and approximately 215 ft of porous sandstone were recovered in the West Sak Formation. There were gas shows in the bottom

  6. Gas hydrates: past and future geohazard?

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  8. Internal contamination by actinides after wounding: a robust rodent model for assessment of local and distant actinide retention.

    PubMed

    Griffiths, N M; Wilk, J C; Abram, M C; Renault, D; Chau, Q; Helfer, N; Guichet, C; Van der Meeren, A

    2012-08-01

    Internal contamination by actinides following wounding may occur in nuclear fuel industry workers or subsequent to terrorist activities, causing dissemination of radioactive elements. Contamination by alpha particle emitting actinides can result in pathological effects, either local or distant from the site of entry. The objective of the present study was to develop a robust experimental approach in the rat for short- and long- term actinide contamination following wounding by incision of the skin and muscles of the hind limb. Anesthetized rats were contaminated with Mixed OXide (MOX, uranium, plutonium oxides containing 7.1% plutonium) or plutonium nitrate (Pu nitrate) following wounding by deep incision of the hind leg. Actinide excretion and tissue levels were measured as well as histological changes from 2 h to 3 mo. Humid swabs were used for rapid evaluation of contamination levels and proved to be an initial guide for contamination levels. Although the activity transferred from wound to blood is higher after contamination with a moderately soluble form of plutonium (nitrate), at 7 d most of the MOX (98%) or Pu nitrate (87%) was retained at the wound site. Rapid actinide retention in liver and bone was observed within 24 h, which increased up to 3 mo. After MOX contamination, a more rapid initial urinary excretion of americium was observed compared with plutonium. At 3 mo, around 95% of activity remained at the wound site, and excretion of Pu and Am was extremely low. This experimental approach could be applied to other situations involving contamination following wounding including rupture of the dermal, vascular, and muscle barriers. PMID:22951478

  9. Interfacial phenomena in gas hydrate systems.

    PubMed

    Aman, Zachary M; Koh, Carolyn A

    2016-03-21

    Gas hydrates are crystalline inclusion compounds, where molecular cages of water trap lighter species under specific thermodynamic conditions. Hydrates play an essential role in global energy systems, as both a hinderance when formed in traditional fuel production and a substantial resource when formed by nature. In both traditional and unconventional fuel production, hydrates share interfaces with a tremendous diversity of materials, including hydrocarbons, aqueous solutions, and inorganic solids. This article presents a state-of-the-art understanding of hydrate interfacial thermodynamics and growth kinetics, and the physiochemical controls that may be exerted on both. Specific attention is paid to the molecular structure and interactions of water, guest molecules, and hetero-molecules (e.g., surfactants) near the interface. Gas hydrate nucleation and growth mechanics are also presented, based on studies using a combination of molecular modeling, vibrational spectroscopy, and X-ray and neutron diffraction. The fundamental physical and chemical knowledge and methods presented in this review may be of value in probing parallel systems of crystal growth in solid inclusion compounds, crystal growth modifiers, emulsion stabilization, and reactive particle flow in solid slurries. PMID:26781172

  10. Novel Hydrogen Hydrate Structures under Pressure

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    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.

  11. Dynamical Disorder in the DNA Hydration Shell.

    PubMed

    Duboué-Dijon, Elise; Fogarty, Aoife C; Hynes, James T; Laage, Damien

    2016-06-22

    The reorientation and hydrogen-bond dynamics of water molecules within the hydration shell of a B-DNA dodecamer, which are of interest for many of its biochemical functions, are investigated via molecular dynamics simulations and an analytic jump model, which provide valuable new molecular level insights into these dynamics. Different sources of heterogeneity in the hydration shell dynamics are determined. First, a pronounced spatial heterogeneity is found at the DNA interface and explained via the jump model by the diversity in local DNA interfacial topographies and DNA-water H-bond interactions. While most of the hydration shell is moderately retarded with respect to the bulk, some water molecules confined in the narrow minor groove exhibit very slow dynamics. An additional source of heterogeneity is found to be caused by the DNA conformational fluctuations, which modulate the water dynamics. The groove widening aids the approach of, and the jump to, a new water H-bond partner. This temporal heterogeneity is especially strong in the minor groove, where groove width fluctuations occur on the same time scale as the water H-bond rearrangements, leading to a strong dynamical disorder. The usual simplifying assumption that hydration shell dynamics is much faster than DNA dynamics is thus not valid; our results show that biomolecular conformational fluctuations are essential to facilitate the water motions and accelerate the hydration dynamics in confined groove sites. PMID:27240107

  12. Fragmentation and hydration of tektites and microtektites

    USGS Publications Warehouse

    Glass, B.P.; Muenow, D.W.; Bohor, B.F.; Meeker, G.P.

    1997-01-01

    An examination of data collected over the last 30 years indicates that the percent of glass fragments vs. whole splash forms in the Cenozoic microtektite strewn fields increases towards the source crater (or source region). We propose that this is due to thermal stress produced when tektites and larger microtektites fall into water near the source crater while still relatively hot (>1150 ??C). We also find evidence (low major oxide totals, frothing when melted) for hydration of most of the North American tektite fragments and microtektites found in marine sediments. High-temperature mass spectrometry indicates that these tektite fragments and microtektites contain up to 3.8 wt% H2O. The H2O-release behavior during the high-temperature mass-spectrometric analysis, plus high Cl abundances (???0.05 wt%), indicate that the North. American tektite fragments and microtektites were hydrated in the marine environment (i.e., the H2O was not trapped solely on quenching from a melt). The younger Ivory Coast and Australasian microtektites do not exhibit much evidence of hydration (at least not in excess of 0.5 wt% H2O); this suggests that the degree of hydration increases with age. In addition, we find that some glass spherules (with 65 wt% SiO2 can undergo simple hydration in the marine environment, while impact glasses (with <65 wt% SiO2) can also undergo palagonitization.

  13. Novel hydrogen hydrate structures under pressure.

    PubMed

    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. PMID:25001502

  14. On the structure selectivity of clathrate hydrates.

    PubMed

    Matsumoto, Masakazu; Tanaka, Hideki

    2011-06-30

    We propose a strategic method to search for a new clathrate hydrate by investigating the selectivity of its crystalline structure, which has been expected to depend mostly on the guest species and less on the thermodynamic conditions. Relative stability among various morphologies is examined in terms of the chemical potential of water of clathrate hydrates in equilibrium with guest gases. This evaluation is performed by calculating the free energy of cage occupancy according to the standard statistical mechanical theory with the aid of the Yarmolyuk and Kripyakevich's rule on the Frank-Kasper type alloys to estimate the numbers of cages of various types. Thus, a comprehensive interpretation of the selectivity of crystalline structures is successfully made. We explain why two major structures are stable in most of the thermodynamic conditions and establish a relation between polymorphism of clathrate hydrate and the guest size and other parameters, thereby suggesting a way to find a new clathrate hydrate by appropriate choice of the guest species and/or the thermodynamic properties. It is found that there is a small room in the above parameter space for the other structure than the major two to be the most stable, including a new structure. In addition, simple but thorough elucidation is given for preferential formation of TS-I structure in bromine hydrate. PMID:21619053

  15. Blue LED irradiation to hydration of skin

    NASA Astrophysics Data System (ADS)

    Menezes, Priscila F. C.; Requena, Michelle B.; Lizarelli, Rosane F., Z.; Bagnato, Vanderlei S.

    2015-06-01

    Blue LED system irradiation shows many important properties on skin as: bacterial decontamination, degradation of endogenous skin chromophores and biostimulation. In this clinical study we prove that the blue light improves the skin hydration. In the literature none authors reports this biological property on skin. Then this study aims to discuss the role of blue light in the skin hydration. Twenty patients were selected to this study with age between 25-35 years old and phototype I, II and III. A defined area from forearm was pre determined (A = 4.0 cm2). The study was randomized in two treatment groups using one blue light device (power of 5.3mW and irradiance of 10.8mW/cm2). The first treatment group was irradiated with 3J/cm2 (277seconds) and the second with 6J/cm2 (555 seconds). The skin hydration evaluations were done using a corneometer. The measurements were collected in 7, 14, 21 and 30 days, during the treatment. Statistical test of ANOVA, Tukey and T-Student were applied considering 5% of significance. In conclusion, both doses were able to improve the skin hydration; however, 6J/cm2 has kept this hydration for 30 days.

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

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  17. Laboratory actinide partitioning - Whitlockite/liquid and influence of actinide concentration levels

    NASA Technical Reports Server (NTRS)

    Benjamin, T. M.; Jones, J. H.; Heuser, W. R.; Burnett, D. S.

    1983-01-01

    The partition coefficients between synthetic whitlockite (beta Ca-phosphate) and coexisting silicate melts are determined for the actinide elements Th, U and Pu. Experiments were performed at 1 bar pressure and 1250 C at oxygen fugacities from 10 to the -8.5 to 10 to the -0.7 bars, and partitioning was determined from trace element radiography combined with conventional electron microprobe analysis. Results show Pu to be more readily incorporated into crystalline phases than U or Th under reducing conditions, which is attributed to the observation that Pu exists primarily in the trivalent state, while U and Th are tetravalent. Corrected partition coefficients for whitlockite of 3.6, less than or equal to 0.6, 1.2, 0.5 and less than or equal to 0.002 are estimated for Pu(+3), Pu(+4), Th(+4), U(+4) and U(+6), respectively. Experiments performed at trace levels and percent levels of UO2 indicate that Si is involved in U substitution in whitlockite, and show a reduced partition coefficient at higher concentrations of U that can be explained by effects on melt structure or the fraction of tetravalent U.

  18. Quantifying hydrate solidification front advancing using method of characteristics

    NASA Astrophysics Data System (ADS)

    You, Kehua; DiCarlo, David; Flemings, Peter B.

    2015-10-01

    We develop a one-dimensional analytical solution based on the method of characteristics to explore hydrate formation from gas injection into brine-saturated sediments within the hydrate stability zone. Our solution includes fully coupled multiphase and multicomponent flow and the associated advective transport in a homogeneous system. Our solution shows that hydrate saturation is controlled by the initial thermodynamic state of the system and changed by the gas fractional flow. Hydrate saturation in gas-rich systems can be estimated by 1-cl0/cle when Darcy flow dominates, where cl0 is the initial mass fraction of salt in brine, and cle is the mass fraction of salt in brine at three-phase (gas, liquid, and hydrate) equilibrium. Hydrate saturation is constant, gas saturation and gas flux decrease, and liquid saturation and liquid flux increase with the distance from the gas inlet to the hydrate solidification front. The total gas and liquid flux is constant from the gas inlet to the hydrate solidification front and decreases abruptly at the hydrate solidification front due to gas inclusion into the hydrate phase. The advancing velocity of the hydrate solidification front decreases with hydrate saturation at a fixed gas inflow rate. This analytical solution illuminates how hydrate is formed by gas injection (methane, CO2, ethane, propane) at both the laboratory and field scales.

  19. Improved Actinide Neutron Capture Cross Sections Using Accelerator Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Bauder, W.; Pardo, R. C.; Kondev, F. G.; Kondrashev, S.; Nair, C.; Nusair, O.; Palchan, T.; Scott, R.; Seweryniak, D.; Vondrasek, R.; Collon, P.; Paul, M.; Youinou, G.; Salvatores, M.; Palmotti, G.; Berg, J.; Maddock, T.; Imel, G.

    2014-09-01

    The MANTRA (Measurement of Actinide Neutron TRAnsmutations) project will improve energy-integrated neutron capture cross section data across the actinide region. These data are incorporated into nuclear reactor models and are an important piece in understanding Generation IV reactor designs. We will infer the capture cross sections by measuring isotopic ratios from actinide samples, irradiated in the Advanced Test Reactor at INL, with Accelerator Mass Spectrometry (AMS) at ATLAS (ANL). The superior sensitivity of AMS allows us to extract multiple cross sections from a single sample. In order to analyze the large number of samples needed for MANTRA and to meet the goal of extracting multiple cross sections per sample, we have made a number of modifications to the AMS setup at ATLAS. In particular, we are developing a technique to inject solid material into the ECR with laser ablation. With laser ablation, we can better control material injection and potentially increase efficiency in the ECR, thus creating less contamination in the source and reducing cross talk. I will present work on the laser ablation system and preliminary results from our AMS measurements. The MANTRA (Measurement of Actinide Neutron TRAnsmutations) project will improve energy-integrated neutron capture cross section data across the actinide region. These data are incorporated into nuclear reactor models and are an important piece in understanding Generation IV reactor designs. We will infer the capture cross sections by measuring isotopic ratios from actinide samples, irradiated in the Advanced Test Reactor at INL, with Accelerator Mass Spectrometry (AMS) at ATLAS (ANL). The superior sensitivity of AMS allows us to extract multiple cross sections from a single sample. In order to analyze the large number of samples needed for MANTRA and to meet the goal of extracting multiple cross sections per sample, we have made a number of modifications to the AMS setup at ATLAS. In particular, we are

  20. Methane hydrates in nature - Current knowledge and challenges

    USGS Publications Warehouse

    Collett, Timothy S.

    2014-01-01

    Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance

  1. Curvature Dependence of Hydrophobic Hydration Dynamics

    NASA Astrophysics Data System (ADS)

    Weiß, R. Gregor; Heyden, Matthias; Dzubiella, Joachim

    2015-05-01

    We investigate the solute curvature dependence of water dynamics in the vicinity of hydrophobic spherical solutes using molecular dynamics simulations. For both the lateral and perpendicular diffusivity, as well as for H-bond kinetics of water in the first hydration shell, we find a nonmonotonic solute-size dependence, exhibiting extrema close to the well-known structural crossover length scale for hydrophobic hydration. Additionally, we find an apparent anomalous diffusion for water moving parallel to the surface of small solutes, which, however, can be explained by topology effects. Our findings regarding the intimate connection between solute curvature and water dynamics has implications for our understanding of hydration dynamics at heterogeneous biomolecular surfaces.

  2. Method for production of hydrocarbons from hydrates

    DOEpatents

    McGuire, Patrick L.

    1984-01-01

    A method of recovering natural gas entrapped in frozen subsurface gas hydrate formations in arctic regions. A hot supersaturated solution of CaCl.sub.2 or CaBr.sub.2, or a mixture thereof, is pumped under pressure down a wellbore and into a subsurface hydrate formation so as to hydrostatically fracture the formation. The CaCl.sub.2 /CaBr.sub.2 solution dissolves the solid hydrates and thereby releases the gas entrapped therein. Additionally, the solution contains a polymeric viscosifier, which operates to maintain in suspension finely divided crystalline CaCl.sub.2 /CaBr.sub.2 that precipitates from the supersaturated solution as it is cooled during injection into the formation.

  3. Fuel cell membrane hydration and fluid metering

    DOEpatents

    Jones, Daniel O.; Walsh, Michael M.

    1999-01-01

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

  4. Fuel cell membrane hydration and fluid metering

    DOEpatents

    Jones, Daniel O.; Walsh, Michael M.

    2003-01-01

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

  5. Relaxation mechanism of the hydrated electron.

    PubMed

    Elkins, Madeline H; Williams, Holly L; Shreve, Alexander T; Neumark, Daniel M

    2013-12-20

    The relaxation dynamics of the photoexcited hydrated electron have been subject to conflicting interpretations. Here, we report time-resolved photoelectron spectra of hydrated electrons in a liquid microjet with the aim of clarifying ambiguities from previous experiments. A sequence of three ultrashort laser pulses (~100 femtosecond duration) successively created hydrated electrons by charge-transfer-to-solvent excitation of dissolved anions, electronically excited these electrons via the s→p transition, and then ejected them into vacuum. Two distinct transient signals were observed. One was assigned to the initially excited p-state with a lifetime of ~75 femtoseconds, and the other, with a lifetime of ~400 femtoseconds, was attributed to s-state electrons just after internal conversion in a nonequilibrated solvent environment. These assignments support the nonadiabatic relaxation model. PMID:24357314

  6. Apparatus investigates geological aspects of gas hydrates

    USGS Publications Warehouse

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

    1999-01-01

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

  7. Aggregation of Calcium Silicate Hydrate Nanoplatelets.

    PubMed

    Delhorme, Maxime; Labbez, Christophe; Turesson, Martin; Lesniewska, Eric; Woodward, Cliff E; Jönsson, Bo

    2016-03-01

    We study the aggregation of calcium silicate hydrate nanoplatelets on a surface by means of Monte Carlo and molecular dynamics simulations at thermodynamic equilibrium. Calcium silicate hydrate (C-S-H) is the main component formed in cement and is responsible for the strength of the material. The hydrate is formed in early cement paste and grows to form platelets on the nanoscale, which aggregate either on dissolving cement particles or on auxiliary particles. The general result is that the experimentally observed variations in these dynamic processes generically called growth can be rationalized from interaction free energies, that is, from pure thermodynamic arguments. We further show that the surface charge density of the particles determines the aggregate structures formed by C-S-H and thus their growth modes. PMID:26859614

  8. Mapping the hydration dynamics of ubiquitin.

    PubMed

    Nucci, Nathaniel V; Pometun, Maxim S; Wand, A Joshua

    2011-08-17

    The nature of water's interaction with biomolecules such as proteins has been difficult to examine in detail at atomic resolution. Solution NMR spectroscopy is potentially a powerful method for characterizing both the structural and temporal aspects of protein hydration but has been plagued by artifacts. Encapsulation of the protein of interest within the aqueous core of a reverse micelle particle results in a general slowing of water dynamics, significant reduction in hydrogen exchange chemistry and elimination of contributions from bulk water thereby enabling the use of nuclear Overhauser effects to quantify interactions between the protein surface and hydration water. Here we extend this approach to allow use of dipolar interactions between hydration water and hydrogens bonded to protein carbon atoms. By manipulating the molecular reorientation time of the reverse micelle particle through use of low viscosity liquid propane, the T(1ρ) relaxation time constants of (1)H bonded to (13)C were sufficiently lengthened to allow high quality rotating frame nuclear Overhauser effects to be obtained. These data supplement previous results obtained from dipolar interactions between the protein and hydrogens bonded to nitrogen and in aggregate cover the majority of the molecular surface of the protein. A wide range of hydration dynamics is observed. Clustering of hydration dynamics on the molecular surface is also seen. Regions of long-lived hydration water correspond with regions of the protein that participate in molecular recognition of binding partners suggesting that the contribution of the solvent entropy to the entropy of binding has been maximized through evolution. PMID:21761828

  9. Component analysis of the protein hydration entropy

    NASA Astrophysics Data System (ADS)

    Chong, Song-Ho; Ham, Sihyun

    2012-05-01

    We report the development of an atomic decomposition method of the protein solvation entropy in water, which allows us to understand global change in the solvation entropy in terms of local changes in protein conformation as well as in hydration structure. This method can be implemented via a combined approach based on molecular dynamics simulation and integral-equation theory of liquids. An illustrative application is made to 42-residue amyloid-beta protein in water. We demonstrate how this method enables one to elucidate the molecular origin for the hydration entropy change upon conformational transitions of protein.

  10. Experimental Study of Gas Hydrate Dynamics

    NASA Astrophysics Data System (ADS)

    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

  11. Simulation of subsea gas hydrate exploitation

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    The recovery of methane from gas hydrate layers that have been detected in several subsea sediments and permafrost regions around the world is a promising perspective to overcome future shortages in natural gas supply. Being aware that conventional natural gas resources are limited, research is going on to develop technologies for the production of natural gas from such new sources. Thus various research programs have started since the early 1990s in Japan, USA, Canada, India, and Germany to investigate hydrate deposits and develop required technologies. In recent years, intensive research has focussed on the capture and storage of CO2 from combustion processes to reduce climate impact. While different natural or man-made reservoirs like deep aquifers, exhausted oil and gas deposits or other geological formations are considered to store gaseous or liquid CO2, the storage of CO2 as hydrate in former methane hydrate fields is another promising alternative. Due to beneficial stability conditions, methane recovery may be well combined with CO2 storage in the form of hydrates. Regarding technological implementation many problems have to be overcome. Especially mixing, heat and mass transfer in the reservoir are limiting factors causing very long process times. Within the scope of the German research project »SUGAR« different technological approaches for the optimized exploitation of gas hydrate deposits are evaluated and compared by means of dynamic system simulations and analysis. Detailed mathematical models for the most relevant chemical and physical processes are developed. The basic mechanisms of gas hydrate formation/dissociation and heat and mass transport in porous media are considered and implemented into simulation programs. Simulations based on geological field data have been carried out. The studies focus on the potential of gas production from turbidites and their fitness for CO2 storage. The effects occurring during gas production and CO2 storage within

  12. Natural gas: Formation of hydrates -- Transportation

    SciTech Connect

    Bhaskara Rao, B.K.

    1998-07-01

    The significant growth of Natural gas based industries in India and elsewhere obviously forced the industry to hunt for new fields and sources. This has naturally led to the phenomenal growth of gas networks. The transportation of gas over thousands of kilometers through caprious ambient conditions requires a great effort. Many difficulties such as condensation of light liquids (NGLS), choking of lines due to formation of hydrates, improper distribution of gas into branches are experienced during pipe line transportation of Natural gas. The thermodynamic conditions suitable for formation of solid hydrates have been derived depending upon the constituents of natural gas. Further effects of branching in pipe line transportation have been discussed.

  13. Arctic Gas hydrate, Environment and Climate

    NASA Astrophysics Data System (ADS)

    Mienert, Jurgen; Andreassen, Karin; Bünz, Stefan; Carroll, JoLynn; Ferre, Benedicte; Knies, Jochen; Panieri, Giuliana; Rasmussen, Tine; Myhre, Cathrine Lund

    2015-04-01

    Arctic methane hydrate exists on land beneath permafrost regions and offshore in shelf and continental margins sediments. Methane or gas hydrate, an ice-like substrate, consists mainly of light hydrocarbons (mostly methane from biogenic sources but also ethane and propane from thermogenic sources) entrapped by a rigid cage of water molecules. The pressure created by the overlying water and sediments offshore stabilizes the CH4 in continental margins at a temperature range well above freezing point; consequently CH4 exists as methane ice beneath the seabed. Though the accurate volume of Arctic methane hydrate and thus the methane stored in hydrates throughout the Quaternary is still unknown it must be enormous if one considers the vast regions of Arctic continental shelves and margins as well as permafrost areas offshore and on land. Today's subseabed methane hydrate reservoirs are the remnants from the last ice age and remain elusive targets for both unconventional energy and as a natural methane emitter influencing ocean environments and ecosystems. It is still contentious at what rate Arctic warming may govern hydrate melting, and whether the methane ascending from the ocean floor through the hydrosphere reaches the atmosphere. As indicated by Greenland ice core records, the atmospheric methane concentration rose rapidly from ca. 500 ppb to ca. 750 ppb over a short time period of just 150 years at the termination of the younger Dryas period ca. 11600 years ago, but the dissociation of large quantities of methane hydrates on the ocean floor have not been documented yet (Brook et al., 2014 and references within). But with the major projected warming and sea ice melting trend (Knies et al., 2014) one may ask, for how long will CH4 stay trapped in methane hydrates if surface and deep-ocean water masses will warm and permafrost continuous to melt (Portnov et al. 2014). How much of the Arctic methane will be consumed by the micro- and macrofauna, how much will

  14. Morphology of methane hydrate host sediments

    USGS Publications Warehouse

    Jones, K.W.; Feng, H.; Tomov, S.; Winters, W.J.; Eaton, M.; Mahajan, D.

    2005-01-01

    The morphological features including porosity and grains of methane hydrate host sediments were investigated using synchrotron computed microtomography (CMT) technique. The sediment sample was obtained during Ocean Drilling Program Leg 164 on the Blake Ridge at water depth of 2278.5 m. The CMT experiment was performed at the Brookhaven National Synchrotron Light Source facility. The analysis gave ample porosity, specific surface area, mean particle size, and tortuosity. The method was found to be highly effective for the study of methane hydrate host sediments.

  15. Mechanical instability of monocrystalline and polycrystalline methane hydrates.

    PubMed

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

    2015-01-01

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

  16. Mechanical instability of monocrystalline and polycrystalline methane hydrates

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  17. Mechanical instability of monocrystalline and polycrystalline methane hydrates

    PubMed Central

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

    2015-01-01

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

  18. Investigating Actinide Molecular Adducts From Absorption Edge Spectroscopy

    SciTech Connect

    Den Auwer, C.; Conradson, S.D.; Guilbaud, P.; Moisy, P.; Mustre de Leon, J.; Simoni, E.; /SLAC, SSRL

    2006-10-27

    Although Absorption Edge Spectroscopy has been widely applied to the speciation of actinide elements, specifically at the L{sub III} edge, understanding and interpretation of actinide edge spectra are not complete. In that sense, semi-quantitative analysis is scarce. In this paper, different aspects of edge simulation are presented, including semi-quantitative approaches. Comparison is made between various actinyl (U, Np) aquo or hydroxy compounds. An excursion into transition metal osmium chemistry allows us to compare the structurally related osmyl and uranyl hydroxides. The edge shape and characteristic features are discussed within the multiple scattering picture and the role of the first coordination sphere as well as contributions from the water solvent are described.

  19. X-Ray Absorption Spectroscopy of the Actinides

    NASA Astrophysics Data System (ADS)

    Antonio, Mark R.; Soderholm, Lynda

    The recent availability of synchrotron radiation has revolutionized actinide chemistry. This is particularly true in environmental studies, where heterogeneous samples add to the already multifaceted chemistry exhibited by these ions. Environmental samples are often inhomogeneous, chemically diverse, and amorphous or poorly crystalline. Even surrogates prepared in the laboratory to simplify the natural complexity are plagued by multiple oxidation state and varied coordination polyhedra that are a reflection of inherent 5f chemistry. For example, plutonium can be found as Pu3+ Pu4+ Pu(V)O2 +, and Pu(VI)O2 2 + within naturally occurring pH-Eh conditions, consequently complex equilibria are found between these oxidation states in one solution. In addition, dissolved actinides have significant affinities for various mineral surfaces, to which they can adsorb with or without concomitant reduction-oxidation (redox) activity, depending on details of the solution and surface conditions.

  20. Actinide-specific sequestering agents and decontamination applications

    SciTech Connect

    Smith, William L.; Raymond, Kenneth N.

    1981-04-07

    With the commercial development of nuclear reactors, the actinides have become very important industrial elements. A major concern of the nuclear industry is the biological hazard associated with nuclear fuels and their wastes. The acute chemical toxicity of tetravalent actinides, as exemplified by Th(IV), is similar to Cr(III) or Al(III). However, the acute toxicity of 239Pu(IV) is similar to strychnine, which is much more toxic than any of the non-radioactive metals such as mercury. Although the more radioactive isotopes of the transuranium elements are more acutely toxic by weight than plutonium, the acute toxicities of 239Pu, 241Am, and 244Cm are nearly identical in radiation dose, ~100 μCi/kg in rodents. Finally and thus, the extreme acute toxicity of 239Pu is attributed to its high specific activity of alpha emission.

  1. The pentavalent actinide solution chemistry in the environment.

    PubMed

    Topin, Sylvain; Aupiais, Jean

    2016-03-01

    With regard to environmental monitoring of certain nuclear facilities, pentavalent actinides, in particular neptunium and plutonium, play a key role, as the chief soluble, mobile forms of actinides. In the past five years, investigations carried out by hyphenating capillary electrophoresis to ICP-MS (CE-ICP-MS) have allowed a number of hitherto unknown thermodynamic data to be determined for Np(V) and Pu(V) interactions with the chief environmentally abundant anions. For the first time, data were provided for Pu(V) interactions with carbonate, sulfate, oxalate, chloride, and nitrate ions, allowing the Np(V)/Pu(V) analogy to be verified experimentally. Knowledge of Np(V) chemistry, especially in carbonate, and sulfate media, was also refined. These CE-ICP-MS studies, combined with some earlier findings, have brought about a renewal in the knowledge of An(V) chemistry in solution. PMID:26808225

  2. Thermodynamics of trivalent lanthanide and actinide elements in carbonate solutions

    SciTech Connect

    Rao, L.; Rai, D.; Felmy, A.R.; Fulton, R.W.

    1995-12-01

    Knowledge of the thermodynamics of actinide and lanthanide elements in various aqueous electrolyte solutions is essential for the development of actinide separation techniques. It is particularly important to understand the thermodynamics of these elements in basic and concentrated electrolyte solutions if the separation techniques are in concentrated electrolytes and to be applied to the treatment of nuclear wastes, since many of these wastes contain concentrated electrolytes and are under strongly basic conditions. Solubility experiments were conducted for neodymium(III) in bicarbonate and carbonate solutions. Experimental results were analyzed with the specific ion-interaction approach of Pitzer. A thermodynamic model was developed to describe the solubilities of corresponding carbonate compounds of neodymium(III) and americium(III) under wide ranges of pH and carbonate concentrations.

  3. Actinide solubility and spectroscopic speciation in alkaline Hanford waste solutions

    SciTech Connect

    Rao, L.; Felmy, A.R.; Rai, D.

    1996-10-01

    Information on the solubility and the speciation of actinide elements, especially plutonium and neptunium, in alkaline solutions is of importance in the development of separation techniques for the Hanford tank HLW supernatant. In the present study, experimental data on the solubilities of plutonium in simulated Hanford tank solutions were analyzed with Pitzer`s specific ion-interaction approach, which is applicable in dilute to highly concentrated electrolyte solutions. In order to investigate the formation of actinide species in alkaline solutions with ligands (e.g., hydroxide, aluminate and carbonate), spectroscopic measurements of neptunium (V), as a chemical analog of plutonium (V), were conducted. Based on the solubility data and available information on both solid and aqueous species, a thermodynamic model was proposed. The applicability and limitations of this model are discussed.

  4. Accuracy Improvement of Neutron Nuclear Data on Minor Actinides

    NASA Astrophysics Data System (ADS)

    Harada, Hideo; Iwamoto, Osamu; Iwamoto, Nobuyuki; Kimura, Atsushi; Terada, Kazushi; Nakao, Taro; Nakamura, Shoji; Mizuyama, Kazuhito; Igashira, Masayuki; Katabuchi, Tatsuya; Sano, Tadafumi; Takahashi, Yoshiyuki; Takamiya, Koichi; Pyeon, Cheol Ho; Fukutani, Satoshi; Fujii, Toshiyuki; Hori, Jun-ichi; Yagi, Takahiro; Yashima, Hiroshi

    2015-05-01

    Improvement of accuracy of neutron nuclear data for minor actinides (MAs) and long-lived fission products (LLFPs) is required for developing innovative nuclear system transmuting these nuclei. In order to meet the requirement, the project entitled as "Research and development for Accuracy Improvement of neutron nuclear data on Minor ACtinides (AIMAC)" has been started as one of the "Innovative Nuclear Research and Development Program" in Japan at October 2013. The AIMAC project team is composed of researchers in four different fields: differential nuclear data measurement, integral nuclear data measurement, nuclear chemistry, and nuclear data evaluation. By integrating all of the forefront knowledge and techniques in these fields, the team aims at improving the accuracy of the data. The background and research plan of the AIMAC project are presented.

  5. Crystalline matrices for immobilization of actinides: Corrosion resistance in water

    NASA Astrophysics Data System (ADS)

    Yudintsev, S. V.; Aleksandrova, E. V.; Livshits, T. S.; Mal'kovskii, V. I.; Bychkova, Ya. V.; Tagirov, B. R.

    2014-10-01

    The rate of leaching of actinide-simulating rare-earth elements from two types of crystalline matrices consisting of titanate and titanozirconate phases was examined. The experiments were carried out at 95°C in distilled water. The rates of REE leaching from the samples were below 10-3 g/m2 day, which satisfied the requirements for the characteristics of matrices for immobilization of actinides. After passing the treated solutions through filters of 450 to 25 nm pore sizes, the REE content was changed slightly or not at all. This fact points to the minor role or to the absence of the colloidal form of REE in the solutions after the experiments.

  6. Observation of large scissors resonance strength in actinides.

    PubMed

    Guttormsen, M; Bernstein, L A; Bürger, A; Görgen, A; Gunsing, F; Hagen, T W; Larsen, A C; Renstrøm, T; Siem, S; Wiedeking, M; Wilson, J N

    2012-10-19

    The orbital M1 scissors resonance has been measured for the first time in the quasicontinuum of actinides. Particle-γ coincidences are recorded with deuteron and (3)He-induced reactions on (232)Th. The residual nuclei (231,232,233)Th and (232,233) Pa show an unexpectedly strong integrated strength of B(M1)=11-15μ(n)(2) in the E(γ)=1.0-3.5 MeV region. The increased γ-decay probability in actinides due to scissors resonance is important for cross-section calculations for future fuel cycles of fast nuclear reactors and may also have an impact on stellar nucleosynthesis. PMID:23215072

  7. Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides.

    PubMed

    Batrice, Rami J; Kefalidis, Christos E; Maron, Laurent; Eisen, Moris S

    2016-02-24

    The unprecedented actinide-catalyzed addition of alcohols to carbodiimides is presented. This represents a rare example of thorium-catalyzed transformations of an alcoholic substrate and the first example of uranium complexes showing catalytic reactivity with alcohols. Using the uranium and thorium amides U[N(SiMe3)2]3 and [(Me3Si)2N]2An[κ(2)-(N,C)-CH2Si(CH3)2N(SiMe3)] (An = Th or U), alcohol additions to unsaturated carbon-nitrogen bonds are achieved in short reaction times with excellent selectivities and high to excellent yields. Computational studies, supported by experimental thermodynamic data, suggest plausible models of the profile of the reaction which allow the system to overcome the high barrier of scission of the actinide-oxygen bond. Accompanied by experimentally determined kinetic parameters, a plausible mechanism is proposed for the catalytic cycle. PMID:26844823

  8. Pulsed photothermal spectroscopy applied to lanthanide and actinide speciation

    SciTech Connect

    Berg, J.M.; Morris, D.E.; Clark, D.L.; Tait, C.D.; Woodruff, W.H. ); Ven Der Sluys, W.G. . Dept. of Chemistry)

    1991-01-01

    Several key elements important for the application of laser-based photothermal spectroscopies to the study of the complexation chemistry of lanthanides and actinides in solution have been demonstrated. The sensitivity of f-f electronic transition energies and band intensities to subtle changes in complexation was illustrated through comparison of visible and near infra-red absorption spectra of well-characterized U(IV) dimers with alkoxide ligands. Significant improvements in spectroscopic band resolution and energy measurement precision for solution species were shown to be achievable through work in frozen glasses at 77 K using a very simple cryogenic apparatus. A pulsed-laser photothermal spectroscopy apparatus was constructed and shown to be sensitive to optical density changes of 10{sup {minus}5} in an aqueous Nd{sup 3+} solution. In addition, the capability of obtaining photothermal lensing spectra of dilute actinide solutions in frozen glasses at 77 K was demonstrated. 6 refs., 5 figs.

  9. Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands

    SciTech Connect

    Schelter, Eric J.; Wu, Ruilian; Veauthier, Jacqueline M.; Bauer, Eric D.; Booth, Corwin H.; Thomson, Robert K.; Graves, Christopher R.; John, Kevin D.; Scott, Brian L.; Thompson, Joe D.; Morris, David E.; Kiplinger, Jaqueline L.

    2010-02-24

    A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are presented for (C{sub 5}Me{sub 5}){sub 2}An[-N=C(Bn)(tpy-M{l_brace}C{sub 5}Me4R{r_brace}{sub 2})]{sub 2} (where An = Th{sup IV}, U{sup IV}; Bn = CH{sub 2}C{sub 6}H{sub 5}; M = La{sup III}, Sm{sup III}, Yb{sup III}, U{sup III}; R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral 'M' site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb{sup III}-U{sup IV}-Yb{sup III}, Sm{sup III}-U{sup IV}-Sm{sup III}, and La{sup III}-U{sup IV}-La{sup III} complexes, [8]{sup -}, [9b]{sup -} and [10b]{sup -}, respectively, whose calculated comproportionation constant K{sub c} is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U{sup III}, U{sup IV}, and U{sup V} reveal small but detectable energy differences in the 'white-line' feature of the uranium L{sub III}-edges consistent with these variations in nominal oxidation state. The sum of this data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4{prime}-cyano-2,2{prime}:6{prime},2{double_prime}-terpyridine is also reported.

  10. Chemical and Ceramic Methods Toward Safe Storage of Actinides

    SciTech Connect

    P.E.D. Morgan; R.M. Housley; J.B. Davis; M.L. DeHaan

    2005-08-19

    A very import, extremely-long-term, use for monazite as a radwaste encapsulant has been proposed. THe use of ceramic La-monazite for sequestering actinides (isolating them from the environment), especially plutonium and some other radioactive elements )e.g., fission-product rare earths), had been especially championed by Lynn Boatner of ORNL. Monazite may be used alone or, copying its compatibility with many other minerals in nature, may be used in diverse composite combinations.

  11. Molecular Characterization of Actinide Oxocations from Protactinium to Plutonium

    NASA Astrophysics Data System (ADS)

    Den Auwer, C.; Guilbaud, P.; Guillaumont, D.; Moisy, P.; Digandomenico, V.; Le Naour, C.; Trubert, D.; Simoni, E.; Hennig, C.; Scheinost, A.; Conradson, S. D.

    2007-02-01

    This presentation addresses the structural characterization by EXAFS of actinide cations at oxidation states (V) and (VI) as one walks across the periodic table from Z = 91 (protactinium) to Z = 94 (plutonium). A structural comparison between Pa, U, Np and Pu oxocations in aqueous solution at formal oxidation states (V) and (VI) is carried out. These results are corroborated by quantum chemical and molecular dynamics calculations.

  12. Impact of actinide recycle on nuclear fuel cycle health risks

    SciTech Connect

    Michaels, G.E.

    1992-06-01

    The purpose of this background paper is to summarize what is presently known about potential impacts on the impacts on the health risk of the nuclear fuel cycle form deployment of the Advanced Liquid Metal Reactor (ALMR){sup 1} and Integral Fast Reactor (IF){sup 2} technology as an actinide burning system. In a companion paper the impact on waste repository risk is addressed in some detail. Therefore, this paper focuses on the remainder of the fuel cycle.

  13. Relativistic effects on the thermal expansion of the actinide elements

    SciTech Connect

    Soederlind, P.; Nordstroem, L.; Lou Yongming; Johansson, B. )

    1990-09-01

    The room-temperature linear thermal-expansion coefficient is calculated for the light actinides thorium, protactinium, uranium, neptunium, and plutonium for the fcc crystal structure. The relativistic spin-orbit interaction is included in these calculations. We show that the spin-orbit splitting of the 5{ital f} band gives rise to a considerable increase of the thermal expansion and to a large extent explains the observed anomalously large thermal expansion for the neptunium and plutonium metals.

  14. Molecular Characterization of Actinide Oxocations from Protactinium to Plutonium

    SciTech Connect

    Den Auwer, C.; Guilbaud, P.; Guillaumont, D.; Moisy, P.; Hennig, C.; Scheinost, A.; Conradson, S. D.

    2007-02-02

    This presentation addresses the structural characterization by EXAFS of actinide cations at oxidation states (V) and (VI) as one walks across the periodic table from Z = 91 (protactinium) to Z = 94 (plutonium). A structural comparison between Pa, U, Np and Pu oxocations in aqueous solution at formal oxidation states (V) and (VI) is carried out. These results are corroborated by quantum chemical and molecular dynamics calculations.

  15. Determination of actinides in urine and fecal samples

    SciTech Connect

    McKibbin, T.T.

    1992-12-31

    A method of determining the radioactivity of specific actinides that are carried in urine or fecal sample material is disclosed. The samples are ashed in a muffle furnace, dissolved in an acid, and then treated in a series of steps of reduction, oxidation, dissolution, and precipitation, including a unique step of passing a solution through a chloride form anion exchange resin for separation of uranium and plutonium from americium.

  16. Determination of actinides in urine and fecal samples

    DOEpatents

    McKibbin, Terry T.

    1993-01-01

    A method of determining the radioactivity of specific actinides that are carried in urine or fecal sample material is disclosed. The samples are ashed in a muffle furnace, dissolved in an acid, and then treated in a series of steps of reduction, oxidation, dissolution, and precipitation, including a unique step of passing a solution through a chloride form anion exchange resin for separation of uranium and plutonium from americium.

  17. Determination of actinides in urine and fecal samples

    DOEpatents

    McKibbin, T.T.

    1993-03-02

    A method of determining the radioactivity of specific actinides that are carried in urine or fecal sample material is disclosed. The samples are ashed in a muffle furnace, dissolved in an acid, and then treated in a series of steps of reduction, oxidation, dissolution, and precipitation, including a unique step of passing a solution through a chloride form anion exchange resin for separation of uranium and plutonium from americium.

  18. Future nuclear fuel cycles: Prospect and challenges for actinide recycling

    NASA Astrophysics Data System (ADS)

    Warin, Dominique

    2010-03-01

    The global energy context pleads in favour of a sustainable development of nuclear energy since the demand for energy will likely increase, whereas resources will tend to get scarcer and the prospect of global warming will drive down the consumption of fossil fuel. In this context, nuclear power has the worldwide potential to curtail the dependence on fossil fuels and thereby to reduce the amount of greenhouse gas emissions while promoting energy independence. How we deal with nuclear radioactive waste is crucial in this context. In France, the public's concern regarding the long-term waste management made the French Governments to prepare and pass the 1991 and 2006 Acts, requesting in particular the study of applicable solutions for still minimizing the quantity and the hazardousness of final waste. This necessitates High Active Long Life element (such as the Minor Actinides MA) recycling, since the results of fuel cycle R&D could significantly change the challenges for the storage of nuclear waste. HALL recycling can reduce the heat load and the half-life of most of the waste to be buried to a couple of hundred years, overcoming the concerns of the public related to the long-life of the waste and thus aiding the "burying approach" in securing a "broadly agreed political consensus" of waste disposal in a geological repository. This paper presents an overview of the recent R and D results obtained at the CEA Atalante facility on innovative actinide partitioning hydrometallurgical processes. For americium and curium partitioning, these results concern improvements and possible simplifications of the Diamex-Sanex process, whose technical feasibility was already demonstrated in 2005. Results on the first tests of the Ganex process (grouped actinide separation for homogeneous recycling) are also discussed. In the coming years, next steps will involve both better in-depth understanding of the basis of these actinide partitioning processes and, for the new promising

  19. Chemical properties of the heavier actinides and transactinides

    SciTech Connect

    Hulet, E.K.

    1981-01-01

    The chemical properties of each of the elements 99 (Es) through 105 are reviewed and their properties correlated with the electronic structure expected for 5f and 6d elements. A major feature of the heavier actinides, which differentiates them from the comparable lanthanides, is the increasing stability of the divalent oxidation state with increasing atomic number. The divalent oxidation state first becomes observable in the anhydrous halides of californium and increases in stability through the series to nobelium, where this valency becomes predominant in aqueous solution. In comparison with the analogous 4f electrons, the 5f electrons in the latter part of the series are more tightly bound. Thus, there is a lowering of the 5f energy levels with respect to the Fermi level as the atomic number increases. The metallic state of the heavier actinides has not been investigated except from the viewpoint of the relative volatility among members of the series. In aqueous solutions, ions of these elements behave as a normal trivalent actinides and lanthanides (except for nobelium). Their ionic radii decrease with increasing nuclear charge which is moderated because of increased screening of the outer 6p electrons by the 5f electrons. The actinide series of elements is completed with the element lawrencium (Lr) in which the electronic configuration is 5f/sup 14/7s/sup 2/7p. From Mendeleev's periodicity and Dirac-Fock calculations, the next group of elements is expected to be a d-transition series corresponding to the elements Hf through Hg. The chemical properties of elements 104 and 105 only have been studied and they indeed appear to show the properties expected of eka-Hf and eka-Ta. However, their nuclear lifetimes are so short and so few atoms can be produced that a rich variety of chemical information is probably unobtainable.

  20. Toward laser ablation Accelerator Mass Spectrometry of actinides

    NASA Astrophysics Data System (ADS)

    Pardo, R. C.; Kondev, F. G.; Kondrashev, S.; Nair, C.; Palchan, T.; Scott, R.; Seweryniak, D.; Vondrasek, R.; Paul, M.; Collon, P.; Deibel, C.; Youinou, G.; Salvatores, M.; Palmotti, G.; Berg, J.; Fonnesbeck, J.; Imel, G.

    2013-01-01

    A project to measure neutron capture cross sections of a number of actinides in a reactor environment by Accelerator Mass Spectrometry (AMS) at the ATLAS facility of Argonne National Laboratory is underway. This project will require the precise and accurate measurement of produced actinide isotopes in many (>30) samples irradiated in the Advanced Test Reactor at Idaho National Laboratory with neutron fluxes having different energy distributions. The AMS technique at ATLAS is based on production of highly-charged positive ions in an electron cyclotron resonance (ECR) ion source followed by acceleration in the ATLAS linac and mass-to-charge (m/q) measurement at the focus of the Fragment Mass Analyzer. Laser ablation was selected as the method of feeding the actinide material into the ion source because we expect it will have higher efficiency and lower chamber contamination than either the oven or sputtering techniques, because of a much narrower angular distribution of emitted material. In addition, a new multi-sample holder/changer to allow quick change between samples and a computer-controlled routine allowing fast tuning of the accelerator for different beams, are being developed. An initial test run studying backgrounds, detector response, and accelerator scaling repeatability was conducted in December 2010. The project design, schedule, and results of the initial test run to study backgrounds are discussed.

  1. A literature review of actinide-carbonate mineral interactions

    SciTech Connect

    Stout, D.L.; Carroll, S.A.

    1993-10-01

    Chemical retardation of actinides in groundwater systems is a potentially important mechanism for assessing the performance of the Waste Isolation Pilot Plant (WIPP), a facility intended to demonstrate safe disposal of transuranic waste. Rigorous estimation of chemical retardation during transport through the Culebra Dolomite, a water-bearing unit overlying the WIPP, requires a mechanistic understanding of chemical reactions between dissolved elements and mineral surfaces. This report represents a first step toward this goal by examining the literature for pertinent experimental studies of actinide-carbonate interactions. A summary of existing models is given, along with the types of experiments on which these models are based. Articles pertaining to research into actinide interactions with carbonate minerals are summarized. Select articles involving trace element-carbonate mineral interactions are also reviewed and may serve as templates for future research. A bibliography of related articles is included. Americium(III), and its nonradioactive analog neodymium(III), partition strongly from aqueous solutions into carbonate minerals. Recent thermodynamic, kinetic, and surface studies show that Nd is preferentially removed from solution, forming a Nd-Ca carbonate solid solution. Neptunium(V) is rapidly removed from solution by carbonates. Plutonium incorporation into carbonates is complicated by multiple oxidation states. Little research has been done on the radium(H) and thorium(IV) carbonate systems. Removal of uranyl ion from solution by calcite is limited to monolayer surface coverage.

  2. RAPID SEPARATION METHOD FOR ACTINIDES IN EMERGENCY SOIL SAMPLES

    SciTech Connect

    Maxwell, S.; Culligan, B.; Noyes, G.

    2009-11-09

    A new rapid method for the determination of actinides in soil and sediment samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used for samples up to 2 grams in emergency response situations. The actinides in soil method utilizes a rapid sodium hydroxide fusion method, a lanthanum fluoride soil matrix removal step, and a streamlined column separation process with stacked TEVA, TRU and DGA Resin cartridges. Lanthanum was separated rapidly and effectively from Am and Cm on DGA Resin. Vacuum box technology and rapid flow rates are used to reduce analytical time. Alpha sources are prepared using cerium fluoride microprecipitation for counting by alpha spectrometry. The method showed high chemical recoveries and effective removal of interferences. This new procedure was applied to emergency soil samples received in the NRIP Emergency Response exercise administered by the National Institute for Standards and Technology (NIST) in April, 2009. The actinides in soil results were reported within 4-5 hours with excellent quality.

  3. Disposition of actinides released from high-level waste glass

    SciTech Connect

    Ebert, W.L.; Bates, J.K.; Buck, E.C.; Gong, M.; Wolf, S.F.

    1994-05-01

    A series of static leach tests was conducted using glasses developed for vitrifying tank wastes at the Savannah River Site to monitor the disposition of actinide elements upon corrosion of the glasses. In these tests, glasses produced from SRL 131 and SRL 202 frits were corroded at 90{degrees}C in a tuff groundwater. Tests were conducted using crushed glass at different glass surface area-to-solution volume (S/V) ratios to assess the effect of the S/V on the solution chemistry, the corrosion of the glass, and the disposition of actinide elements. Observations regarding the effects of the S/V on the solution chemistry and the corrosion of the glass matrix have been reported previously. This paper highlights the solution analyses performed to assess how the S/V used in a static leach test affects the disposition of actinide elements between fractions that are suspended or dissolved in the solution, and retained by the altered glass or other materials.

  4. Role of Strong Correlations in Disproportionation of Aqueous Actinides

    NASA Astrophysics Data System (ADS)

    Horowitz, Steven E.

    2005-03-01

    We study the role of strong electronic correlations in the disproportionation of aqueous actinide complexes An(aq) and AnO2(aq) where An = U, Np, and Pu. Correlations are expected to be important due to the localized nature of the actinide 5f orbitals. We first confirm that relativisitic DFTootnotetextADF2004.01, SCMhttp://www.scm.com, Theoretical Chemistry, Vrije Universiteit., despite yielding reasonable geometries and bond lengths, fails to reproduceootnotetextP. J. Hay, R. L. Martin, and G. Schreckenbach, J. Phys. Chem. A 104, 6259 (2000). experimentally observed degeneracies of the redox potentialsootnotetextD. L. Clark in Los Alamos Science No. 26 Vol. II (2000).. By using a continuum model for the water beyond the first solvation sphere we are able to construct and diagonalize reduced Hubbard-like models of the actinide complexes, and incorporate the missing physics of strong intra-atomic Coulomb repulsionootnotetextM. X. LaBute et al., J. Chem. Phys. 116, 3681 (2002). ootnotetextD. V. Efremov et al., cond-mat/0303414http://arxiv.org/abs/cond-mat/?0303414; E. Runge et al., cond-mat/0402124http://arxiv.org/abs/cond-mat/?0402124..

  5. Crystalline matrices for the immobilization of plutonium and actinides

    SciTech Connect

    Anderson, E.B.; Burakov, E.E.; Galkin, Ya.B.; Starchenko, V.A.; Vasiliev, V.G.

    1996-05-01

    The management of weapon plutonium, disengaged as a result of conversion, is considered together with the problem of the actinide fraction of long-lived high level radioactive wastes. It is proposed to use polymineral ceramics based on crystalline host-phases: zircon ZrSiO{sub 4} and zirconium dioxide ZrO{sub 2}, for various variants of the management of plutonium and actinides (including the purposes of long-term safe storage or final disposal from the human activity sphere). It is shown that plutonium and actinides are able to form with these phases on ZrSiO{sub 4} and ZrO{sub 2} was done on laboratory level by the hot pressing method, using the plasmochemical calcination technology. To incorporate simulators of plutonium into the structure of ZrSiO{sub 4} and ZrO{sub 2} in the course of synthesis, an original method developed by the authors as a result of studying the high-uranium zircon (Zr,U) SiO{sub 4} form Chernobyl {open_quotes}lavas{close_quotes} was used.

  6. The EBR-II X501 Minor Actinide Burning Experiment

    SciTech Connect

    M. K. Meyer; S. L. Hayes; W. J. Carmack; H. Tsai

    2009-07-01

    The X501 experiment was conducted in EBR-II as part of the IFR (Integral Fast Reactor) program to demonstrate minor actinide burning through the use of a homogeneous recycle scheme. The X501 subassembly contained two metallic fuel elements loaded with relatively small quantities of americium and neptunium. Interest in the behavior of minor actinides (MA) during fuel irradiation has prompted further examination of existing X501 data, and generation of new data where needed in support of the U.S. waste transmutation effort. The X501 experiment is one of the few minor actinide-bearing fuel irradiation tests conducted worldwide and knowledge can be gained by understanding the changes in fuel behavior due to addition of MA’s. Of primary interest are the affect of the MA’s on fuel-cladding-chemical-interaction, and the redistribution behavior of americium. The quantity of helium gas release from the fuel and any effects of helium on fuel performance are also of interest. It must be stressed that information presented at this time is based on the limited PIE conducted in 1995-1996, and currently represents a set of observations rather than a complete understanding of fuel behavior. This paper provides a summary of the X501 fabrication, characterization, irradiation, and post irradiation examination.

  7. Behavior of actinides in the Integral Fast Reactor fuel cycle

    SciTech Connect

    Courtney, J.C.; Lineberry, M.J.

    1994-06-01

    The Integral Fast Reactor (IFR) under development by Argonne National Laboratory uses metallic fuels instead of ceramics. This allows electrorefining of spent fuels and presents opportunities for recycling minor actinide elements. Four minor actinides ({sup 237}Np, {sup 240}Pu, {sup 241}Am, and {sup 243}Am) determine the waste storage requirements of spent fuel from all types of fission reactors. These nuclides behave the same as uranium and other plutonium isotopes in electrorefining, so they can be recycled back to the reactor without elaborate chemical processing. An experiment has been designed to demonstrate the effectiveness of the high-energy neutron spectra of the IFR in consuming these four nuclides and plutonium. Eighteen sets of seven actinide and five light metal targets have been selected for ten day exposure in the Experimental Breeder Reactor-2 which serves as a prototype of the IFR. Post-irradiation analyses of the exposed targets by gamma, alpha, and mass spectroscopy are used to determine nuclear reaction-rates and neutron spectra. These experimental data increase the authors` confidence in their ability to predict reaction rates in candidate IFR designs using a variety of neutron transport and diffusion programs.

  8. The EBR-II X501 Minor Actinide Burning Experiment

    SciTech Connect

    Jon Carmack; S. L. Hayes; M. K. Meyer; H. Tsai

    2008-06-01

    The X501 experiment was conducted in EBR-II as part of the IFR (Integral Fast Reactor) program to demonstrate minor actinide burning through the use of a homogeneous recycle scheme. The X501 subassembly contained two metallic fuel elements loaded with relatively small quantities of americium and neptunium. Interest in the behavior of minor actinides (MA) during fuel irradiation has prompted further examination of existing X501 data, and generation of new data where needed in support of the U.S. waste transmutation effort. The X501 experiment is one of the few minor actinide-bearing fuel irradiation tests conducted worldwide and knowledge can be gained by understanding the changes in fuel behavior due to addition of MA’s. Of primary interest are the affect of the MA’s on fuel-cladding-chemical-interaction, and the redistribution behavior of americium. The quantity of helium gas release from the fuel and any effects of helium on fuel performance are also of interest. It must be stressed that information presented at this time is based on the limited PIE conducted in 1995-1996, and currently represents a set of observations rather than a complete understanding of fuel behavior.

  9. RAPID SEPARATION METHOD FOR ACTINIDES IN EMERGENCY AIR FILTER SAMPLES

    SciTech Connect

    Maxwell, S.; Noyes, G.; Culligan, B.

    2010-02-03

    A new rapid method for the determination of actinides and strontium in air filter samples has been developed at the Savannah River Site Environmental Lab (Aiken, SC, USA) that can be used in emergency response situations. The actinides and strontium in air filter method utilizes a rapid acid digestion method and a streamlined column separation process with stacked TEVA, TRU and Sr Resin cartridges. Vacuum box technology and rapid flow rates are used to reduce analytical time. Alpha emitters are prepared using cerium fluoride microprecipitation for counting by alpha spectrometry. The purified {sup 90}Sr fractions are mounted directly on planchets and counted by gas flow proportional counting. The method showed high chemical recoveries and effective removal of interferences. This new procedure was applied to emergency air filter samples received in the NRIP Emergency Response exercise administered by the National Institute for Standards and Technology (NIST) in April, 2009. The actinide and {sup 90}Sr in air filter results were reported in {approx}4 hours with excellent quality.

  10. Isomorphism of actinides and REE in synthetic ferrite garnets

    NASA Astrophysics Data System (ADS)

    Livshits, T. S.

    2010-02-01

    The reprocessing of spent nuclear fuel (SNF) is accompanied by the formation of liquid high-level radioactive waste (HLW). To increase the safety of handling HLW, it is proposed to extract actinide isotopes (An) and REE from them. These elements may be incorporated into crystalline matrices, e.g., based on ferrites with garnet structure, and then disposed in a geologic repository. The actinide-REE fraction is characterized by a complex composition. In addition to major components (An and REE), Al, Si, Na, and Sn occur therein in small amounts (a few wt %). Possible incorporation of the admixtures into ferrite garnets, as well as their effect on the phase composition of matrices and Th, Ce, Gd, and La contents were studied. It was shown that admixtures enter into garnet by means of isomorphic replacement. The properties of samples change only when admixtures are added in amounts exceeding their concentrations in HLW. The ability of ferrite garnets to accumulate significant amounts of An, REE, and admixture elements makes them suitable for use as matrices in immobilizing actinide-REE HLW of complex composition.

  11. Studies of Nuclear Structure and Decay Properties of Actinide Nuclei

    SciTech Connect

    Kondev, F. G.; Ahmad, I.; Carpenter, M. P.; Chiara, C. J.; Greene, J. P.; Janssens, R. V. F.; Khoo, T. L.; Lauritsen, T.; Lister, C. J.; Moore, E. F.; Seweryniak, D.; Zhu, S.; Kellett, M. A.; Nichols, A. L.

    2009-01-28

    The identification of single-particle states in heavy actinide nuclei by means of studying their decay schemes plays a seminal role in understanding the structure of the heaviest elements and testing the predictive power of modern theoretical models. The heaviest odd-mass nuclides available in sufficient quantity for detailed decay spectroscopic studies are 20-h {sup 255} Fm(for neutrons) and 20-d {sup 253}Es(for protons). Decay spectra of these isotopes, together with those for the odd-odd 276-d {sup 254}Es nuclide, were measured using a variety of {alpha}-particle and {gamma}-ray spectroscopy techniques. Well-defined decay data are also essential pre-requisites for the detection and accurate characterization of fissile radionuclides. The parameters of greatest relevance include actinide half-lives, branching fractions, and {alpha}-particle and {gamma}-ray energies and emission probabilities. Their quantification to good accuracy provides the means of monitoring their presence, behavior and transport in nuclear facilities as well as any clandestine movement and usage. As a consequence of recommendations made at recent IAEA research coordination meetings on 'Updated Decay Data Library for Actinides,' measurements were undertaken to determine specific decay data of the more inadequately defined radionuclides.

  12. Supercritical Fluid Extraction and Separation of Uranium from Other Actinides

    SciTech Connect

    Donna L. Quach; Bruce J. Mincher; Chien M. Wai

    2014-06-01

    This paper investigates the feasibility of separating uranium from other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of an extraction and counter current stripping technique, which would be a more efficient and environmentally benign technology for used nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U(VI), Np(VI), Pu(IV), and Am(III)) were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, the separation of uranium from plutonium in sc-CO2 modified with TBP was successful at nitric acid concentrations of less than 3 M in the presence of acetohydroxamic acid or oxalic acid, and the separation of uranium from neptunium was successful at nitric acid concentrations of less than 1 M in the presence of acetohydroxamic acid, oxalic acid, or sodium nitrite.

  13. Elastic properties of gas hydrate-bearing sediments

    USGS Publications Warehouse

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

    2001-01-01

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

  14. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

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

  15. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

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

  16. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

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

  17. 21 CFR 582.2729 - Hydrated sodium calcium aluminosilicate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

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

  18. 21 CFR 182.2729 - Sodium calcium aluminosilicate, hydrated.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

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

  19. Videos of Experiments from ORNL Gas Hydrate Research

    DOE Data Explorer

    Gas hydrate research performed by the Environmental Sciences Division utilizes the ORNL Seafloor Process Simulator, the Parr Vessel, the Sapphire Cell, a fiber optic distributed sensing system, and Raman spectroscopy. The group studies carbon sequestration in the ocean, desalination, gas hydrates in the solar system, and nucleation and dissociation kinetics. The videos available at the gas hydrates website are very short clips from experiments.

  20. Method for the concentration and separation of actinides from biological and environmental samples

    DOEpatents

    Horwitz, E. Philip; Dietz, Mark L.

    1989-01-01

    A method and apparatus for the quantitative recover of actinide values from biological and environmental sample by passing appropriately prepared samples in a mineral acid solution through a separation column of a dialkyl(phenyl)-N,N-dialylcarbamoylmethylphosphine oxide dissolved in tri-n-butyl phosphate on an inert substrate which selectively extracts the actinide values. The actinide values can be eluted either as a group or individually and their presence quantitatively detected by alpha counting.