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Sample records for uranyl selenates organo-neorganicheskie

  1. Topologically and geometrically flexible structural units in seven new organically templated uranyl selenates and selenite-selenates

    Science.gov (United States)

    Gurzhiy, Vladislav V.; Kovrugin, Vadim M.; Tyumentseva, Olga S.; Mikhaylenko, Pavel A.; Krivovichev, Sergey V.; Tananaev, Ivan G.

    2015-09-01

    Single crystals of seven novel uranyl oxysalts of selenium with protonated methylamine molecules, [C2H8N]2[(UO2)(SeO4)2(H2O)] (I), [C2H8N]2[(UO2)2(SeO4)3(H2O)] (II), [C4H15N3][H3O]0.5[(UO2)2(SeO4)2.93(SeO3)0.07(H2O)](NO3)0.5 (III), [C2H8N]3[H5O2][(UO2)2(SeO4)3(H2O)2]2(H2O)5 (IV), [C2H8N]2[H3O][(UO2)3(SeO4)4(HSeO3)(H2O)](H2SeO3)0.2 (V), [C4H12N]3[H3O][(UO2)3(SeO4)5(H2O)] (VI), and [C2H8N]3(C2H7N)[(UO2)3(SeO4)4(HSeO3)(H2O)] (VII) have been prepared by isothermal evaporation from aqueous solutions. Their crystal structures have been solved by direct methods and their uranyl selenate and selenite-selenate units investigated using black-and-white graphs from the viewpoints of topology of interpolyhedral linkages and isomeric variations. The crystal structure of IV is based upon complex layers with unique topology, which has not been observed previously in uranyl selenates. Investigations of the statistics and local distribution of the U-Obr-Se bond angles demonstrates that shorter angles associate with undulations, whereas larger angles correspond to planar areas of the uranyl selenite layers.

  2. Dehydration-driven evolution of topological complexity in ethylamonium uranyl selenates

    Energy Technology Data Exchange (ETDEWEB)

    Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru [Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg (Russian Federation); Krivovichev, Sergey V. [Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg (Russian Federation); Tananaev, Ivan G. [Far Eastern Federal University, Suhanova st. 8, 690950 Vladivostok (Russian Federation)

    2017-03-15

    Single crystals of four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules, (C{sub 2}H{sub 8}N){sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) (I), (C{sub 2}H{sub 8}N){sub 3}[(UO{sub 2})(SeO{sub 4}){sub 2}(HSeO{sub 4})] (II), (C{sub 2}H{sub 8}N)[(UO{sub 2})(SeO{sub 4})(HSeO{sub 3})] (III), and (C{sub 2}H{sub 8}N)(H{sub 3}O)[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (IV) have been prepared by isothermal evaporation from aqueous solutions. Uranyl-containing 1D and 2D units have been investigated using topological approach and information-based complexity measurements that demonstrate the evolution of structural units and the increase of topological complexity with the decrease of H{sub 2}O content. - Graphical abstract: Single crystals of four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules have been prepared by isothermal evaporation from aqueous solutions. Structural analysis and information-based topological complexity calculations points to the possible sequence of crystalline phases formation, showing both topological and structural branches of evolution. - Highlights: • Single crystals of four novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • Dehydration processes drives the evolution of topological complexity of 1D and 2D structural units.

  3. Syntheses, structures, and IR spectroscopic characterization of new uranyl sulfate/selenate 1D-chain, 2D-sheet and 3D-framework

    Energy Technology Data Exchange (ETDEWEB)

    Ling Jie; Sigmon, Ginger E.; Ward, Matthew; Roback, Nancy; Burns, Peter C. [Dept. of Civil Engineering and Geological Science, Univ. of Notre Dame, IN (United States)

    2010-07-01

    Three uranyl sulfates, (C{sub 6}H{sub 20}N{sub 4})[(UO{sub 2}){sub 2} . (SO{sub 4}){sub 4}(H{sub 2}O){sub 2}](H{sub 2}O){sub 6} (TETAUS), (C{sub 15}H{sub 14}N{sub 3})[(UO{sub 2}) . (SO{sub 4}){sub 2}](NO{sub 3})(H{sub 2}O){sub 2} (TPUS), and K{sub 2}[(UO{sub 2})(SO{sub 4}){sub 2}(H{sub 2}O)] . H{sub 2}O (KUS), and two uranyl selenates, K(H{sub 3}O)[(UO{sub 2}){sub 2} . (SeO{sub 4}){sub 3}(H{sub 2}O)](H{sub 2}O){sub 6} (KUSe) and (H{sub 3}O){sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3} . (H{sub 2}O)] (USe), were synthesized by slow evaporation of aqueous solutions at room temperature. TETAUS crystallizes in space group P anti 1, a = 6.7186(5) A, b = 9.2625(7) A, c = 13.1078(9) A, {alpha} = 72.337(2) , {beta} = 89.198(2) , {gamma} = 70.037(1) , V = 726.89(9) A{sup 3}, Z = 1. TPUS is triclinic, P anti 1, a = 6.9732(7) A, b = 13.569(1) A, c = 13.641(1) A, {alpha} = 111.809(2) , {beta} = 102.386(2) , {gamma} = 93.833(2) , V = 1150.0(2) A{sup 3}, Z = 2. KUS is orthorhombic, Cmca, a = 12.171(2) A, b = 16.689(3) A, c = 10.997(2) A, V = 2233.8(6) A{sup 3}, Z = 8. These uranyl sulfates are built from infinite one-dimensional uranyl sulfate chains with different topologies. KUSe is monoclinic, P2{sub 1}/n, a = 14.715(1) A, b = 10.1557(7) A, c = 15.833(1) A, {beta} = 114.415(1) , V = 2154.5(3) A{sup 3}, Z = 4. Its structure is based on a two-dimensional uranyl selenate sheet. USe crystallizes in space group P2{sub 1}/c, a = 10.6124(2) A, b = 14.7717(3) A, c = 13.7139(3) A, {beta} = 96.989(1) , V = 2133.86(8) A{sup 3}, Z = 4, with a complex three-dimensional uranyl selenate framework containing channels extending in three directions. (orig.)

  4. Synthesis and crystal structure of new uranyl selenite(IV)-selenate(VI) [C5H14N][(UO2)3(SeO4)4(HSeO3)(H2O)](H2SeO3)(HSeO4)

    International Nuclear Information System (INIS)

    Krivovichev, S.V.; Tananaev, I.G.; Myasoedov, B.F.; Kalenberg, V.

    2006-01-01

    Crystals of new uranyl selenite(IV)-selenate(VI) [C 5 H 14 N][(UO 2 ) 3 (SeO 4 ) 4 (HSeO 3 )(H 2 O)](H 2 SeO 3 )(HSeO 4 ) are obtained by the method of evaporation from aqueous solutions. Compound has triclinic lattice, space group P1-bar, a=11.7068(9), b=14.8165(12), c=16.9766(15), α=73.899(6), β=76.221(7), γ=89.361(6) Deg, V=2743.0(4) A 3 , Z=2. Laminated complexes (UO 2 ) 3 (SeO 4 ) 4 (HSeO 3 )(H 2 O)] 3- are the basis of the structure. [HSe(VI)O 4 ] - , [H 2 Se(IV)O 3 ] complexes and protonated methylbutylamine cations are disposed between layers [ru

  5. Learning Lunar Science Through the Selene Videogame

    Science.gov (United States)

    Reese, D. D.; Wood, C. A.

    2010-03-01

    Selene is a videogame to promote and assess learning of lunar science concepts. As players build and modify a Moon, Selene measures learning as it occurs. Selene is a model for 21st century learning and embedded assessment.

  6. The study of complex equilibria of uranium(VI) with selenate

    International Nuclear Information System (INIS)

    Lubal, P.; Havel, J.

    1997-01-01

    Uranyl (M)-selenate (L) complex equilibria in solution were investigated by spectrophotometry in visible range and potentiometry by means of uranyl ion selective electrode. The formation ML and ML 2 species was proved and the corresponding stability constants calculated were: log β 1 = 1.57 6 ± 0.01 6 , log β 2 = 2.42 3 ± 0.01 3 (I 3.0 mol 1 -1 Na(ClO 4 , SeO 4 ) (spectrophotometry) at 298.2 K. Using potentiometry the values for infinite dilution (I → 0 mol 1 -1 ) were: log β 1 = 2.64 ± 0.01, log β 2 ≤ 3.4 at 298.2 K. Absorption spectra of the complexes were calculated and analysed by deconvolution technique. Derivative spectrophotometry for the chemical model determination has also been successfully applied. (author)

  7. SELENE

    Indian Academy of Sciences (India)

    Institute of Space and Astronautical Science, Japan Aerospace Exploration ... launch target is rescheduled for 2006 due to delay of completion of launch vehicle, H-IIA. ... Mapping of subsurface structure using active sounding, frequency 5MHz,.

  8. Selene: A Videogame for Learning about the Moon

    Science.gov (United States)

    Wood, C. A.; Reese, D. D.

    2008-06-01

    The Selene game-based, metaphor-enhanced (GaME) learning object prepares players with concrete knowledge of basic lunar geology processes. Selene is embedded within an online research environment studying learning and assessment within videogames.

  9. On uranyl phosphites

    International Nuclear Information System (INIS)

    Avduevskaya, K.A.; Ragulina, N.B.; Rozanov, I.A.; Koval', E.M.

    1978-01-01

    The medium and single-substituted uranyl phosphites of the UO 2 HPO 3 x 3H 2 O and UO 2 (H 2 PO 3 ) 2 x3H 2 O composition were separated in crystal state for the first time. The medium phosphite is fully dehydrated above H 2 SO 4 , intermediate hydrates not being formed. Waterless phosphite decomposes at the temperature above 360 deg C into the mixture of uranium and uranyl phosphates, hydrogen being liberated. The thermal decomposition of single-substituted phosphite starts at the temperature above 150 deg C and is accompanied by the full reduction of uranium up to U(4). The product of calcination is identified as cubic UP 2 O 7

  10. Analysis Ratio of Uranyl/Urea and Uranyl/HMTA on the ComplexesUranyl-Urea and Uranyl-HMTA with Spectrophotometry Method

    International Nuclear Information System (INIS)

    Simbolon, Sahat

    2000-01-01

    Reaction between uranyl and urea and uranyl and HMTA was investigated atpH = 4 and room temperature. The result of the reaction was measured withspectrophotometer, each absorbance was pictured between mol fraction andabsorbance for uranyl - urea and uranyl - HMTA. The linear and horizontalcurve was found for reaction uranyl - urea, meanwhile S curve for thereaction uranyl and HMTA. It was found that reaction between uranyl and HMTAon mol fraction value less than 0.25 was complexes meanwhile on the range of0.25 and 0.5 the reaction between uranyl and HMTA was stoichiometries.(author)

  11. Volatile uranyl hexafluoroacetoacetonate complexes

    International Nuclear Information System (INIS)

    Dines, M.B.; Hall, R.B.; Kaldor, A.; Kramer, G.M.; Maas, E.T. Jr.

    1980-01-01

    A composition of matter is described, characterized by the formula UO 2 (CF 3 COCHCOCF 3 ).L where L is a ligand selected from isopropanol, ethanol, isobutanol, tert-butanol, methanol, tetrahydrofuran, acetone, dimethylformamide, n-propanol and ethyl acetate. A process for producing the complex comprises reacting uranyl chloride with a hexafluoroacetylacetonate dissolved in a ligand L: experimental details are given. (U.K.)

  12. Uranyl Oxalate Solubility

    Energy Technology Data Exchange (ETDEWEB)

    Leturcq, G.; Costenoble, S.; Grandjean, S. [CEA Marcoule DEN/DRCP/SCPS/LCA - BP17171 - 30207 Bagnols sur Ceze cedex (France)

    2008-07-01

    The solubility of uranyl oxalate was determined at ambient temperature by precipitation in oxalic-nitric solutions, using an initial uranyl concentration of 0.1 mol/L. Oxalic concentration varied from 0.075 to 0.3 mol/L while nitric concentration ranged between 0.75 and 3 mol/L. Dissolution tests, using complementary oxalic-nitric media, were carried out for 550 hours in order to study the kinetic to reach thermodynamic equilibrium. Similar solubility values were reached by dissolution and precipitation. Using the results, it was possible to draw the solubility surface versus oxalic and nitric concentrations and to determine both the apparent solubility constant of UO{sub 2}C{sub 2}O{sub 4}, 3H{sub 2}O (Ks) and the apparent formation constant of the first uranyl-oxalate complex UO{sub 2}C{sub 2}O{sub 4} (log {beta}1), for ionic strengths varying between 1 and 3 mol/L. Ks and log {beta}1 values were found to vary from 1.9 10{sup -8} to 9.2 10{sup -9} and from 5.95 to 6.06, respectively, when ionic strength varied from 1 to 3 mol/L. A second model may fit our data obtained at an ionic strength of 3 mol/L suggesting as reported by Moskvin et al. (1959) that no complexes are formed for [H{sup +}] at 3 M. The Ks value would then be 1.3 10{sup -8}. (authors)

  13. Uranyl sorption onto alumina

    International Nuclear Information System (INIS)

    Jacobsson, A.M.M.

    1997-01-01

    The mechanism for the adsorption of uranyl onto alumina from aqueous solution was studied experimentally and the data were modeled using a triple layer surface complexation model. The experiments were carried out at low uranium concentrations (9 x 10 -11 --5 x 10 -8 M) in a CO 2 free environment at varying electrolyte concentrations (0.01--1 M) and pH (4.5--12). The first and second acid dissociation constants, pK a1 and pK a2 , of the alumina surface were determined from potentiometric titrations to be 7.2 ± 0.6 and 11.2 ± 0.4, respectively. The adsorption of uranium was found to be independent of the electrolyte concentration. The authors therefore conclude that the uranium binds as an inner sphere complex. The results were modeled using the code FITEQL. Two reactions of uranium with the surface were needed to fit the data, one forming a uranyl complex with a single surface hydroxyl and the other forming a bridged or bidentate complex reacting with two surface hydroxyls of the alumina. There was no evidence from these experiments of site heterogeneity. The constants used for the reactions were based in part on predictions made utilizing the Hard Soft Acid Base, HSAB, theory, relating the surface complexation constants to the hydrolysis of the sorbing metal ion and the acid dissociation constants of the mineral oxide surface

  14. Barium uranyl diphosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, Anna-Gay D., E-mail: nelsoa@umich.edu [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States); Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Alekseev, Evgeny V. [Institute of Energy and Climate Research (IEK-6), Forschungszentrum Juelich Wilhelm-Johnen-Strasse, Juelich 52428 (Germany); Ewing, Rodney C. [Department of Earth and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005 (United States); Albrecht-Schmitt, Thomas E. [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States)

    2012-08-15

    Three Ba{sup 2+}/UO{sub 2}{sup 2+} methylenediphosphonates have been prepared from mild hydrothermal treatment of uranium trioxide, methylendiphosphonic acid (C1P2) with barium hydroxide octahydrate, barium iodate monohydrate, and small aliquots of HF at 200 Degree-Sign C. These compounds, Ba[UO{sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{center_dot}1.4H{sub 2}O (Ba-1), Ba{sub 3}[(UO{sub 2}){sub 4}(CH{sub 2}(PO{sub 3}){sub 2}){sub 2}F{sub 6}]{center_dot}6H{sub 2}O (Ba-2), and Ba{sub 2}[(UO{sub 2}){sub 2}(CH{sub 2}(PO{sub 3}){sub 2})F{sub 4}]{center_dot}5.75H{sub 2}O (Ba-3) all adopt layered structures based upon linear uranyl groups and disphosphonate molecules. Ba-2 and Ba-3 are similar in that they both have UO{sub 5}F{sub 2} pentagonal bipyramids that are bridged and chelated by the diphosphonate moiety into a two-dimensional zigzag anionic sheet (Ba-2) and a one-dimensional ribbon anionic chain (Ba-3). Ba-1, has a single crystallographically unique uranium metal center where the C1P2 ligand solely bridges to form [UO{sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{sup 2-} sheets. The interlayer space of the structures is occupied by Ba{sup 2+}, which, along with the fluoride ion, mediates the structure formed and maintains overall charge balance. - Graphical abstract: Illustration of the stacking of the layers in Ba{sub 3}[(UO{sub 2}){sub 4}(CH{sub 2}(PO{sub 3}){sub 2}){sub 2})F{sub 6}]{center_dot}6H{sub 2}O viewed along the c-axis. The structure is constructed from UO{sub 7} pentagonal bipyramidal units, U(1)O{sub 7}=gray, U(2)O{sub 7}=yellow, barium=blue, phosphorus=magenta, fluorine=green, oxygen=red, carbon=black, and hydrogen=light peach. Highlights: Black-Right-Pointing-Pointer The polymerization of the UO{sub 2}{sup 2+} sites to form uranyl dimers leads to structural variations in compounds. Black-Right-Pointing-Pointer Barium cations stitch uranyl diphosphonate anionic layers together, and help mediate structure formation. Black-Right-Pointing-Pointer HF acts as both a

  15. Double selenates of rare earths and ammonium

    International Nuclear Information System (INIS)

    Iskhakova, L.D.; Kozlova, N.P.; Makarevich, L.G.

    1991-01-01

    Double selenates of rare earths with ammonium were prepared in result of crystallization. It is shown that NH 4 Ln(SeO 4 ) · nH 2 O crystalline hydrates are presented by penta-and trihydrates. Existance of two modifications was revealed for NH 4 Ln(SeO 4 ) · 5H 2 O: monoclinic form of NH 4 La(SeO 4 ) 2 · 5H 2 O, isostructural RbCe(SeO 4 ) 2 · 5H 2 O, and earlier unknown rhombic form of salts with Ln = Pr, Nd. Trihydrates with Ln = Sm-Yb belong to structural type of RbNd(SeO 4 ) 2 · 3H 2 O. Anhydrous salts NH 4 Ln(SeO 4 ) 2 are isostructural with monoclinic KNd(SO 4 ) 2 modification. Lattice parameters of binary selenates are presented

  16. Selen og vitamin E til svin

    DEFF Research Database (Denmark)

    Nielsen, H. E.; Danielsen, V.; Nielsen, Gunnar Gissel

    1975-01-01

    , kan der let opstå selenmangel. Vitamin E kan i nogen grad erstatte selen, men kun indenfor visse grænser. De senere års erfaringer har tydeligt vist, at der ofte opstår selenmangel, selvom der findes rigeligt E-vitamin i foderet. Resultaterne fra dette forsøg tyder på, at en nedsættelse af...

  17. Investigation of uranyl-ion hydrolysis in uranyl pertechnetate and uranyl perchlorates solutions by two-phases potentiometric titration method

    International Nuclear Information System (INIS)

    Volk, V.I.; Belikov, A.D.

    1977-01-01

    The applicability of the method of two-phase potentiometric titration for studying hydrolysis of multi-charge ions has been shown. Hydrolysis of uranyl-ion has been investigated and hydrolysis constants in the solutions of uranyl pertechnetate and perchlorate have been calculated equal to (6.2+-0.15)x10 -5 and (9.25+-0.5)10 -5 , respectively. Infrared spectra of the initial crystallohydrates of uranyl pertechnetate and perchlorate has been analyzed. The data on hydrolysis of an uranyl-ion and IR spectra of crystallohydrates of the investigated salts have revealed the ability of pertechnetate ion to complexing with an uranyl group

  18. Charge-density matching in organic-inorganic uranyl compounds

    International Nuclear Information System (INIS)

    Krivovichev, S.V.; Krivovichev, S.V.; Tananaev, I.G.; Myasoedov, B.F.

    2007-01-01

    Single crystals of [C 10 H 26 N 2 ][(UO 2 )(SeO 4 ) 2 (H 2 O)](H 2 SeO 4 ) 0.85 (H 2 O) 2 (1), [C 10 H 26 N 2 ][(UO 2 )(SeO 4 ) 2 ] (H 2 SeO 4 ) 0.50 (H 2 O) (2), and [C 8 H 20 N] 2 [(UO 2 )(SeO 4 ) 2 (H 2 O)] (H 2 O) (3) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amines. The structures of the compounds have been solved by direct methods and structural models have been obtained. The structures of the compounds 1, 2, and 3 contain U and Se atoms in pentagonal bipyramidal and tetrahedral coordinations, respectively. The UO 7 and SeO 4 polyhedra polymerize by sharing common O atoms to form chains (compound 1) or sheets (compounds 2 and 3). In the structure of 1, the layers consisting of hydrogen-bonded [UO 2 (SeO 4 ) 2 (H 2 O)] 2- chains are separated by mixed organic-inorganic layers comprising from [NH 3 (CH 2 ) 10 NH 3 ] 2+ molecules, H 2 O molecules, and disordered electroneutral (H 2 SeO 4 ) groups. The structure of 2 has a similar architecture but a purely inorganic layer is represented by a fully connected [UO 2 (SeO 4 ) 2 ] 2- sheet. The structure of 3 does not contain disordered (H 2 SeO 4 ) groups but is based upon alternating [UO 2 (SeO 4 ) 2 (H 2 O)] 2- sheets and 1.5-nm-thick organic blocks consisting of positively charged protonated octylamine molecules, [NH 3 (CH 2 ) 7 CH 3 ] + . The structures may be considered as composed of anionic inorganic sheets (2D blocks) and cationic organic blocks self-organized according to competing hydrophilic-hydrophobic interactions. Analysis of the structures allows us to conclude that the charge-density matching principle is observed in uranyl compounds. In order to satisfy some basic peculiarities of uranyl (in general, actinyl) chemistry, it requires specific additional mechanisms: (a) in long-chain-amine-templated compounds, protonated amine molecules inter-digitate; (b) in long-chain-diamine-templated compounds, incorporation of acid-water interlayers into

  19. SELENE - Self-Forming Extensible Lunar EVA Network, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — The overall objective of this research effort (Phase I and Phase II) by Scientific Systems Company, Inc. and BBN Technologies is to develop the SELENE network --...

  20. Uranyl fluoride luminescence in acidic aqueous solutions

    International Nuclear Information System (INIS)

    Beitz, J.V.; Williams, C.W.

    1996-01-01

    Luminescence emission spectra and decay rates are reported for uranyl species in acidic aqueous solutions containing HF or added NaF. The longest luminescence lifetime, 0.269 ± 0.006 ms, was observed from uranyl in 1 M HF + 1 M HClO 4 at 296 K and decreased with increasing temperature. Based on a luminescence dynamics model that assumes equilibrium among electronically excited uranyl fluoride species and free fluoride ion, this long lived uranyl luminescence in aqueous solution is attributed primarily to UO 2 F 2 . Studies on the effect of added LiNO 3 or Na 2 WO 4 ·2H 2 O showed relatively weak quenching of uranyl fluoride luminescence which suggests that high sensitivity determination of the UF 6 content of WF 6 gas should be feasible via uranyl luminescence analysis of hydrolyzed gas samples of impure WF 6

  1. Rate of oxygen isotope exchange between selenate and water.

    Science.gov (United States)

    Kaneko, Masanori; Poulson, Simon R

    2012-04-17

    The rate of oxygen isotope exchange between selenate and water was investigated at conditions of 10 to 80 °C and pH -0.6 to 4.4. Oxygen isotope exchange proceeds as a first-order reaction, and the exchange rate is strongly affected by reaction temperature and pH, with increased rates of isotope exchange at higher temperature and lower pH. Selenate speciation (HSeO(4)(-) vs SeO(4)(2-)) also has a significant effect on the rate of isotope exchange. The half-life for isotope exchange at example natural conditions (25 °C and pH 7) is estimated to be significantly in excess of 10(6) years. The very slow rate of oxygen isotope exchange between selenate and water under most environmental conditions demonstrates that selenate-δ(18)O signatures produced by biogeochemical processes will be preserved and hence that it will be possible to use the value of selenate-δ(18)O to investigate the biogeochemical behavior of selenate, in an analogous fashion to the use of sulfate-δ(18)O to study the biogeochemical behavior of sulfate.

  2. EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

    Science.gov (United States)

    Furman, N.H.; Mundy, R.J.

    1957-12-10

    An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.

  3. Chemistry of the uranyl group

    International Nuclear Information System (INIS)

    Zarli, B.; Dall'olio, G.; Sindellari, L.

    1976-01-01

    Some uranyl complexes with hexamethylphosphoramide (HMPA) and urea were prepared and characterized. The compounds with the former ligand have the general formula UO 2 X 2 .HMPA (where X = (C 2 H 5 ) 2 NCSe 2 - , (C 2 H 5 ) 2 NCS 2 - or CH 3 COO - ). For the acetato derivatives a dimeric acetato-bridged structure is suggested. Some properties of UO 2 (NO 3 ) 2 .2(HMPA) are also described. With the latter ligand, in addition to the complexes UO 2 (NO 3 ) 2 .2urea and [UO 2 (urea) 4 (H 2 0)](NO 3 ) 2 already known, the novel complexes UO 2 (pycrate) 2 .4urea and [UO 2 (CH 3 COO) 2 .urea]sub(n) (where n is probably 2) have been prepared. All attempts to obtain urea complexes of uranyl diethyldithio- or diethyldiselenocarbamate failed and only adducts of unsatisfactory stoichiometry were isolated. (author)

  4. Determination of Proteinaceous Selenocysteine in Selenized Yeast

    Directory of Open Access Journals (Sweden)

    Katarzyna Bierla

    2018-02-01

    Full Text Available A method for the quantitation of proteinaceous selenocysteine (SeCys in Se-rich yeast was developed. The method is based on the reduction of the Se-Se and S-Se bridges with dithiotretiol, derivatization with iodoacetamide (carbamidomethylation, followed by HPLC-ICP MS. The chromatographic conditions were optimized for the total recovery of the proteinaceous selenocysteine, the minimum number of peaks in the chromatogram (reduction of derivatization products of other Se-species present and the baseline separation. A typical chromatogram of a proteolytic digest of selenized yeast protein consisted of up to five peaks (including SeMet, carbamidomethylated (CAM-SeCys, and Se(CAM2 identified by retention time matching with available standards and electrospray MS. Inorganic selenium non-specifically attached to proteins and selenomethionine could be quantified (in the form of Se(CAM2 along with SeCys. Selenocysteine, selenomethionine, inorganic selenium, and the water soluble-metabolite fraction accounted for the totality of selenium species in Se-rich yeast.

  5. Thermal analysis studies of ammonium uranyl carbonate

    International Nuclear Information System (INIS)

    Cao Xinsheng; Ma Xuezhong; Wang Fapin; Liu Naixin; Ji Changhong

    1988-01-01

    The simultaneous thermogravimetry and differential thermal analysis of the ammonium uranyl carbonate powder were performed with heat balance in the following atmosphers: Air, Ar and Ar-8%H 2 . The thermogravimetry and differential thermal analysis curves of the ammonium uranyl carbonate powder obtained from different source were reported and discussed

  6. Thin film solar cells by selenization sulfurization using diethyl selenium as a selenium precursor

    Science.gov (United States)

    Dhere, Neelkanth G.; Kadam, Ankur A.

    2009-12-15

    A method of forming a CIGSS absorber layer includes the steps of providing a metal precursor, and selenizing the metal precursor using diethyl selenium to form a selenized metal precursor layer (CIGSS absorber layer). A high efficiency solar cell includes a CIGSS absorber layer formed by a process including selenizing a metal precursor using diethyl selenium to form the CIGSS absorber layer.

  7. Preparation, characterization and thermal behaviour study of double selenates of lanthanides, yttrium and beryllium

    International Nuclear Information System (INIS)

    Ribeiro, C.A.

    1988-01-01

    The lanthanides (III) and yttrium (III) double selenates were studied using common analytical methods, atomic absorption, X-ray diffraction infra-red absorption, thermogravimetry and differential thermal analysis. These compounds were prepared from the mixture of lanthanides (III) and yttrium (III) selenates aqueous solution and basic beryllium selenates aqueous solution, obeying equimolar relation (1:1) to the cation

  8. Sorption of uranyl ions on hydrous oxides

    International Nuclear Information System (INIS)

    Gupta, A.R.; Venkataramani, B.

    1988-01-01

    Sorption of uranyl ions on hydrous titanium oxide (HTiO), magnetite (MAG), and hydrous thorium oxide (HThO) has been studied as a function of pH. Hydrous oxides have been characterized by their pH-titration curves, intrinsic dissociation constants (pK ai * ) and point of zero charge (pH pzc ). The fraction of protonated surface hydroxyl groups as well as the surface pH (pH surf ) as a function of solution pH have been computed. The distribution of various hydrolyzed species of uranyl ions with solution pH have been compared with uranyl sorption isotherm on these oxides. Sorption edge in all the cases occurs when free hydroxyl groups are available on the surface and pH surf is sufficiently high to favor the formation of dimer-like species on the surface. A new model for the sorption process, called surface hydrolysis model, which explains these and other features of uranyl sorption on hydrous oxides has been proposed. The model visualizes the sorption process as linking of uranyl ions with two adjacent free surface hydroxyl groups without deprotonation (provided the surface pH is high for the hydrolysis of uranyl ions) and formation of dimer-like structures on the surface. The new model has been successfully applied to the present and other available data on uranyl ion sorption on hydrous oxides. (author)

  9. Selective Se-for-S substitution in Cs-bearing uranyl compounds

    Energy Technology Data Exchange (ETDEWEB)

    Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru [Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia Federation (Russian Federation); Tyumentseva, Olga S.; Krivovichev, Sergey V. [Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia Federation (Russian Federation); Tananaev, Ivan G. [Far Eastern Federal University, Suhanova st. 8, Vladivostok 690950 (Russian Federation)

    2017-04-15

    Phase formation in the mixed sulfate-selenate aqueous system of uranyl nitrate and cesium nitrate has been investigated. Two types of crystalline compounds have been obtained and characterized using a number of experimental (single crystal XRD, FTIR, SEM) and theoretical (information-based complexity calculations, topological analysis) techniques. No miscibility gaps have been observed for Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se), which crystallizes in tetragonal system, P-42{sub 1}m, a =9.616(1)–9.856(2), c =8.105(1)–8.159(1) Å, V =749.6(2)–792.5(3) Å{sup 3}. Nine phases with variable amount of S and Se have been structurally characterized. The structures of the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) compounds are based upon the [(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]{sup 2-} layers of corner-sharing uranyl pentagonal bipyramids and TO{sub 4} tetrahedra. The layers contain two types of tetrahedral sites: T1 (3-connected, i.e. having three O atoms shared by adjacent uranyl polyhedra) and T2 (4-connected). The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded T2 site. Crystallization in the pure Se system starts with the formation of Cs{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) crystals, its subsequent dissolution and formation of Cs{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}]. The information-based structural complexity calculations for these two phases support the rule that more topologically complex structures form at the latest stages of crystallization. - Graphical abstract: Nine phases representing the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) solid solution series with variable amount of S and Se have been prepared by isothermal evaporation from aqueous solutions and characterized using a number of experimental and theoretical techniques. No immiscibility is observed between the

  10. Respiration of arsenate and selenate by hyperthermophilic archaea.

    Science.gov (United States)

    Huber, R; Sacher, M; Vollmann, A; Huber, H; Rose, D

    2000-10-01

    A novel, strictly anaerobic, hyperthermophilic, facultative organotrophic archaeon was isolated from a hot spring at Pisciarelli Solfatara, Naples, Italy. The rod-shaped cells grew chemolithoautotrophically with carbon dioxide as carbon source, hydrogen as electron donor and arsenate, thiosulfate or elemental sulfur as electron acceptor. H2S was formed from sulfur or thiosulfate, arsenite from arsenate. Organotrophically, the new isolate grew optimally in the presence of an inorganic electron acceptor like sulfur, selenate or arsenate. Cultures, grown on arsenate and thiosulfate or arsenate and L-cysteine, precipitated realgar (As2S2). During growth on selenate, elemental selenium was produced. The G+C content of the DNA was 58.3 mol%. Due to 16S rRNA gene sequence analysis combined with physiological and morphological criteria, the new isolate belongs to the Thermoproteales order. It represents a new species within the genus Pyrobaculum, the type species of which we name Pyrobaculum arsenaticum (type strain PZ6*, DSM 13514, ATCC 700994). Comparative studies with different Pyrobaculum-species showed, that Pyrobaculum aerophilum was also able to grow organotrophically under anaerobic culture conditions in the presence of arsenate, selenate and selenite. During growth on selenite, elemental selenium was formed as final product. In contrast to P. arsenaticum, P. aerophilum could use selenate or arsenate for lithoautotrophic growth with carbon dioxide and hydrogen.

  11. The dehydration of uranyl nitrate hexahydrate

    International Nuclear Information System (INIS)

    Badalov, A.; Kamalov, D.D.; Khamidov, B.O.; Mirsaidov, I.U.; Eshbekov, N.R.

    2010-01-01

    Present article is devoted to study of dehydration process of uranyl nitrate hexahydrate. The dehydration process of uranyl nitrate hexahydrate was studied by means of tensimeter method with membrane zero-manometer. The research was carried out under equilibrium conditions. It was defined that in studied temperature ranges (300-450 K) the dehydration process of UO_2(NO_3)_2 has a three stage character.

  12. Orbit Determination of the SELENE Satellites Using Multi-Satellite Data Types and Evaluation of SELENE Gravity Field Models

    Science.gov (United States)

    Goossens, S.; Matsumoto, K.; Noda, H.; Araki, H.; Rowlands, D. D.; Lemoine, F. G.

    2011-01-01

    The SELENE mission, consisting of three separate satellites that use different terrestrial-based tracking systems, presents a unique opportunity to evaluate the contribution of these tracking systems to orbit determination precision. The tracking data consist of four-way Doppler between the main orbiter and one of the two sub-satellites while the former is over the far side, and of same-beam differential VLBI tracking between the two sub-satellites. Laser altimeter data are also used for orbit determination. The contribution to orbit precision of these different data types is investigated through orbit overlap analysis. It is shown that using four-way and VLBI data improves orbit consistency for all satellites involved by reducing peak values in orbit overlap differences that exist when only standard two-way Doppler and range data are used. Including laser altimeter data improves the orbit precision of the SELENE main satellite further, resulting in very smooth total orbit errors at an average level of 18m. The multi-satellite data have also resulted in improved lunar gravity field models, which are assessed through orbit overlap analysis using Lunar Prospector tracking data. Improvements over a pre-SELENE model are shown to be mostly in the along-track and cross-track directions. Orbit overlap differences are at a level between 13 and 21 m with the SELENE models, depending on whether l-day data overlaps or I-day predictions are used.

  13. Charge-density matching in organic-inorganic uranyl compounds

    Energy Technology Data Exchange (ETDEWEB)

    Krivovichev, S.V. [Saint Petersburg State Univ., Dept. of Crystallography, Faculty of Geology (Russian Federation); Krivovichev, S.V.; Tananaev, I.G.; Myasoedov, B.F. [Russian Academy of Sciences, A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow (Russian Federation)

    2007-10-15

    Single crystals of [C{sub 10}H{sub 26}N{sub 2}][(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}SeO{sub 4}){sub 0.85}(H{sub 2}O){sub 2} (1), [C{sub 10}H{sub 26}N{sub 2}][(UO{sub 2})(SeO{sub 4}){sub 2}] (H{sub 2}SeO{sub 4}){sub 0.50}(H{sub 2}O) (2), and [C{sub 8}H{sub 20}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (H{sub 2}O) (3) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amines. The structures of the compounds have been solved by direct methods and structural models have been obtained. The structures of the compounds 1, 2, and 3 contain U and Se atoms in pentagonal bipyramidal and tetrahedral coordinations, respectively. The UO{sub 7} and SeO{sub 4} polyhedra polymerize by sharing common O atoms to form chains (compound 1) or sheets (compounds 2 and 3). In the structure of 1, the layers consisting of hydrogen-bonded [UO{sub 2}(SeO{sub 4}){sub 2}(H{sub 2}O)]{sup 2-} chains are separated by mixed organic-inorganic layers comprising from [NH{sub 3}(CH{sub 2}){sub 10}NH{sub 3}]{sup 2+} molecules, H{sub 2}O molecules, and disordered electroneutral (H{sub 2}SeO{sub 4}) groups. The structure of 2 has a similar architecture but a purely inorganic layer is represented by a fully connected [UO{sub 2}(SeO{sub 4}){sub 2}]{sup 2-} sheet. The structure of 3 does not contain disordered (H{sub 2}SeO{sub 4}) groups but is based upon alternating [UO{sub 2}(SeO{sub 4}){sub 2}(H{sub 2}O)]{sup 2-} sheets and 1.5-nm-thick organic blocks consisting of positively charged protonated octylamine molecules, [NH{sub 3}(CH{sub 2}){sub 7}CH{sub 3}]{sup +}. The structures may be considered as composed of anionic inorganic sheets (2D blocks) and cationic organic blocks self-organized according to competing hydrophilic-hydrophobic interactions. Analysis of the structures allows us to conclude that the charge-density matching principle is observed in uranyl compounds. In order to satisfy some basic peculiarities of uranyl (in

  14. Photochemical reduction of uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Duerksen, W.K.

    1993-10-20

    The photochemical reduction of uranyl nitrate solutions to tetravalent uranium was investigated as a means of producing uranium dioxide feed for the saltless direct oxide reduction (SDOR) process. At high uranium concentrations, reoxidation of U{sup +4} occurs rapidly. The kinetics of the nitric oxidation of tetravalent uranium depend on the concentrations of hydrogen ion, nitrate ion, nitrous acid, and tetravalent uranium in the same manner as was reported elsewhere for the nitrate oxidation of PU{sup +3}. Reaction rate data were successfully correlated with a mechanism in which nitrogen dioxide is the reactive intermediate. Addition of a nitrous acid scavenger suppresses the reoxidation reaction. An immersion reactor employing a mercury vapor lamp gave reduction times fast enough for routine production usage. Precipitation techniques for conversion of aqueous U(NO{sub 3}){sub 4} to hydrous UO{sub 2} were evaluated. Prolonged dewatering times tended to make the process time consuming. Use of 3- to 4-M aqueous NaOH gave the best dewatering times observed. Reoxidation of the UO{sub 2} by water of hydration was encountered, which required the drying process to be carried out under a reducing atmosphere.

  15. Metal complex derivatives of hydrogen uranyl phosphate

    International Nuclear Information System (INIS)

    Grohol, D.; Blinn, E.L.

    1994-01-01

    Derivatives of hydrogen uranyl phosphate were prepared by incorporating transition metal complexes into the uranyl phosphate matrix. The transition metal complexes employed include bis(ethylenediamine)copper(II), bis(1,3-propanediamine)copper(II) chloride, (triethylenetetramine)copper(II), (1,4,8,11-tetraazacyclotetradecane)copper(II), (1,4,8,12-tetraazacyclopentadecane)copper(II), (1,4,8,11-tetraazacyclotetradecane)nickel(II) chloride, (triethylenetetramine)nickel(II) and others. The chemical analyses of these derivatives indicated that the incorporation of the transition metal complexes into the uranyl phosphate matrix via ion exchange was not stoichiometric. The extent of ion exchange is dependent on the size and structure of the transition metal complex. All complexes were characterized by X-ray powder diffractometry, electronic and infrared spectra, thermal analyses and chemical analysis. An attempt was made to correlate the degree of quenching of the luminescence of the uranyl ion to the spacing between the uranyl phosphate layers in the derivatives

  16. Thermochemical investigations on uranyl phosphates and arsenates

    International Nuclear Information System (INIS)

    Barten, H.

    1986-11-01

    The results are described of a study of the thermochemical stability of anhydrous uranyl phosphates and arsenates. A number of aspects of chemical technological importance are indicated in detail. The synthesized anhydrous uranyl phosphates and arsenates were very hygroscopic, so that experiments on these compounds had to be carried out under moisture-free conditions. Further characterisation of these compounds are given, including a study of their thermal stabilities and phase relations. The uranyl phosphates reduced reversibly at temperatures of the order of 1100 to 1600 0 C. This makes it possible to express their relative stabilities quantitatively, in terms of the oxygen pressures of the reduction reactions. The thermal decomposition of uranyl arsenates did not occur by reduction, as for the phosphates, but by giving off arsenic oxide vapour. The results of measurements of enthalpies of solution led to the determination of the enthalpies of formation, heat capacity and the standard entropies of the uranyl arsenates. The thermochemical functions at high-temperatures could consequently be calculated. Attention is paid to the possible formation of uranium arsenates, whose uranium has a valency lower than six, hitherto not reported in literature. It was not possible to prepare arsenates of tetravalent uranium. However, three new compounds were observed, one of these, UAsO 5 , was studied in some detail. (Auth.)

  17. Entwicklung und Anwendung von Methoden zur Bestimmung von Selen-Spezies in human-biologischem Material

    OpenAIRE

    Jäger, Thomas

    2014-01-01

    Selen ist essentieller Bestandteil von mehr als 25 physiologisch wichtigen menschlichen Enzymen. Der tägliche Bedarf wird überwiegend in Form von organischen Selenverbindungen wie Selenmethionin oder Selenocystein aus der Nahrung aufgenommen. Weitere Expositionswege sind die Einnahme von Nahrungsergänzungsmitteln zur Selensupplementation sowie die inhalative oder dermale Aufnahme von in erster Linie anorganischen Selenverbindungen oder elementarem Selen an Arbeitsplätzen der Selen-verarbeiten...

  18. The chemical consequences of thermal neutron capture in alkali selenates

    International Nuclear Information System (INIS)

    Duplatre, G.; Vargas, J.I.

    1977-01-01

    The initial retention of the SeO 4 2- ion after thermal neutron capture has been studied in various matrices by chemical analysis. A comparison between the thermal behaviour of the chemically analyzed Sesup(IV) and the disappearance of the E.P.R. species SeO 3 - and SeO 4 3- showed that the retention fraction would include all species with oxidation state higher or equal to VI. The retentions observed in the different matrices show the existence of four families with respective retentions of: 2.6%[K 2 SeO 4 diluted in (NH 4 ) 2 SO 4 ], 9.2% [anhydrous and hydrated Li and Ca selenates; K 2 SeO 4 diluted in NaIO 3 ; Se + implanted in K 2 SeO 4 ; Triglycine selenate], 21.5% [K 2 SeO 4 diluted in KNO 3 , K 2 SO 4 , Na 2 WO 4 and Na 2 WO 4 .2H 2 O] and 32.0% [Na,K and Cs selenates]. Whereas chemical considerations may be invoked for the (NH 4 ) 2 SO 4 matrix, a mechanical model is proposed for the three other groups. (author)

  19. Variation in electrical properties of gamma irradiated cadmium selenate nanowires

    Science.gov (United States)

    Chauhan, R. P.; Rana, Pallavi; Narula, Chetna; Panchal, Suresh; Choudhary, Ritika

    2016-07-01

    Preparation of low-dimensional materials attracts more and more interest in the last few years, mainly due to the wide field of potential commercial applications ranging from life sciences, medicine and biotechnology to communication and electronics. One-dimensional systems are the smallest dimension structures that can be used for efficient transport of electrons and thus expected to be critical to the function and integration of nanoscale devices. Nanowires with well controlled morphology and extremely high aspect ratio can be obtained by replicating a nanoporous polymer ion-track membrane with cylindrical pores of controlled dimensions. With this technique, materials can be deposited within the pores of the membrane by electrochemical reduction of the desired ion. In the present study, cadmium selenate nanowires were synthesized potentiostatically via template method. These synthesized nanowires were then exposed to gamma rays by using a 60Co source at the Inter University Accelerator Centre, New Delhi, India. Structural, morphological, electrical and elemental characterizations were made in order to analyze the effect of gamma irradiation on the synthesized nanowires. I-V measurements of cadmium selenate nanowires, before and after irradiation were made with the help of Keithley 2400 source meter and Ecopia probe station. A significant change in the electrical conductivity of cadmium selenate nanowires was found after gamma irradiation. The crystallography of the synthesized nanowires was also studied using a Rigaku X-ray diffractrometer equipped with Cu-Kα radiation. XRD patterns of irradiated samples showed no variation in the peak positions or phase change.

  20. Variation in electrical properties of gamma irradiated cadmium selenate nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Chauhan, R.P., E-mail: chauhanrpc@gmail.com; Rana, Pallavi, E-mail: prana.phy@gmail.com; Narula, Chetna; Panchal, Suresh; Choudhary, Ritika

    2016-07-15

    Preparation of low-dimensional materials attracts more and more interest in the last few years, mainly due to the wide field of potential commercial applications ranging from life sciences, medicine and biotechnology to communication and electronics. One-dimensional systems are the smallest dimension structures that can be used for efficient transport of electrons and thus expected to be critical to the function and integration of nanoscale devices. Nanowires with well controlled morphology and extremely high aspect ratio can be obtained by replicating a nanoporous polymer ion-track membrane with cylindrical pores of controlled dimensions. With this technique, materials can be deposited within the pores of the membrane by electrochemical reduction of the desired ion. In the present study, cadmium selenate nanowires were synthesized potentiostatically via template method. These synthesized nanowires were then exposed to gamma rays by using a {sup 60}Co source at the Inter University Accelerator Centre, New Delhi, India. Structural, morphological, electrical and elemental characterizations were made in order to analyze the effect of gamma irradiation on the synthesized nanowires. I–V measurements of cadmium selenate nanowires, before and after irradiation were made with the help of Keithley 2400 source meter and Ecopia probe station. A significant change in the electrical conductivity of cadmium selenate nanowires was found after gamma irradiation. The crystallography of the synthesized nanowires was also studied using a Rigaku X-ray diffractrometer equipped with Cu-Kα radiation. XRD patterns of irradiated samples showed no variation in the peak positions or phase change.

  1. Inhibition of synthesis of heparan sulfate by selenate: Possible dependence on sulfation for chain polymerization

    International Nuclear Information System (INIS)

    Dietrich, C.P.; Nader, H.B.; Buonassisi, V.; Colburn, P.

    1988-01-01

    Selenate, a sulfation inhibitor, blocks the synthesis of heparan sulfate and chondroitin sulfate by cultured endothelial cells. In contrast, selenate does not affect the production of hyaluronic acid, a nonsulfated glycosaminoglycan. No differences in molecular weight, [ 3 H]glucosamine/[ 35 S]sulfuric acid ratios, or disaccharide composition were observed when the heparan sulfate synthesized by selenate-treated cells was compared with that of control cells. The absence of undersulfated chains in preparations from cultures exposed to selenate supports the concept that, in the intact cell, the polymerization of heparan sulfate might be dependent on the sulfation of the saccharide units added to the growing glycosaminoglycan chain

  2. Photochemical reduction of uranyl ion with triphenylphosphine

    International Nuclear Information System (INIS)

    Brar, A.S.; Sidhu, M.S.; Sandhu, S.S.

    1981-01-01

    Photochemical reduction of uranyl ion with triphenylphosphine has been studied in acetone-water medium in the presence of sulphuric acid at 346nm, 400nm and 434nm wavelengths. The photochemical reduction is of second order and increases with increase in hydrogen ion concentration. Absorption spectra of uranyl ion in acidic medium and uranyl ion with triphenylphosphine do not show any ground state complex formation. The value of quantum yield increases with the wavelength of the radiation increase from 346 to 434nm. Plots of reciprocal of quantum yield for the formation of U(IV) versus reciprocal [triphenylphosphine] are linear. Products characterized by UV and visible, IR and TLC show the formation of U(IV) and triphenylphosphine oxide. On the basis of above observations mechanism of the photochemical reduction has been proposed. (author)

  3. Infrared Spectroscopy of Discrete Uranyl Anion Complexes

    International Nuclear Information System (INIS)

    Groenewold, G. S.; Gianotto, Anita K.; McIIwain, Michael E.; Van Stipdonk, Michael J.; Kullman, Michael; Moore, David T.; Polfer, Nick; Oomens, Jos; Infante, Ivan A.; Visscher, Lucas; Siboulet, Bertrand; De Jong, Wibe A.

    2008-01-01

    The Free-Electron Laser for Infrared Experiments (FELIX) w 1 as used to study the wavelength-resolved multiple photon photodissociation of discrete, gas phase uranyl (UO2 2 2+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was either hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands, and are comparable to solution phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm-1 higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data, and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity

  4. Thermal decomposition of uranyl sulphate hydrate

    International Nuclear Information System (INIS)

    Sato, T.; Ozawa, F.; Ikoma, S.

    1980-01-01

    The thermal decomposition of uranyl sulphate hydrate (UO 2 SO 4 .3H 2 O) has been investigated by thermogravimetry, differential thermal analysis, X-ray diffraction and infrared spectrophotometry. As a result, it is concluded that uranyl sulphate hydrate decomposes thermally: UO 2 SO 4 .3H 2 O → UO 2 SO 4 .xH 2 O(2.5 = 2 SO 4 . 2H 2 O → UO 2 SO 4 .H 2 O → UO 2 SO 4 → α-UO 2 SO 4 → β-UO 2 SO 4 → U 3 O 8 . (author)

  5. Extraction of uranyl sulfate with primary amine

    International Nuclear Information System (INIS)

    Mrnka, M.; Bizek, V.; Nekovar, P.; Cizevska, S.; Schroetterova, D.

    1984-01-01

    PRIMENE JM-T was used for extraction. Its composition was found to approach the general formula C 21 H 43 NH 2 . It was found that the extraction of uranyl sulfate is lower in case of a higher steady-state concentration of sulfuric acid in the aqueous phase. Extraction is accompanied with coextraction of water. The results obtained showed that uranyl sulfate passes into the organic phase by two mechanisms: extraction with amine sulfate and extraction with free amine. A mathematical description of the process was made based on the obtained results. (E.S.)

  6. Splitting of the luminescent excited state of the uranyl ion

    International Nuclear Information System (INIS)

    Flint, C.D.; Sharma, P.; Tanner, P.A.

    1982-01-01

    The luminescence spectra of some uranyl compounds has been studied. It has been proposed that the splitting of the luminescent excited state of the uranyl ion is due to a descent in symmetry experienced by the uranyl ion when it is placed in a crystal field. In recent years there has been developed a highly successful model of the electronic structure of the uranyl ion. In this paper the authors use this model to interpret the luminescence spectra of a variety of uranyl compounds

  7. Luminescence enhancement of uranyl ion by benzoic acid in acetonitrile

    International Nuclear Information System (INIS)

    Satendra Kumar; Maji, S.; Joseph, M.; Sankaran, K.

    2014-01-01

    Uranyl ion is known for its characteristic green luminescence and therefore luminescence spectroscopy is a suitable technique for characterizing different uranyl species. In aqueous medium, luminescence of uranyl ion is generally weak due to its quenching by water molecules and therefore in order to enhance the luminescence of uranyl ion in aqueous medium, luminescence enhancing reagents such as H 3 PO 4 , H 2 SO 4 , HCIO 4 have been widely used. The other method to enhance the uranyl luminescence is by ligand sensitized luminescence, a method well established for lanthanides. In this work, luminescence of uranyl ion is found to be enhanced by benzoic acid in acetonitrile medium. In aqueous medium benzoic acid does not enhance the uranyl luminescence although it forms 1:1 and 1:2 complexes with uranyl ion. Luminescence spectra of uranyl benzoate revealed that enhancement is due to sensitization of uranyl luminescence by benzoate ions. UV-Vis spectroscopy has been utilized to characterize the specie formed in the in acetonitrile medium. UV-Vis spectroscopy along with luminescence spectra revealed that the specie to be tribenzoate complex of uranyl (UO 2 (C 6 H 5 COO) 3 ) - having D 3 h symmetry. (author)

  8. Uranyl tris-beta-diketonate complexes

    International Nuclear Information System (INIS)

    Sidorenko, G.V.; Adamov, V.M.; Shcherbakova, L.L.; Suglubov, D.N.

    1986-01-01

    Uranyl tris-pivaloyltrifluoroacetonates (M/IOTA/UO 2 L 3 ; M/IOTA/ = Na, K, Cs, 1/2Ba, NR 4 ; R = C 8 H 17 ) and tris-dipivaloylmethanate (M/IOTA/UO 2 L/IOTA/ 3 , M/IOTA/ = K) have been synthesized for the first time. The compounds were characterized by chemical analysis and IR, NMR, and mass spectra. NaUO 2 L 3 , KUO 2 L 3 , CsUO 2 L 3 and Ba(UO 2 ) 2 L 6 sublime in high vacuum with partial decomposition. Specifically, decomposition gives UL 4 , identified by mass spectrometry. All the tris-complexes except those with outer-sphere NR 4 cation are characterized by an asymmetric structure of the uranyl group, recorded by IR spectroscopy using isotopic substitution of 18 O in uranyl. NMR spectra of the tris-complexes indicate the equivalence of all beta-diketonate groups, i.e., a coordination number of six for uranyl

  9. Photochemical reduction of uranyl ion with amides

    International Nuclear Information System (INIS)

    Brar, A.S.; Chander, R.; Sandhu, S.S.

    1981-01-01

    The photochemical reduction of uranyl ion by formamide, acetamide, propionamide, butyramide, iso butyramids, n-methylformamide, N, N-dimethylformamide and N, N-diethylformamide in aqueous medium using radiation >= 380 nm from a medium pressure mercury vapour lamp has been investigated. The reduction with the said amides has been found to obey pseudo first order kinetics. The magnitude of the rate of reduction for the simple amides has been found to follow the following order formamide > isobutyramide approx. butyramide > propionamide > acetamide while the rate order for N-alkylformamides compared with that of the formamide has been found to be formamide > N-methylformamide > N,N-diethylformamide approx. N,N-dimethylformamide. The pseudo first order rate constants and quenching constants have been found from the kinetic data. It has been found that physical and chemical quenching compete with each other. Plots of reciprocal of quantum yields versus reciprocal [amide] have been found to be linear with intercepts on the ordinate axis. Absorption spectra of uranyl ion in doubly distilled water, in the presence of acid and in the presence of acid and amide reveal that there is no ground state interaction between uranyl ion and the amide. A mechanism of photoreduction of uranyl ion with amides has been proposed. (author)

  10. Treatment of uranyl nitrate and flouride solutions

    International Nuclear Information System (INIS)

    Rodrigo Otero, A.; Rodrigo Vilaseca, F.; Morales Calvo, G.

    1977-01-01

    A theoretical study on the fluoride complexes contained in uranyl and aluminium solutions has been carried out. Likewise concentration limits and Duhring diagrams for those solutions have been experimentally established. As a result, the optimum operation conditions for concentration by evaporation in the treatment plant, have been deduced. (Author) 12 refs

  11. Scaling Equation of State for Ferroelectric Triglycine Selenate at T ≈ Tc

    NARCIS (Netherlands)

    Iglesias, T.; Noheda, B.; Gallego, B.; Fernández del Castillo, J.R.; Lifante, G.; Gonzalo, J.A.

    1994-01-01

    Digital data of polarization vs. field on triglycine selenate at closely spaced temperature intervals (ΔT ≈ 0.015) in the vicinity of the quasi-tricritical point of triglycine selenate have been collected. These data fulfill very well the scaling equation of state ê± = ±p + (1/5)p5 (where ê- and ê+

  12. Thermal decomposition of double selenates of lanthanides (III), yttrium (III) and ammonium

    International Nuclear Information System (INIS)

    Crespi, M.S.

    1989-01-01

    Double selenates of lanthanides, yttrium and ammonium were prepared by treating mixtures of simple selenates with equimolar amounts and then dried in a vacuum desiccator containing anhydrous calcium chloride, protected from light. The compounds were studied using the conventional analytical methods such as infrared absorption spectra, X-ray diffraction, differential thermal analysis (DTA), and thermogravimetry (TG). (author)

  13. Modeling selenate adsorption behavior on oxides, clay minerals, and soils using the triple layer model

    Science.gov (United States)

    Selenate adsorption behavior was investigated on amorphous aluminum oxide, amorphous iron oxide, goethite, clay minerals: kaolinites, montmorillonites, illite, and 18 soil samples from Hawaii, and the Southwestern and the Midwestern regions of the US as a function of solution pH. Selenate adsorpti...

  14. Uptake and Distribution of Added Selenite and Selenate by Barley and Red Clover as Influenced by Sulphur

    DEFF Research Database (Denmark)

    Nielsen, Gunnar Gissel

    1973-01-01

    The uptake of added Se from selenite and selenate by barley and red clover was investigated in a pot experiment. Much more of selenate than of selenite was taken up but the Se concentrations in the plants declined more with time when selenate was the source. Increasing sulphate addition to the soil...

  15. The influence of temperature on selenate adsorption by goethite

    Energy Technology Data Exchange (ETDEWEB)

    Kersten, M.; Vlasova, N. [Mainz Univ. (Germany). Geosciences Inst.

    2013-08-01

    Acid-base batch titration data up to 75 C were used to constrain a temperature-dependent 1-pK basic Stern model of the surface protonation reactions of goethite. Experimental data for the temperature dependence of pH{sub PZC} (as determined using the two-term Van't Hoff extrapolation) yielded a negative value of -44.9 kJ/mol for the surface protonation enthalpy, and therefore a shift of the zero point of charge towards lower pH values with increasing temperature. Batch titrations at selenate concentrations of between 10 and 100 {mu}M showed an increased degree of adsorption in the acidic pH range, which appeared to be sensitive to the ionic strength of the solution. The selenate adsorption edges shifted towards more acidic pH values with increasing temperature. A 1-pK charge distribution multi-site surface complexation (CD-MUSIC) model was applied, assuming the formation of an outer-spheric surface complex together with an inner-spheric one, in agreement with published spectroscopic information. The temperature behaviour of the intrinsic equilibrium constants were well represented by a linear Van't Hoff log K vs. 1/T plot, from which negative enthalpy values could be derived for both adsorption reactions. The adsorption of the selenate was therefore exothermic and became weaker with increasing temperature. The bidentate inner-spheric complex was more sensitive to rises in temperature (-70 kJ/mol), compared to the outer-spheric complex (-36 kJ/mol). The latter ultimately became the dominating adsorption process at the highest temperature studied. (orig.)

  16. The influence of temperature on selenate adsorption by goethite

    International Nuclear Information System (INIS)

    Kersten, M.; Vlasova, N.

    2013-01-01

    Acid-base batch titration data up to 75 C were used to constrain a temperature-dependent 1-pK basic Stern model of the surface protonation reactions of goethite. Experimental data for the temperature dependence of pH PZC (as determined using the two-term Van't Hoff extrapolation) yielded a negative value of -44.9 kJ/mol for the surface protonation enthalpy, and therefore a shift of the zero point of charge towards lower pH values with increasing temperature. Batch titrations at selenate concentrations of between 10 and 100 μM showed an increased degree of adsorption in the acidic pH range, which appeared to be sensitive to the ionic strength of the solution. The selenate adsorption edges shifted towards more acidic pH values with increasing temperature. A 1-pK charge distribution multi-site surface complexation (CD-MUSIC) model was applied, assuming the formation of an outer-spheric surface complex together with an inner-spheric one, in agreement with published spectroscopic information. The temperature behaviour of the intrinsic equilibrium constants were well represented by a linear Van't Hoff log K vs. 1/T plot, from which negative enthalpy values could be derived for both adsorption reactions. The adsorption of the selenate was therefore exothermic and became weaker with increasing temperature. The bidentate inner-spheric complex was more sensitive to rises in temperature (-70 kJ/mol), compared to the outer-spheric complex (-36 kJ/mol). The latter ultimately became the dominating adsorption process at the highest temperature studied. (orig.)

  17. Preparation of SnSe thin films by encapsulated selenization

    International Nuclear Information System (INIS)

    Sabar D. Hutagalung; Samsudi Sakrani; Yussof Wahab

    1994-01-01

    Tin selenide thin films were prepared by encapsulated selenization. A stacked layer of evaporated Sn and Se films were annealed in a carbon block at temperatures 100 - 500 degree Celsius for 3 hours. X-ray analysis and SEM (Scanning electron) micrograph results showed that SnSe was initially formed at 150 degree Celsius with crystal size 30.0 nm and reached optimum formation at 200 daximum of 57.4 % yield of 5-decene. Other factors such as reaction temperatures, types of solvent and wt% of rhenium loadings influence the activity of the catalytic system

  18. Characteristics of CuInSe sub 2 thin films grown by the selenization method

    CERN Document Server

    Kim, S D; Adurodija, F O; Yoon, K H; Song, J S

    1999-01-01

    CuInSe sub 2 thin films were formed from a selenization of co-sputtered Cu-In alloy layers which consisted of only two phases, CuIn sub 2 and Cu sub 1 sub 1 In sub 9. A linear dependence of the Cu-In alloy film composition on the Cu/In sputtering power was found. The metallic layers were selenized in vacuum or at 1 atm. A small number of Cu-Se and In-Se compounds was observed during the early stage of selenization, and single-phase CuInSe sub 2 was more easily formed in vacuum than at atmospheric pressure. Therefore, CuInSe sub 2 films selenized in vacuum showed larger grain sizes, smoother surfaces, and denser microstructures than those selenized at 1 atm.

  19. Characteristics of CuInSe2 thin films grown by the selenization method

    International Nuclear Information System (INIS)

    Kim, Sang Deok; Kim, Hyeong Joon; Adurodija, Frederick Ojo; Yoon, Kyeong Hoon; Song, Jin Soo

    1999-01-01

    CuInSe 2 thin films were formed from a selenization of co-sputtered Cu-In alloy layers which consisted of only two phases, CuIn 2 and Cu 11 In 9 . A linear dependence of the Cu-In alloy film composition on the Cu/In sputtering power was found. The metallic layers were selenized in vacuum or at 1 atm. A small number of Cu-Se and In-Se compounds was observed during the early stage of selenization, and single-phase CuInSe 2 was more easily formed in vacuum than at atmospheric pressure. Therefore, CuInSe 2 films selenized in vacuum showed larger grain sizes, smoother surfaces, and denser microstructures than those selenized at 1 atm

  20. Selenate as a novel ligand for keplerate chemistry. New {W72Mo60} keplerates with selenates inside the cavity.

    Science.gov (United States)

    Korenev, Vladimir S; Abramov, Pavel A; Vicent, Cristian; Zhdanov, Artem A; Tsygankova, Alphiya R; Sokolov, Maxim N; Fedin, Vladimir P

    2015-05-21

    The synthesis and characterization of three novel keplerate-type compounds containing the {W72Mo60} mixed-metal core are reported. Complexes (NH4)72[{W6O21(H2O)6}12{Mo2O4(SeO4)}30]·150H2O·6(NH4)2SeO4 (1a) and (NH4)25(NH2Me2)47[{W6O21(H2O)6}12{Mo2O4(SeO4)}30]·130H2O·3(NH4)2SeO4 (1b) were prepared by ligand substitution from the acetate anionic complex [{W6O21(H2O)5(CH3COO)0.5}12{Mo2O4(CH3COO)}30](48-) and selenate. The selenate anions in keplerate ions [{W6O21(H2O)6}12{Mo2O4(SeO4)}30](72-) are very labile and easily aquate with the formation of [{W6O21(H2O)6}12{Mo2O4}30(SeO4)20(H2O)20](52-), which was isolated as (NH4)20(NH2Me2)32[{W6O21(H2O)6}12{Mo2O4}30(SeO4)20(H2O)20]·150H2O (2) and structurally characterized. In the crystal structure of 2 selenate has several coordination modes, preferentially bonding to the {Mo2O4}(2+) units, and, additionally, to the {(W)W5} pentagonal blocks. The compounds have been characterized by elemental analysis, Raman, IR and (77)Se NMR spectroscopy, and by ESI mass spectrometry. Capillary electrophoresis was used for characterization of keplerates in solution for the first time.

  1. Separation of uranyl ion using polyaniline

    International Nuclear Information System (INIS)

    Jayshree Ramkumar; Chandramouleeswaran, S.

    2013-01-01

    Polyaniline (Pani) was synthesized by the chemical oxidation of aniline. The use of persulphate instead of dichromate was desired in order to avoid the incorporation of chromium in the polymer matrix. The presence of chromium in the matrix, when dichromate was used as an oxidant, was confirmed by various techniques. The batch mode experiments showed that Pani could be used for separation of different metal ions. These ions were converted into their anionic complexes using suitable complexing agents. It was found that EDTA was used as a suitable reagent for the separation of Cu 2+ from Zn 2+ whereas the uranyl ion uptake could be increased to about 95 % when carbonate was used instead of EDTA as complexing agent. A possible application of the above exchange system to preconcentration of uranyl ion from seawater has also been examined. (author)

  2. Micro-SHINE Uranyl Sulfate Irradiations at the Linac

    Energy Technology Data Exchange (ETDEWEB)

    Youker, Amanda J. [Argonne National Lab. (ANL), Argonne, IL (United States); Kalensky, Michael [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey [Argonne National Lab. (ANL), Argonne, IL (United States); Schneider, John [Argonne National Lab. (ANL), Argonne, IL (United States); Byrnes, James [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2016-08-01

    Peroxide formation due to water radiolysis in a uranyl sulfate solution is a concern for the SHINE Medical Technologies process in which Mo-99 is generated from the fission of dissolved low enriched uranium. To investigate the effects of power density and fission on peroxide formation and uranyl-peroxide precipitation, uranyl sulfate solutions were irradiated using a 50-MeV electron linac as part of the micro-SHINE experimental setup. Results are given for uranyl sulfate solutions with both high and low enriched uranium irradiated at different linac powers.

  3. Cyanex based uranyl sensitive polymeric membrane electrodes.

    Science.gov (United States)

    Badr, Ibrahim H A; Zidan, W I; Akl, Z F

    2014-01-01

    Novel uranyl selective polymeric membrane electrodes were prepared using three different low-cost and commercially available Cyanex extractants namely, bis(2,4,4-trimethylpentyl) phosphinic acid [L1], bis(2,4,4-trimethylpentyl) monothiophosphinic acid [L2] and bis(2,4,4-trimethylpentyl) dithiophosphinic acid [L3]. Optimization and performance characteristics of the developed Cyanex based polymer membrane electrodes were determined. The influence of membrane composition (e.g., amount and type of ionic sites, as well as type of plasticizer) on potentiometric responses of the prepared membrane electrodes was studied. Optimized Cyanex-based membrane electrodes exhibited Nernstian responses for UO₂(2+) ion over wide concentration ranges with fast response times. The optimized membrane electrodes based on L1, L2 and L3 exhibited Nernstian responses towards uranyl ion with slopes of 29.4, 28.0 and 29.3 mV decade(-1), respectively. The optimized membrane electrodes based on L1-L3 showed detection limits of 8.3 × 10(-5), 3.0 × 10(-5) and 3.3 × 10(-6) mol L(-1), respectively. The selectivity studies showed that the optimized membrane electrodes exhibited high selectivity towards UO₂(2+) ion over large number of other cations. Membrane electrodes based on L3 exhibited superior potentiometric response characteristics compared to those based on L1 and L2 (e.g., widest linear range and lowest detection limit). The analytical utility of uranyl membrane electrodes formulated with Cyanex extractant L3 was demonstrated by the analysis of uranyl ion in different real samples for nuclear safeguards verification purposes. The results obtained using direct potentiometry and flow-injection methods were compared with those measured using the standard UV-visible and inductively coupled plasma spectroscopic methods. © 2013 Published by Elsevier B.V.

  4. Studies on conductance of uranyl soaps

    International Nuclear Information System (INIS)

    Mehrotra, K.N.; Sharma, M.; Gahlaut, A.S.

    1987-01-01

    Specific conductance of uranyl soaps in dimethylformamide indicates two critical micelle concentrations CMC(I) and CMC(II). The value of CMC(II) decreases with the increase in chain length of the soap, whereas CMC(I) does not vary at all. The results show that the soaps behave as simple electrolyte. The major conductance at infinite dilution (μsub(o)) and dissociation constant (K) of these soaps have been evaluated. (author). 12 refs

  5. Thermal decomposition kinetics of ammonium uranyl carbonate

    International Nuclear Information System (INIS)

    Kim, E.H.; Park, J.J.; Park, J.H.; Chang, I.S.; Choi, C.S.; Kim, S.D.

    1994-01-01

    The thermal decomposition kinetics of AUC [ammonium uranyl carbonate; (NH 4 ) 4 UO 2 (CO 3 ) 3 [ in an isothermal thermogravimetric (TG) reactor under N 2 atmosphere has been determined. The kinetic data can be represented by the two-dimensional nucleation and growth model. The reaction rate increases and activation energy decreases with increasing particle size and precipitation time which appears in the particle size larger than 30 μm in the mechano-chemical phenomena. (orig.)

  6. The bare uranyl(2+) ion, UO22+

    International Nuclear Information System (INIS)

    Cornehl, H.H.; Heinemann, C.; Marcalo, J.; Pires de Matos, A.; Schwarz, H.

    1996-01-01

    Ion-molecule reactions between U 2+ and oxygen donors or charge-stripping collisions between singly charged UO 2 2 ions and O 2 collision partners generate uranyl(2+) ions in the gas phase. These do not readily dissociate into singly charged fragments. The standard enthalpy of formation for UO 2 2+ is estimated to be 371±60 kcal mol -1 , in accord with the results of ab initio calculations. (orig.)

  7. Process for obtaining ammonium uranyl tri carbonate

    International Nuclear Information System (INIS)

    Santos, L.R. dos; Riella, H.G.

    1992-01-01

    The procedure adopted for obtaining Ammonium Uranyl Carbonate (AUC) from uranium hexafluoride (U F 6 ) in a aqueous solutions of ammonium hydrogen carbonate is described in this work. The precipitation is made in temperature and pH controlled. This process consists of three steps: evaporation of U F 6 , AUC precipitation and filtration of the AUC slurry. An attempt is made of correlate the parameters involved in the precipitation process of AUC with its and U O 2 characteristics. (author)

  8. Spectroscopic characterization of alkaline earth uranyl carbonates

    International Nuclear Information System (INIS)

    Amayri, Samer; Reich, Tobias; Arnold, Thuro; Geipel, Gerhard; Bernhard, Gert

    2005-01-01

    A series of alkaline uranyl carbonates, M[UO 2 (CO 3 ) 3 ].nH 2 O (M=Mg 2 , Ca 2 , Sr 2 , Ba 2 , Na 2 Ca, and CaMg) was synthesized and characterized by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS) after nitric acid digestion, X-ray powder diffraction (XRD), and thermal analysis (TGA/DTA). The molecular structure of these compounds was characterized by extended X-ray absorption fine-structure (EXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). Crystalline Ba 2 [UO 2 (CO 3 ) 3 ].6H 2 O was obtained for the first time. The EXAFS analysis showed that this compound consists of (UO 2 )(CO 3 ) 3 clusters similar to the other alkaline earth uranyl carbonates. The average U-Ba distance is 3.90+/-0.02A.Fluorescence wavelengths and life times were measured using time-resolved laser-induced fluorescence spectroscopy (TRLFS). The U-O bond distances determined by EXAFS, TRLFS, XPS, and Raman spectroscopy agree within the experimental uncertainties. The spectroscopic signatures observed could be useful for identifying uranyl carbonate species adsorbed on mineral surfaces

  9. Magnetic biosorbent for removal of uranyl ions

    International Nuclear Information System (INIS)

    Yamamura, Amanda P.G.; Yamaura, Mitiko; Costa, Caroline H.

    2009-01-01

    In this work magnetic biosorbent, which consisted of sugarcane bagasse as polymeric matrix with magnetite nanoparticles, was prepared. This magnetic composite has the purpose to remove uranyl ions from aqueous effluents. The magnetite was synthetized by simultaneous precipitation by addition a solution of NaOH to the aqueous solution containing Fe2+ and Fe3+. This magnetic bagasse biosorbent have presented superparamagnetic properties, that is, it have showed a high magnetization of saturation without hysteresis. The magnetic biosorbent was utilized to remove uranyl ions from water. Radioactive uranium waste is generated in hospitals, universities and it is used as fuel for nuclear power plants. Variables of adsorption process of uranyl ions by magnetic biosorbent in nitric solutions were investigated, such as, time required for the uranium-magnetic bagasse biosorbent equilibrium in the interval from 20 to 90 min, pH in the intervals from 2 to 5 and 10, stirring speed from 240 to 500 r.p.m. and biosorbent dose from 2 to 25 g.L-1 were investigated. Equilibrium isotherm was verified according to the Langmuir and Freundlich adsorption isotherm models. The highest adsorption capacity reached 17 mg.g-1. The Gibbs free energy indicated to be spontaneous adsorption. This work updates the paper was presented on the 2007 INAC.

  10. Thermochemical investigations on uranyl phosphates and arsenates

    International Nuclear Information System (INIS)

    Barten, H.

    1986-01-01

    Results are described of a study of the thermochemical stability of anhydrous phosphates and arsenates. The results of phase studies deal with compound formation and characterization, coexisting phases and limiting physical or chemical properties. The uranyl phosphates evolve oxygen at higher temperatures and the arsenates lose arsenic oxide vapour. These phenomena give the possibility to describe their thermodynamic stabilities. Thus oxygen pressures of uranyl phosphates have been measured using a static, non-isothermal method. Having made available the pure anhydrous compounds in the course of this investigation, molar thermodynamic quantities have been measured as well. These include standard enthalpies of formation from solution calorimetry and high-temperature heat-capacity functions derived from enthalpy increments measured. Some attention is given to compounds with uranium in valencies lower than six which have been met during the investigation. An evaluation is made of the thermodynamics of the compounds studied, to result in tabulized high-temperature thermodynamic functions. Relative stabilities within the systems are discussed and comparisons of the uranyl phosphates and the arsenates are made. (Auth.)

  11. Simultaneous selenate reduction and denitrification by a consortium of enriched mine site bacteria.

    Science.gov (United States)

    Subedi, Gaurav; Taylor, Jon; Hatam, Ido; Baldwin, Susan A

    2017-09-01

    Increasing selenium concentrations in aquatic environments downstream of mine sites is of great concern due to selenium's bioaccumulation propensity and teratogenic toxicity. Removal of selenium from mine influenced water is complicated by the presence of nitrate, which is also elevated in mine influenced water due to the use of explosives in mining. In many biological treatment processes, nitrate as a thermodynamically more preferable electron acceptor inhibits selenate reduction. Here we report on an enrichment of a bacterial assemblage from a mine impacted natural marsh sediment that was capable of simultaneous selenate reduction and denitrification. Selenate reduction followed first order kinetics with respect to the concentration of total dissolved selenium. The kinetic rate constant was independent of initial nitrate concentration over the range 3-143 mg L -1 -NO 3 - -N. The initial concentration of selenate inhibited selenate reduction kinetics over the range 1-24 mg-Se L -1 . Dominant taxa that grew in selenate only medium were classified in the genera Pseudomonas, Lysinibacillus and Thauera. When nitrate was introduced in addition to selenate, previously rare taxa that became dominant were relatives of Exiguobacterium, Tissierella and Clostridium. Open reading frames (ORFs) associated with dissimilatory denitrification were identified for Pseudomonas, Thauera and Clostridium. In addition, ORFs were found that were homologous with known selenate reductase subunits (SerA and SerB). These findings suggest that native mine site bacteria can be used for removing selenate and nitrate from mine wastewater. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

  12. Uranyl sulfate irradiations at the Van de Graaff: A means to combat uranyl peroxide precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Youker, Amanda J. [Argonne National Lab. (ANL), Argonne, IL (United States); Kalensky, Michael [Argonne National Lab. (ANL), Argonne, IL (United States); Quigley, Kevin J. [Argonne National Lab. (ANL), Argonne, IL (United States); Brossard, Thomas [Argonne National Lab. (ANL), Argonne, IL (United States); Chemerisov, Sergey D. [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2017-05-01

    As part of an effort to support SHINE Medical Technologies in developing a process to produce Mo-99 by neutron-induced fission, a series of irradiation experiments was performed with a 3 MeV Van de Graaff accelerator to generate high radiation doses in 0.5–2 mL uranyl sulfate solutions. The purpose was to determine what conditions result in uranyl peroxide precipitation and what can be done to prevent its formation. The effects of temperature, dose rate, uranium concentration, and the addition of known catalysts for the destruction of peroxide were determined.

  13. Determination of uranyl ion by potentiometric titration using an uranyl-selective electrode

    International Nuclear Information System (INIS)

    Nassory, N.S.

    1990-01-01

    A potentiometric titration of uranyl ion is described using an uranyl selective electrode based on a membrane containing a complex of UO 2 -bis[di-4-(1,1,3,3-tetramethylbutyl)phenyl phosphate] as an ion-exchanger and tritolyl phosphate as a solvent mediator. The titrations were carried out with various titrants: Sodium hydroxide, potassium fluoride and sodium salts of acetate, oxalate and citrate. The equivalence points were determined by Gran's method. Good results were obtained by using sodium oxalate as a titrant for the determination of uranium in several samples of ammonium diuranate. The results were quite comparable with those obtained by X-ray fluorescence spectrometry. (orig.)

  14. Preliminary observations on the effects of selenate on the development of the embryonic skate, Raja eglanteria

    Science.gov (United States)

    Conrad, G. W.; Luer, C. A.; Paulsen, A. Q.; Funderburgh, J. L.; Spooner, B. S. (Principal Investigator)

    1993-01-01

    Morphogenesis of the clearnose skate, Raja eglanteria, was not significantly inhibited as a result of 7 days of exposure to 1-2 mM selenate in the sea water during Days 59-69 of embryonic development (hatching would normally have occurred at 82 +/- 4 days of incubation). Although corneal transparency appeared normal in the eye, preliminary measurements of the thickness of Bowman's layer of the cornea suggested that it was significantly thinner in the corneas of embryos exposed to 1-2 mM selenate. Selenate is an ion reported to inhibit sulfation of glycosaminoglycans in connective tissue.

  15. Observation of Possible Lava Tube Skylights by SELENE cameras

    Science.gov (United States)

    Haruyama, Junichi; Hiesinger, Harald; van der Bogert, Carolyn

    We have discovered three deep hole-structures on the Moon in the Terrain Camera and Multi-band Imager on the SELENE. These holes are large depth to diameter ratios: Marius Hills Hole (MHH) is 65 m in diameter and 88-90 m in depth, Mare Tranquillitatis Hole (MTH) is 120 x 110 m in diameter and 180 m in depth, and Mare Ingenii Hole (MIH) is 140 x 110 m in diameter and deeper than 90 m. No volcanic material from the holes nor dike-relating pit craters is seen around the holes. They are possible lava tube skylights. These holes and possibly connected tubes have a lot of scientific interests and high potentialities as lunar bases.

  16. Infrared absorption spectra of selenate compounds of indium (3)

    International Nuclear Information System (INIS)

    Kharitonov, Yu.Ya.; Kadoshnikova, N.V.; Tananaev, I.V.

    1979-01-01

    Obtained and discussed are infrared absorption spectra (400-4000 cm -1 ) of the following indium selenates: In 2 (SeO 4 ) 3 x5H 2 O, In 2 (SeO 4 ) 3 x9H 2 O, NaIn(SeO 4 ) 2 x6H 2 O, NaIn(SeO 4 ) 2 xH 2 O, MIn(SeO 4 ) 2 x4H 2 O (M=NH 4 , K, Rb), CsIn(SeO 4 ) 2 x2H 2 O, Na 3 In(SeO 4 ) 3 x7H 2 O, MIn(SeO 4 ) 2 (M=NH 4 , Na, K, Rb, Cs), M 2 InOH(SeO 4 ) 2 xyH 2 O (M=NH 4 , Na, K, Rb) and K 2 InOD(SeO 4 ) 2 xyD 2 O

  17. Can uranyl complexes encapsulate to carbon nanotubes? A ...

    Indian Academy of Sciences (India)

    K SRINIVASU

    We find that uranyl-aqua complex ([UO2(H2O)5]2+) binds stronger as compared to uranyl-hydroxo-complex .... until the maximum Hellmann–Feynman force on each atom ..... porters and near-infrared agents for selective cancer cell.

  18. Uranyl ion recovery from waste waters by microbiological collectors

    International Nuclear Information System (INIS)

    Cecal, Alexandru; Palamaru, Iliana; Navrotescu, Tinca

    1995-01-01

    This study deals with the bioaccumulation of uranyl ions from radioactive effluents by Scenedesmus quadricauda alga. From the experimental data one can observe a greater retaining capacity of uranyl ions after four days of contact time. Filtered uranium and alga content was determined by the arsenazo III spectrophotometric method. The colored compound was determined by using wavelength λ=665 nm. (authors)

  19. New insights into the acid mediated disproportionation of pentavalent uranyl

    Energy Technology Data Exchange (ETDEWEB)

    Mougel, Victor; Biswas, Biplab; Pecaut, Jacques; Mazzanti, Marinella [Laboratoire de Reconnaissance Ionique et Chimie de Coordination, SCIB, UMR-E 3 CEA-UJF FRE 3200 CNRS, INAC, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cedex 09 (France)

    2010-07-01

    The reaction of benzoic acid with the uranyl(V) complex [(UO{sub 2}Py{sub 5})(KI{sub 2}Py{sub 2})] in pyridine leads to immediate disproportionation with formation of a hexa-nuclear U(IV) benzoate cluster, a bis-benzoate complex of uranyl(VI) and water. (authors)

  20. Densities concentrations of aqueous of uranyl nitrate solutions

    International Nuclear Information System (INIS)

    Rodrigo Otero, A.; Rodriguez Hernandez, B.; Fernandez Rodriguez, L.

    1966-01-01

    The ratio density-concentration of aqueous uranyl nitrate solutions expressed as U 3 O 8 grams/liter, U grams/liter and hexahydrate uranyl nitrate weight percent at different temperatures, are established. Experimental values are graphically correlated and compared whit some published data. (Author) 2 refs

  1. Bioavailability of selenium from fish, yeast and selenate: A comparative study in humans using stable isotopes

    NARCIS (Netherlands)

    Fox, T.E.; Heuvel, E.G.H.M. van den; Atherton, C.A.; Dainty, J.R.; Lewis, D.J.; Langford, N.J.; Crews, H.M.; Luten, J.B.; Lorentzen, M.; Sieling, F.W.; Aken-Schneyder, P. van; Hoek, M.; Kotterman, M.J.J.; Dael, P. van; Firweather-Tail, S.J.

    2004-01-01

    Objective: To measure the bioavailability of selenium from cooked and raw fish in humans by estimating and comparing apparent absorption and retention of selenium in biosynthetically labelled fish with labelled selenate and biosynthetically labelled selenium in brewers yeast. Design: The

  2. Bioavailibility of selenium from fish, yeast and selenate: a comparative study in humans using stable isotopes

    NARCIS (Netherlands)

    Fox, T.E.; Heuvel, van den E.G.H.M.; Atherton, C.A.; Luten, J.B.; Hoek-van Nieuwenhuizen, van M.; Kotterman, M.J.J.

    2004-01-01

    Objective: To measure the bioavailability of selenium from cooked and raw fish in humans by estimating and comparing apparent absorption and retention of selenium in biosynthetically labelled fish with labelled selenate and biosynthetically labelled selenium in brewers yeast. Design: The

  3. Quantification of uranyl in presence of citric acid

    International Nuclear Information System (INIS)

    Garcia G, N.; Barrera D, C.E.; Ordonez R, E.

    2007-01-01

    To determine the influence that has the organic matter of the soil on the uranyl sorption on some solids is necessary to have a detection technique and quantification of uranyl that it is reliable and sufficiently quick in the obtaining of results. For that in this work, it intends to carry out the uranyl quantification in presence of citric acid modifying the Fluorescence induced by UV-Vis radiation technique. Since the uranyl ion is very sensitive to the medium that contains it, (speciation, pH, ionic forces, etc.) it was necessary to develop an analysis technique that stands out the fluorescence of uranyl ion avoiding the out one that produce the organic acids. (Author)

  4. Infrared spectra of volatile adduct of uranyl pivaloyltrifluoroacetonate with hexamethylphosphorotriamide

    International Nuclear Information System (INIS)

    Bukhmarina, V.N.; Dushin, R.B.; Sidorenko, G.V.; Suglobov, D.N.

    1983-01-01

    Adduct of uranyl pivaloyltrifluoroacetonate with hexamethylphosphortriamide (1), sublimated without decomposition and characterized by a high thermal stability, has been synthesized, as well as adducts of uranyl dipivaloylmethanate with hexamethylphosphortriamide (2) and dimethyl sulfoxide (3), sublimated with partial dissociation. IR spectra of crystalline adducts 1-3, their solutions in benzene; gaseous and matrix-isolated adduct 1 have been measured. It is shown that in gaseous phase 1 exists practically completely in non-dissociated form. It is detected that uranyl group in crystalline 1 and 2 and in matrix-isolated 1 in contrast to crystalline 3 and previously studied adducts of uranyl β-diketonates has an asymmetric structure. Strength constants of uranyl group in crystalline 1-3 and matrix-isolated 1 are determined

  5. Specific capture of uranyl protein targets by metal affinity chromatography

    International Nuclear Information System (INIS)

    Basset, C.; Dedieu, A.; Guerin, P.; Quemeneur, E.; Meyer, D.; Vidaud, C.

    2008-01-01

    To improve general understanding of biochemical mechanisms in the field of uranium toxicology, the identification of protein targets needs to be intensified. Immobilized metal affinity chromatography (IMAC) has been widely developed as a powerful tool for capturing metal binding proteins from biological extracts. However uranyl cations (UO 2 2+ ) have particular physico-chemical characteristics which prevent them from being immobilized on classical metal chelating supports. We report here on the first development of an immobilized uranyl affinity chromatography method, based on the cation-exchange properties of amino-phosphonate groups for uranyl binding. The cation distribution coefficient and loading capacity on the support were determined. Then the stability of the uranyl-bonded phase under our chromatographic conditions was optimized to promote affinity mechanisms. The successful enrichment of uranyl binding proteins from human serum was then proven using proteomic and mass spectral analysis. (authors)

  6. Optimum Exploration for the Self-Ordering of Anodic Porous Alumina Formed via Selenic Acid Anodizing

    OpenAIRE

    Akiya, Shunta; Kikuchi, Tatsuya; Natsui, Shungo; Suzuki, Ryosuke O.

    2015-01-01

    Improvements of the regularity of the arrangement of anodic porous alumina formed by selenic acid anodizing were investigated under various operating conditions. The oxide burning voltage increased with the stirring rate of the selenic acid solution, and the high applied voltage without oxide burning was achieved by vigorously stirring the solution. The regularity of the porous alumina was improved as the anodizing time and surface flatness increased. Conversely, the purity of the 99.5–99.999...

  7. Uranyl oxalate hydrates: structures and IR spectra

    International Nuclear Information System (INIS)

    Giesting, P.A.; Porter, N.J.; Burns, P.C.

    2006-01-01

    The novel compound (UO 2 ) 2 C 2 O 4 (OH) 2 (H 2 O) 2 (UrOx2A) and the previously studied compound UO 2 C 2 O 4 (H 2 O) 3 (UrOx3) have been synthesized by mild hydrothermal methods. Single crystal diffraction data collected at 125 K using MoK α radiation and a CCD-based area detector were used to solve and refine the crystal structures by full-matrix least-squares techniques to agreement indices (UrOx2A, UrOx3) wR 2 = 0.037, 0.049 for all data, and R1 0.015, 0.024 calculated for 1285, 2194 unique reflections respectively. The compound UrOx2A is triclinic, space group P1, Z = 1, a = 5.5353(4), b 6.0866(4), c = 7.7686(6) Aa, α = 85.6410(10) , β = 89.7740(10) , γ = 82.5090(10) , V = 258.74(3) Aa 3 . The compound UrOx3 is monoclinic, space group P2 1 /c, Z = 4, a = 5.5921(4), b = 16.9931(13), c = 9.3594(7) Aa, β = 99.5330(10) , V = 877.11(11) Aa 3 . The structures consist of chains of uranyl pentagonal bipyramids connected by oxalate groups and, in UrOx2A, hydroxyl groups; UrOx2A is also notable for its high (2:1) ratio of uranyl to oxalate groups, higher than any observed in other published structures of uranyl oxalates. The structure determined for UrOx3, previously studied by Jayadevan and Chackraburtty (1972); Mikhailov et al. (1999) is in agreement with the previous results; however, the increased precision of the present low-temperature structure refinement allows for the assignment of H atom positions based on the difference Fourier map of electron density. The infrared spectra of these two materials collected at room temperature are also presented and compared with previous work on uranyl oxalate systems. (orig.)

  8. Preparation and properties of uranyl bromate monohydrate

    International Nuclear Information System (INIS)

    Weigel, F.

    1983-01-01

    Uranyl bromate monohydrate UO 2 (BrO 3 ) 2 .H 2 O was obtained as a greenish-yellow solid by the metathesis of a uranyl sulfate solution with a stoichiometric amount of barium bromate solution. On evaporation of the supernatant of the precipitated BaSO 4 a greenish-yellow syrup was obtained which, on dehydration with anhydrous carbon tetrachloride, yielded a free-flowing greenish-yellow powder with stoichiometry UO 2 (BrO 3 ) 2 .H 2 O. Powder diffraction diagrams of UO 2 (BrO 3 ) 2 .H 2 O obtained using the Guinier method yielded an orthorhombic lattice (space group, Pbcn (no. 60)) with a = 8.533 +- 0.003 A, b = 7.639 +- 0.003 A and c = 12.293 +- 0.004 A; the X-ray density was 4.507 g cm -3 . The compound was characterized by chemical analysis, IR spectroscopy and differential thermal analysis. (Auth.)

  9. Structure and spectroscopy of uranyl salicylaldiminate complexes

    Energy Technology Data Exchange (ETDEWEB)

    Tamasi, A.L.; Barnes, C.L.; Walensky, J.R. [Missouri Univ., Columbia, MO (United States). Dept. of Chemistry

    2013-07-01

    The synthesis of uranyl complexes coordinated to tridentate, monoanionic salicylaldiminate (Schiff base) ligands was achieved by the reaction of UO{sub 2}Cl{sub 2}(THF){sub 3}, 1, with one equivalent of the corresponding sodium salicylaldiminate salts affording [(C{sub 9}H{sub 6}N)N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 2, [(NC{sub 5}H{sub 4})N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 3, and [(C{sub 6}H{sub 4}SCH{sub 3})N=C(H)C{sub 6}H{sub 2}'Bu{sub 2}O]UO{sub 2}Cl(THF), 4. These are uncommon examples of uranyl complexes with a monoanionic ancillary ligand to stabilize the coordination sphere and one chloride ligand. Compounds 2-4 have been characterized by {sup 1}H and {sup 13}C NMR spectroscopy as well as IR and UVVis spectroscopy and their structures determined by X-ray crystallography. (orig.)

  10. Uranyl soaps - thermal, electronic and infrared spectral study

    International Nuclear Information System (INIS)

    Solanki, A.K.; Bhandari, A.M.

    1981-01-01

    The electronic and infrared spectra and TGA thermogram of uranyl soaps (laurate, mystrate, palmitate and stearate) have been studied. The environment about the UO 2+ 2 ion would comprise two 'short bite' bidentate carboxylate groups and oxygen atoms bridging from adjacent carboxylic molecules. The uranyl soaps have UO 2+ 2 vibronic absorption (approx. equal to 22730 cm -1 ) in the range found for eight coordinate uranyl complexes. The greater resistance to thermal degradation (approx. equal to 300 0 C) of these soaps and their stepwise thermal degradation infer strong metal-ligand interaction. (orig.) [de

  11. Broadband and polarization reflectors in the lookdown, Selene vomer.

    Science.gov (United States)

    Zhao, Shulei; Brady, Parrish Clawson; Gao, Meng; Etheredge, Robert Ian; Kattawar, George W; Cummings, Molly E

    2015-03-06

    Predator evasion in the open ocean is difficult because there are no objects to hide behind. The silvery surface of fish plays an important role in open water camouflage. Various models have been proposed to account for the broadband reflectance by the fish skin that involve one-dimensional variations in the arrangement of guanine crystal reflectors, yet the three-dimensional organization of these guanine platelets have not been well characterized. Here, we report the three-dimensional organization and the optical properties of integumentary guanine platelets in a silvery marine fish, the lookdown (Selene vomer). Our structural analysis and computational modelling show that stacks of guanine platelets with random yaw angles in the fish skin produce broadband reflectance via colour mixing. Optical axes of the guanine platelets and the collagen layer are aligned closely and provide bulk birefringence properties that influence the polarization reflectance by the skin. These data demonstrate how the lookdown preserves or alters polarization states at different incident polarization angles. These optical properties resulted from the organization of these guanine platelets and the collagen layer may have implications for open ocean camouflage in varying light fields. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

  12. Thermal decomposition of ammonium diuranate, uranyl nitrate hexahydrate and uranyl peroxide

    International Nuclear Information System (INIS)

    Yulianto, T.; Mutiara, E.

    2011-01-01

    The behaviors of three types of starting powder had been investigated during their thermal decomposition processes in nitrogen, air, and hydrogen. The powder types were the products of uranyl nitrate precipitation, i.e. ADU (ammonium diuranate), UNH (uranyl nitrate hexahydrate), and UPO (uranyl peroxide). The objective of the investigation was to find out the best atmosphere that would result in good quality powder in a thermal decomposition process with the lowest temperature and the shortest period of time in order to reduce the cost of UO 2 powder preparation. Before the thermal decomposition process was initiated, all powder types were characterized for their crystal structures. The investigation was conducted by TG-DTA instrument at temperature up to 800°C and the heating rate of 10°C/minute. The crystal structures were identified by X-Ray Diffractometer with Cu-Ka radiation. The specific surface area of the powder was also observed using BET method, especially for the powder that underwent the process in hydrogen heated up to 800°C. The Results showed that the process took place faster in hydrogen, and UNH required lower thermal decomposition temperature in relations with other types of powder. (author)

  13. Quasirelativistic pseudopotential study of species isoelectronic to uranyl and the equatorial coordination of uranyl

    International Nuclear Information System (INIS)

    Pyykkoe, P.; Li, J.; Runeberg, N.

    1994-01-01

    The calculated trends of geometries and vibrational frequencies of several uranyl isoelectronic species, like the known NUN and CUO, and the unknown CUN - , NUO + , and NUF 2+ , are reported. The NUN and CUO results support the matrix spectroscopic assignments. The simplest example of equatorial coordination to uranyl is the C 2d species UO 3 . Its calculated vibrational frequencies also support matrix spectroscopic ones. We earlier suggested that the large range of uranyl bond lengths in UO 6 6- -type systems could be interpreted in terms of a open-quotes frozen, soft e g vibrational modeclose quotes. Further studies on UF 6 , U(OH) 6 , [(OUO)(F eq ) n ] (n-2) -, [(OUO)(NO 3 ) 3 ] - , and [(OUO)(CO 3 ) 3 ] 4- show only small variation of R ax as function of R eq . Thus, the all-oxide case is a special one, where all ligands are capable of single and multiple bonding. 44 refs., 10 figs., 7 tabs

  14. Solid solutions of hydrogen uranyl phosphate and hydrogen uranyl arsenate. A family of luminescent, lamellar hosts

    International Nuclear Information System (INIS)

    Dorhout, P.K.; Rosenthal, G.L.; Ellis, A.B.

    1988-01-01

    Hydrogen uranyl phosphate, HUO 2 PO 4 x 4H 2 O (HUP), and hydrogen uranyl arsenate, HUO 2 AsO 4 x 4H 2 O (HUAs), form solid solutions of composition HUO 2 (PO 4 ) 1-x (AsO 4 )x (HUPAs), representing a family of lamellar, luminescent solids that can serve as hosts for intercalation chemistry. The solids are prepared by aqueous precipitation reactions from uranyl nitrate and mixtures of phosphoric and arsenic acids; thermogravimetric analysis indicates that the phases are tetrahydrates, like HUP and HUAs. Powder x-ray diffraction data reveal the HUPAs solids to be single phases whose lattice constants increase with X, in rough accord with Vegard's law Spectral shifts observed for the HUPAs samples. Emission from the solids is efficient (quantum yields of ∼ 0.2) and long-lived (lifetimes of ∼ 150 μs), although the measured values are uniformly smaller than those of HUP and HUAs; unimolecular radiative and nonradiative rate constants for excited-state decay of ∼ 1500 and 5000 s -1 , respectively, have been calculated for the compounds. 18 refs., 5 figs., 2 tabs

  15. Electrospray ionization of uranyl-citrate complexes

    Science.gov (United States)

    Somogyi, Árpád; Pasilis, Sofie P.; Pemberton, Jeanne E.

    2007-09-01

    Results presented here demonstrate the usefulness of electrospray ionization and gas-phase ion-molecule reactions to predict structural and electronic differences in complex inorganic ions. Electrospray ionization of uranyl citrate solutions generates positively and negatively charged ions that participate in further ion-molecule reactions in 3D ion trap and FT-ICR mass analyzers. Most ions observed are derived from the major solution uranyl-citrate complexes and involve species of {(UO2)2Cit2}2-, (UO2)3Cit2, and {(UO2)3Cit3}3-, where Cit indicates the citrate trianion, C6H5O73-. In a 3D ion trap operated at relatively high pressure, complex adducts containing solvent molecules, alkali and ammonium cations, and nitrate or chloride anions are dominant, and proton/alkali cation (Na+, K+) exchange is observed for up to six exchangeable protons in an excess of alkali cations. Adduct formation in a FT-ICR cell that is operated at lower pressures is less dominant, and direct detection of positive and negative ions of the major solution complexes is possible. Multiply charged ions are also detected, suggesting the presence of uranium in different oxidation states. Changes in uranium oxidation state are detected by He-CID and SORI-CID fragmentation, and certain fragments undergo association reactions in trapping analyzers, forming "exotic" species such as [(UO2)4O3]-, [(UO2)4O4]-, and [(UO2)4O5]-. Ion-molecule reactions with D2O in the FT-ICR cell indicate substantial differences in H/D exchange rate and D2O accommodation for different ion structures and charge states. Most notably, the positively charged ions [H2(UO2)2Cit2(H)]+ and [(UO2)2(Cit)]+ accommodate two and three D2O molecules, respectively, which reflects well the structural differences, i.e., tighter uranyl-citrate coordination in the former ion than in the latter. The corresponding negatively charged ions accommodate zero or two D2O molecules, which can be rationalized using suggested solution phase structures

  16. Colorimetric peroxidase mimetic assay for uranyl detection in sea water

    KAUST Repository

    Zhang, Dingyuan; Chen, Zhuo; Omar, Haneen; Deng, Lin; Khashab, Niveen M.

    2015-01-01

    Uranyl (UO2 2+) is a form of uranium in aqueous solution that represents the greatest risk to human health because of its bioavailability. Different sensing techniques have been used with very sensitive detection limits especially the recently

  17. Uranyl phosphate mineral in Gapyeong area

    International Nuclear Information System (INIS)

    Chung, S.J.

    1980-01-01

    An uranyl phosphate crystal from Gapeong area is studied by means of single crystal x-ray diffraction and electron microscopic qualitative analysis of chemical contents. The crystal is identified as meta-ankoleite which has a unit cell of super structure with a=b=6.99 A, c=17.69 A and space group P4 2 22. There exists some indication in the total fluorescent spectrum of the sample that potassium may be partially substituted by calcium. The chemical formula of this meta-ankoleite may be expressed by Ksub(1-2x)Casub(x)(UO 2 PO 4 ) (H 2 O)sub(3-x). (Author)

  18. Glutathione attenuates uranyl toxicity in Lactococcus lactis

    Energy Technology Data Exchange (ETDEWEB)

    Fahmy, Karim; Oertel, Jana [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biophysics; Obeid, M. [Technische Univ. Dresden (Germany); Solioz, M. [Bern Univ. (Switzerland)

    2017-06-01

    We investigated the role of intracellular glutathione (GSH), which in a large number of taxa plays a role in the protection against the toxicity of heavy metals. Anaerobically grown Lactococcus lactis containing an inducible GSH synthesis pathway was used as a model organism allowing the study of GSH-dependent uranyl detoxification without interference from additional reactive oxygen species. Microcalorimetric measurements of the metabolic heat showed that intracellular GSH attenuates the toxicity of uranium at a concentration in the range of 10-150 μM. Isothermal titration calorimetry revealed the endothermic binding of U(VI) to the carboxyl group(s) of GSH. The data indicate that the primary detoxifying mechanism is the intracellular sequestration of carboxyl-coordinated U(VI) into an insoluble complex with GSH.

  19. Glutathione attenuates uranyl toxicity in Lactococcus lactis

    International Nuclear Information System (INIS)

    Fahmy, Karim; Oertel, Jana; Solioz, M.

    2017-01-01

    We investigated the role of intracellular glutathione (GSH), which in a large number of taxa plays a role in the protection against the toxicity of heavy metals. Anaerobically grown Lactococcus lactis containing an inducible GSH synthesis pathway was used as a model organism allowing the study of GSH-dependent uranyl detoxification without interference from additional reactive oxygen species. Microcalorimetric measurements of the metabolic heat showed that intracellular GSH attenuates the toxicity of uranium at a concentration in the range of 10-150 μM. Isothermal titration calorimetry revealed the endothermic binding of U(VI) to the carboxyl group(s) of GSH. The data indicate that the primary detoxifying mechanism is the intracellular sequestration of carboxyl-coordinated U(VI) into an insoluble complex with GSH.

  20. Thermodynamics of dehydration process of uranyl nitrate pentahydrate of thorium

    International Nuclear Information System (INIS)

    Khamidov, F.A.; Mirsaidov, I.U.; Nazarov, K.M.; Nasriddinov, S.K.; Badalov, A.B.

    2010-01-01

    Present article is devoted to thermodynamics of dehydration process of uranyl nitrate pentahydrate of thorium. The results of researches of dehydration process of uranyl nitrate pentahydrate of thorium Th(NO_3)_4·5H_2O were considered. The researches were carried out by means of tensimeter method with membrane zero-manometer under equilibrium conditions and at 300-450 K temperature ranges. The thermodynamic characteristics of dehydration process of initial crystalline hydrate was defined.

  1. Radiolysis studies of uranyl nitrate solution in nitric acid medium

    International Nuclear Information System (INIS)

    Siri, Sandra; Mondino, Angel V.

    2005-01-01

    The radiolysis of acidic uranyl nitrate solutions was investigated using Co-60 gamma radiation. Hydrogen peroxide was determined as a function of increasing dose. The UV-vis absorption spectra of the irradiated solutions were measured and the spectral changes were analyzed. The increasing dose increases the absorbance intensities, possibly by an increment in nitrate concentration produced by radiolysis, which can originate the formation of different uranyl complexes in solution. (author)

  2. Influence of nitric acid on the kinetic of complexation of uranyl nitrate extracted by TBP

    International Nuclear Information System (INIS)

    Pushlenkov, M.F.; Zimenkov, V.V.

    1982-02-01

    The effect of nitric acid on the solvatation rate of uranyl nitrate with tributyl phosphate is studied. In the process of mass transfer, it is shown that nitric acid enables the extraction of uranyl nitrate, therefore its concentration in the organic phase exceeds that in equilibrium solution. Subsequently uranyl nitrate ''displaces'' nitric acid. The presence of the acid in aqueous and organic phases affects in a complicated manner the rate of solvatation of uranyl nitrate with tributyl phosphate [fr

  3. Orientational order and dynamics of water in bulk and in aqueous solutions of uranyl ions

    International Nuclear Information System (INIS)

    Chopra, Manish; Choudhury, Niharendu

    2014-01-01

    Molecular dynamics simulations in canonical ensemble of aqueous solutions of uranyl nitrate and bulk water at ambient condition have been carried out to investigate orientational order and dynamics of water. The orientational distributions of water around a central water molecule in bulk water and around a uranyl ion in an aqueous uranyl solution have been calculated. Orientational dynamics of water in bulk and in aqueous uranyl nitrate solution have also been analysed. (author)

  4. Photochemical reduction of uranyl ion by acetonitrile and propionitrile

    International Nuclear Information System (INIS)

    Brar, A.S.; Chander, R.; Sandhu, S.S.

    1979-01-01

    The photochemical reduction of uranyl ion by acetonitrile, propionitrile, benzonitrile, phenylacetonitrile, cyanoacetic acid and malononitrile in aqueous or aq. acetone medium using radiations >= 400 nm from a medium pressure mercury vapour lamp has been investigated. Except acetonitrile and propionitrile all other nitriles fail to bring about the reduction of uranyl ion. The reduction with aceto- and propionitriles has been found to obey pseudo-first order kinetics. The magnitude of rate of reduction with propionitrile is higher than that with acetonitrile. The pseudo-first order rate constants and quenching constant have been calculated from the kinetic data. It has been found that physical and chemical quenching compete with each other. The plot of reciprocal of quantum yield versus reciprocal (nitrile) is linear with a small intercept on the ordinate axis. Absorption spectra of uranyl ion in pure water, in the presence of acid and in the presence of acid+nitrile reveal that there is no ground state interaction between uranyl ion and the nitrile. A mechanism of photochemical reduction of uranyl ion based on α-hydrogen abstraction from the nitrile has been proposed. (auth.)

  5. Benchmarking uranyl peroxide capsule chemistry in organic media

    Energy Technology Data Exchange (ETDEWEB)

    Neal, Harrison A.; Nyman, May [Department of Chemistry, Oregon State University, Corvallis, OR (United States); Szymanowski, Jennifer; Fein, Jeremy B.; Burns, Peter C. [Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN (United States)

    2017-01-03

    Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X-ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post-extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Benchmarking uranyl peroxide capsule chemistry in organic media

    International Nuclear Information System (INIS)

    Neal, Harrison A.; Nyman, May; Szymanowski, Jennifer; Fein, Jeremy B.; Burns, Peter C.

    2017-01-01

    Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X-ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post-extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Preparation, solubility, infrared spectra and radiolysis of tetramethylammonium hydrogenselenate monohydrate and lithium tetramethylammonium selenate tetrahydrate

    Czech Academy of Sciences Publication Activity Database

    Havlíček, D.; Turek, L.; Plocek, Jiří; Mička, Z.

    2006-01-01

    Roč. 71, č. 3 (2006), s. 411-422 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z40320502 Keywords : tetramethylammonium salts * hydrogenselenates * selenates Subject RIV: CA - Inorganic Chemistry Impact factor: 0.881, year: 2006

  8. Selenization of CIS and CIGS layers deposited by chemical spray pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Babu, B. J.; Egaas, B.; Velumani, S.

    2018-03-21

    Cu(In1-xGax)Se2 (CIGS) thin films with x=0 (CIS) and x=0.3 (CIGS) were prepared on Mo-coated glass substrate by using chemical spray pyrolysis at a substrate temperature of 350 degrees C, followed by selenization treatment at 550 degrees C in selenium environment under N2 gas flow. X-ray diffraction patterns of as-deposited CIGS layers on Mo showed polycrystalline chalcopyrite phase with an intense (112) plane. Splitting of (204)/(220) and (116)/(312) planes for the film with x=0.3 reveals deviation of tetragonal nature. Field emission scanning electron microscopy cross-sectional images of selenized films showed clear re-crystallization of grains. During the selenization process of the CIGS absorber, a thin interface layer of MoSe2 is formed. Line mapping of Mo/CIGS layer showed more gallium segregation at the interface of back contact resulting in band gap grading. Chemical composition and mapping of the as-deposited and selenized samples were determined by energy dispersive analysis of X-rays. This work leads to fabrication of low cost and large scale Mo/CIGS/CdS/ZnO/ZnO:Al device structure.

  9. A novel selenization technique for fabrication of superconducting FeSex thin film

    International Nuclear Information System (INIS)

    Chai Qinglin; Tu Hailing; Hua Zhiqiang; Wang Lei; Qu Fei

    2011-01-01

    A novel selenization technique was applied to prepare superconducting FeSe x films with pre-set FeS films. The combination of reactive sputtering deposition with elemental diffusion technique would extend to prepare films of other iron-based superconductors. The results of transport measurement got close or greater than that of previous reports. T c,onset and T c,0 got to 10.2 K and 4 K respectively. We believe that increase of the content of Fe 7 Se 8 could not only reduce T c but also slow down the decline of resistivity. A combinative method with reactive sputtering deposition and selenization technique was applied to prepare superconducting FeSe x films on LaAlO 3 substrates successfully. The influence of selenizing temperature on film components was studied. FeSe 0.96 and FeSe films had similar and good performances in transport measurement but little difference in magnetic property. The critical onset temperature got to 11.2 K and T c,0 got to 4 K approximately. X-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy were used to analyze the ratio of constituents and morphology of several selenized films. FeSe x film had a porous structure on surface and no well preferred orientation, which were confirmed to have little influence on superconducting properties.

  10. Chemistry of the uranyl group. VI. Complexes of uranyl with hexamethylphosphoramide and urea

    Energy Technology Data Exchange (ETDEWEB)

    Zarli, B; Dall' olio, G; Sindellari, L [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi

    1976-01-01

    Some uranyl complexes with hexamethylphosphoramide (HMPA) and urea were prepared and characterized. The compounds with the former ligand have the general formula UO/sub 2/X/sub 2/.HMPA (where X = (C/sub 2/H/sub 5/)/sub 2/NCSe/sub 2//sup -/, (C/sub 2/H/sub 5/)/sub 2/NCS/sub 2//sup -/ or CH/sub 3/COO/sup -/). For the acetato derivatives a dimeric acetato-bridged structure is suggested. Some properties of UO/sub 2/(NO/sub 3/)/sub 2/.2(HMPA) are also described. With the latter ligand, in addition to the complexes UO/sub 2/(NO/sub 3/)/sub 2/.2urea and (UO/sub 2/(urea)/sub 4/(H/sub 2/0))(NO/sub 3/)/sub 2/ already known, the novel complexes UO/sub 2/(pycrate)/sub 2/.4urea and (UO/sub 2/(CH/sub 3/COO)/sub 2/.urea)sub(n) (where n is probably 2) have been prepared. All attempts to obtain urea complexes of uranyl diethyldithio- or diethyldiselenocarbamate failed and only adducts of unsatisfactory stoichiometry were isolated.

  11. Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

    International Nuclear Information System (INIS)

    Kubatko, K.; Helean, K.; Navrotsky, A.; Burns, P.C.

    2005-01-01

    The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO 2 ) 4 O(OH) 6 ](H 2 O) 5 , metaschoepite; β-UO 2 (OH) 2 ; CaUO 4 ; Ca(UO 2 ) 6 O 4 (OH) 6 (H 2 O) 8 , becquerelite; Ca(UO 2 ) 4 O 3 (OH) 4 (H 2 O) 2 ; Na(UO 2 )O(OH), clarkeite; Na 2 (UO 2 ) 6 O 4 (OH) 6 (H 2 O) 7 , the sodium analogue of compreignacite and Pb 3 (UO 2 ) 8 O 8 (OH) 6 (H 2 O) 2 , curite. The enthalpy of formation from the binary oxides, ΔH f-ox , at 298 K was calculated for each compound from the respective drop solution enthalpy, ΔH ds . The standard enthalpies of formation from the elements, ΔH f o , at 298 K are -1791.0 ± 3.2, -1536.2 ± 2.8, -2002.0 ± 3.2, -11389.2 ± 13.5, -6653.1 ± 13.8, -1724.7 ± 5.1, -10936.4 ± 14.5 and -13163.2 ± 34.4 kJ mol -1 , respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments

  12. Hydrothermal Phase Relations Among Uranyl Minerals at the Nopal I Analog Site

    International Nuclear Information System (INIS)

    Murphy, William M.

    2007-01-01

    Uranyl mineral paragenesis at Nopal I is an analog of spent fuel alteration at Yucca Mountain. Petrographic studies suggest a variety of possible hydrothermal conditions for uranium mineralization at Nopal I. Calculated equilibrium phase relations among uranyl minerals show uranophane stability over a broad range of realistic conditions and indicate that uranyl mineral variety reflects persistent chemical potential heterogeneity. (author)

  13. Global Lunar Gravity Field Determination Using Historical and Recent Tracking Data in Preparation for SELENE

    Science.gov (United States)

    Goossens, S.; Matsumoto, K.; Namiki, N.; Hanada, H.; Iwata, T.; Tsuruta, S.; Kawano, N.; Sasaki, S.

    2006-12-01

    In the near future, a number of satellite missions are planned to be launched to the Moon. These missions include initiatives by China, India, the USA, as well as the Japanese SELENE mission. These missions will gather a wealth of lunar data which will improve the knowledge of the Moon. One of the main topics to be addressed will be the lunar gravity field. Especially SELENE will contribute to improving the knowledge of the gravity field, by applying 4-way Doppler tracking between the main satellite and a relay satellite, and by applying a separate differential VLBI experiment. These will improve the determination of the global gravity field, especially over the far side and at the lower degrees (mostly for degrees lower than 30), as is shown by extensive simulations of the SELENE mission. This work focuses on the determination of the global lunar gravity field from all available tracking data to this date. In preparation for the SELENE mission, analysis using Lunar Prospector tracking data, as well as Clementine data and historical data from the Apollo and Lunar Orbiter projects is being conducted at NAOJ. Some SMART-1 tracking data are also included. The goal is to combine the good-quality data from the existing lunar missions up to this date with the tracking data from SELENE in order to derive a new lunar gravity field model. The focus therefore currently lies on processing the available data and extracting lunar gravity field information from them. It is shown that the historical tracking data contribute especially to the lower degrees of the global lunar gravity field model. Due to the large gap in tracking data coverage over the far side for the historical data, the higher degrees are almost fully determined by the a priori information in the form of a Kaula rule. The combination with SELENE data is thus expected to improve the estimate for the lower degrees even further, including coverage of the far side. Since historical tracking data are from orbits with

  14. Potentiometric titration of selenic and telluric acids with titanium(III) chloride in nonaqueous solvents

    International Nuclear Information System (INIS)

    Yoshimura, Chozo; Miyamoto, Kiyoshige

    1985-01-01

    Selenic and Telluric acids were titrated potentiometrically with titanium(III) chloride solution by using Pt-Cu · Hg bimetallic electrodes in nonaqueous solvents such as N, N-dimethyl-formamide (DMF), dimethyl sulfoxide (DMSO), isopropyl alcohol (IPA) and the mixtures of these solvents. It was found that selenic and telluric acids were titrated directly at room temperature in DMF solution without hydrochloric acid. The molar ratios of selenic and telluric acids to titanium(III) chloride was 1 : 6. However, the corresponding reactions to SeO 4 2- → SeO 3 2- or TeO 4 2- → TeO 3 2- were not confirmed in the titration curve in DMF. In the titration of selenic acid in mixed solvents of DMF and IPA in 1 : 1 or 1 : 2 ratio, two steps were observed. The first and the second steps were appeared on the titration curve at molar ratios of 1 : 2 and 1 : 6, respectively. It was interpreted that the first step corresponded to the intermediate reaction of SeO 4 2- → SeO 3 2- . Mixed solution of selenic and telluric acids were determined by the proposed method. Three steps were observed on the titration curve. It was interpreted that the first, second and third steps corresponded to the reaction of SeO 4 2- → SeO 3 2- , SeO 3 2- → Se(0), and TeO 4 2- → Te(0), respectively. Less than 5 % of water gave no influence on the titration. (author)

  15. Preparation of working calibration and test materials: uranyl nitrate solution

    International Nuclear Information System (INIS)

    Yamamura, S.S.; Spraktes, F.W.; Baldwin, J.M.; Hand, R.L.; Lash, R.P.

    1977-05-01

    Reliable working calibration and test materials (WCTMs) are essential to a meaningful analytical measurements quality assurance program. This report describes recommended methods for the preparation of uranyl nitrate solution WCTMs for testing analytical methods, for calibrating methods, and for testing personnel. Uranyl nitrate solution WCTMs can be synthesized from characterized starting materials or prepared from typical plant materials by thorough characterization with reference to primary or secondary reference calibration and test materials (PRCTMs or SRCTMs). Recommended starting materials are described along with detailed procedures for (a) preparing several widely-used types of uranyl nitrate solution WCTMs, (b) packaging the WCTMs, (c) analyzing the WCTMs to establish the reference values or to confirm the synthesis, and (d) statistically evaluating the analytical data to assign reference values and to assess the accuracy of the WCTMs

  16. Infrared studies on complexes between octaethyltetraamidepyrophosphate (OETAPP) and uranyl salts

    International Nuclear Information System (INIS)

    Grychowski, P.; Mikulski, J.; Moravets, Ya.; Shara, V.; Shourkova, L.

    1981-01-01

    Uranyl nitrate and uranyl chloride were extracted from the water phase with CHCl 3 solution of octaethyltetraamidepyrophosphate (OETAPP). Infrared spectra of the organic phases were recorded before and after the extraction. For both systems, the frequency of the P=O stretching mode of OETAPP after the extraction was lowered, which indicates for the formation of OETAPP UO 2 (NO 3 ) 2 and OETAPP UO 2 Cl 2 complexes. If uranyl nitrate was extracted with OETAPP in CCl 4 a precipitate was formed in the solution. From the analysis of the IR spectrum of the precipitate it was concluded that the complex OETAPP UO 2 (NO 3 ) 2 was formed also in this case, however, the complex was insoluble in CCl 4 . (author)

  17. A study of precipitation from pure solutions of uranyl nitrate

    International Nuclear Information System (INIS)

    Decrop, J.; Holder, J.; Sauteron, J.

    1961-01-01

    After its purification by extraction of the uranyl nitrate from the organic solvent, uranium has to be converted into solid form again: uranium trioxide (UO 3 ). It can be done either by thermal decomposition of uranyl nitrate or by precipitation of uranium, followed by filtration and calcination. Only the second method has been studied for now at the Bouchet plant. This paper reports the bench-scale and pilot-scale experiments of the studies of the precipitation of pure solutions of uranyl nitrate using ammonia (gaseous or in solution) or ammonium carbonate. These have been carried out at the Bouchet plant. It investigates the chemical aspect (pH, precipitates chemical composition) and the technical aspect of the different ways of precipitation (conditions of precipitation, decantation and filtration of precipitates). (M.P.)

  18. Uranyl Sulfate Nanotubules Templated by N-phenylglycine

    Directory of Open Access Journals (Sweden)

    Oleg I. Siidra

    2018-04-01

    Full Text Available The synthesis, structure, and infrared spectroscopy properties of the new organically templated uranyl sulfate Na(phgH+7[(UO26(SO410](H2O3.5 (1, obtained at room temperature by evaporation from aqueous solution, are reported. Its structure contains unique uranyl sulfate [(UO26(SO410]8− nanotubules templated by protonated N-phenylglycine (C6H5NH2CH2COOH+. Their internal diameter is 1.4 nm. Each of the nanotubules is built from uranyl sulfate rings sharing common SO4 tetrahedra. The template plays an important role in the formation of the complex structure of 1. The aromatic rings are stacked parallel to each other due to the effect of π–π interaction with their side chains extending into the gaps between the nanotubules.

  19. DNA conformational analysis in solution by uranyl mediated photocleavage

    DEFF Research Database (Denmark)

    Nielsen, Peter E.; Møllegaard, N E; Jeppesen, C

    1990-01-01

    Uranyl mediated photocleavage of double stranded DNA is proposed as a general probing for DNA helix conformation in terms of minor groove width/electronegative potential. Specifically, it is found that A/T-tracts known to constitute strong distamycin binding sites are preferentially photocleaved ......, uranyl photocleavage of the internal control region (ICR) of the 5S-RNA gene yields a cleavage modulation pattern fully compatible with that obtained by DNase I which also--in a more complex way--senses DNA minor groove width....

  20. Critical experiment study on uranyl nitrate solution experiment facility

    International Nuclear Information System (INIS)

    Zhu Qingfu; Shi Yongqian; Wang Jinrong

    2005-01-01

    The Uranyl Nitrate Solution Experiment Facility was constructed for the research on nuclear criticality safety. In this paper, the configuration of the facility is introduced; a series of critical experiments on uranyl nitrate solution is described later, which were performed for various uranium concentrations under different conditions, i.e. with or without neutron absorbers in the core and with or without water-reflector outside the core. Critical volume and the minimum 235U critical mass for different uranium concentrations are presented. Finally, theoretical analysis is made on the experimental results. (authors)

  1. Molecular approach of uranyl/mineral surfaces: theoretical approach

    International Nuclear Information System (INIS)

    Roques, J.

    2009-01-01

    As migration of radio-toxic elements through the geosphere is one of the processes which may affect the safety of a radioactive waste storage site, the author shows that numerical modelling is a support to experimental result exploitation, and allows the development of new interpretation and prediction codes. He shows that molecular modelling can be used to study processes of interaction between an actinide ion (notably a uranyl ion) and a mineral surface (a TiO 2 substrate). He also reports the predictive theoretical study of the interaction between an uranyl ion and a gibbsite substrate

  2. Uranyl peroxide enhanced nuclear fuel corrosion in seawater.

    Science.gov (United States)

    Armstrong, Christopher R; Nyman, May; Shvareva, Tatiana; Sigmon, Ginger E; Burns, Peter C; Navrotsky, Alexandra

    2012-02-07

    The Fukushima-Daiichi nuclear accident brought together compromised irradiated fuel and large amounts of seawater in a high radiation field. Based on newly acquired thermochemical data for a series of uranyl peroxide compounds containing charge-balancing alkali cations, here we show that nanoscale cage clusters containing as many as 60 uranyl ions, bonded through peroxide and hydroxide bridges, are likely to form in solution or as precipitates under such conditions. These species will enhance the corrosion of the damaged fuel and, being thermodynamically stable and kinetically persistent in the absence of peroxide, they can potentially transport uranium over long distances.

  3. Electronic structure and properties of uranyl compounds. Problems of electron-donor conception

    International Nuclear Information System (INIS)

    Glebov, V.A.

    1982-01-01

    Comparison of the series of the ligand mutual substitution in the uranyl compounds with the ligand series of d-elements and with the uranyl ''covalent model'', is made. The data on ionization potentials of the ligand higher valent levels and on the structure of some uranyl nitrate compounds are considered. It is concluded that the mechanism of the ligand effect on the properties of uranyl grouping is more complex, than it is supposed in the traditional representations on the nature of electron-donor interactions in the uranyl compounds

  4. The interaction of uranyl ions with inorganic pyrophosphatase from baker's yeast

    International Nuclear Information System (INIS)

    Bienwald, B.; Heitmann, P.

    1978-01-01

    The interaction of uranyl ions with inorganic pyrophosphatase from baker's yeast was investigated by measurement of their effect on the protein fluorescence. Fluorescence titrations of the native enzyme with uranyl nitrate show that there is a specific binding of uranyl ions to the enzyme. It was deduced that each subunit of the enzyme binds one uranyl ion. The binding constant was estimated to be in the order of 10 7 M -1 . The enzyme which contains a small number of chemically modified carboxyl groups was not able to bind uranyl ions specifically. The modification of carboxyl groups was carried out by use of a water soluble carbodiimide and the nucleophilic reagent N-(2,4-dinitro-phenyl)-hexamethylenediamine. The substrate analogue calcium pyrophosphate displaced the uranyl ions from their binding sites at the enzyme From the results it is concluded that carboxyl groups of the active site are the ligands for the binding of uranyl ions. (author)

  5. Thermodynamics of Uranyl Minerals: Enthalpies of Formation of Uranyl Oxide Hydrates

    Energy Technology Data Exchange (ETDEWEB)

    K. Kubatko; K. Helean; A. Navrotsky; P.C. Burns

    2005-05-11

    The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO{sub 2}){sub 4}O(OH){sub 6}](H{sub 2}O){sub 5}, metaschoepite; {beta}-UO{sub 2}(OH){sub 2}; CaUO{sub 4}; Ca(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 8}, becquerelite; Ca(UO{sub 2}){sub 4}O{sub 3}(OH){sub 4}(H{sub 2}O){sub 2}; Na(UO{sub 2})O(OH), clarkeite; Na{sub 2}(UO{sub 2}){sub 6}O{sub 4}(OH){sub 6}(H{sub 2}O){sub 7}, the sodium analogue of compreignacite and Pb{sub 3}(UO{sub 2}){sub 8}O{sub 8}(OH){sub 6}(H{sub 2}O){sub 2}, curite. The enthalpy of formation from the binary oxides, {Delta}H{sub f-ox}, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}H{sub ds}. The standard enthalpies of formation from the elements, {Delta}H{sub f}{sup o}, at 298 K are -1791.0 {+-} 3.2, -1536.2 {+-} 2.8, -2002.0 {+-} 3.2, -11389.2 {+-} 13.5, -6653.1 {+-} 13.8, -1724.7 {+-} 5.1, -10936.4 {+-} 14.5 and -13163.2 {+-} 34.4 kJ mol{sup -1}, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

  6. Solvent extraction of uranyl nitrate (1962); Extraction du nitrate d'uranyle par solvant (1962)

    Energy Technology Data Exchange (ETDEWEB)

    Talmont, X; Regnaut, P [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires; Durandet, J; Renault, Ph; Gladel, Y L [Institut Francais du Petrole (IFP), Dept. de Physico-Chimie Appliquee, 92 - Rueil-Malmaison (France)

    1962-07-01

    The transfer of uranyl nitrate from an aqueous acid phase into a solvent (dilute tributylphosphate) is attended by nitric acid transfer. In these conditions, equilibrium data cannot be represented by a plane curve, which complicates the determination of the efficiency of the extractor used, i.e. the calculation of either the number of theoretical plates or the number of transfer units equivalent to the apparatus. The authors are presenting a simple method for estimating the efficiency of a column, based upon either uranium or acid transfer. This method can be used when the profile of uranium and acid concentrations in a phase circulating in the equipment bas been previously determined. On another hand, it enables to study the variation of local efficiency, i.e. the efficiency of different sections of the column. (authors) [French] Le transfert du nitrate d'uranyle d'une phase aqueuse acide dans un solvant (phosphate de tributyle dilue) s'accompagne d'un transfert d'acide nitrique. Dans ces conditions, les donnees d'equilibre ne sont pas representees par une courbe plane, ce qui complique la determination de l'efficacite de l'extracteur utilise, c'est-a-dire le calcul, soit du nombre d'etages theoriques, soit du nombre d'unites de transfert auquel l'appareil est equivalent. Les auteurs presentent une methode simple d'evaluation de l'efficacite d'une colonne basee, soit sur le transfert d'uranium, soit sur celui d'acide. Cette methode est utilisable lorsqu'en a determine au prealable le profil des concentrations en uranium et en acide d'une phase circulant dans l'appareil. Elle permet, d'autre part, d'etudier la variation de l'efficacite locale, c'est-a-dire l'efficacite de differentes sections de la colonne. (auteurs)

  7. Sorption of uranyl ions on hydrous silicon dioxide

    International Nuclear Information System (INIS)

    Lieser, K.H.; Quandt-Klenk, S.; Thybusch, B.

    1992-01-01

    Sorption of uranyl ions on SiO 2 .χH 2 O (silica gel) is investigated in absence and in presence of carbonate as function of pH. The curves obtained are very similar to those observed for sorption of uranyl ion on TiO 2 .χH 2 O, indicating the dominating influence of the uranium species in solution. Between pH 2 and 5 the sorption ratio R s increases with hydrolysis of uranyl ions (formation of UO 2 OH + ), around pH 7 it is nearly independent of pH, and at higher pH it decreases again. The equilibrium constants are calculated for these ranges. In presence of carbonate R s decreases drastically above pH 6, due to the formation of carbonato complexes in solution. Sorption of uranyl ions on SiO 2 .χH 2 O, on TiO 2 .χH 2 O, and on cryst. SiO 2 and Al 2 O 3 is compared. The problems of 'surface complexation' modelling are discussed. (orig.)

  8. Synthesis of pyrimidine carboxamide derivatives catalyzed by uranyl

    African Journals Online (AJOL)

    2014-09-02

    (Received September 2, 2014; revised January 1, 2016). ABSTRACT. An efficient and simple method was developed for the synthesis pyrimidine-5-carboxamides using. UO2(NO3)2.6H2O catalyst under conventional and microwave irradiation. The synthesis of dihydropyrimidine using uranyl nitrate had shown many ...

  9. Density functional study of uranyl (VI) amidoxime complexes

    International Nuclear Information System (INIS)

    Chi Fang-Ting; Xiong Jie; Hu Sheng; Xia Xiu-Long; Wang Xiao-Lin; Li Peng; Gao Tao

    2012-01-01

    Uranyl (VI) amidoxime complexes are investigated using relativistic density functional theory. The equilibrium structures, bond orders, and Mulliken populations of the complexes have been systematically investigated under a generalized gradient approximation (GGA). Comparison of (acet) uranyl amidoxime complexes ([UO 2 (AO) n ] 2−n , 1 ≤ n ≤ 4) with available experimental data shows an excellent agreement. In addition, the U−O(1), U−O(3), C(1)−N(2), and C(3)−N(4) bond lengths of [UO 2 (CH 3 AO) 4 ] 2− are longer than experimental data by about 0.088, 0.05, 0.1, and 0.056 Å. The angles of N(3)−O(3)−U, O(2)−N(1)−C(1), N(3)−C(3)−N(4), N(4)−C(3)−C(4), and C(4)−C(3)−N(3) are different from each other, which is due to existing interaction between oxygen in uranyl and hydrogen in amino group. This interaction is found to be intra-molecular hydrogen bond. Studies on the bond orders, Mulliken charges, and Mulliken populations demonstrate that uranyl oxo group functions as hydrogen-bond acceptors and H atoms in ligands act as hydrogen-bond donors forming hydrogen bonds within the complex

  10. Studying of the dehydration process of uranyl nitrate hexahydrate (Unh)

    International Nuclear Information System (INIS)

    Badalov, A.; Kamalov, J.J.; Homidov, B.J.; Mirsaidov, I.U.; Eshbekov, N.R.

    2005-01-01

    By the tensimeteric method is studying the dehydration process of uranyl nitrate hexahydrate (Unh). It is shown, that the temperature interval 300-400 K in equilibrium conditions the dehydration process of Unh runs in three stages. According to the equations of dependence of saturated steam pressure from temperature, the thermodynamic characteristics of each stage of the dehydration process of Unh are calculated

  11. Colorimetric peroxidase mimetic assay for uranyl detection in sea water

    KAUST Repository

    Zhang, Dingyuan

    2015-03-04

    Uranyl (UO2 2+) is a form of uranium in aqueous solution that represents the greatest risk to human health because of its bioavailability. Different sensing techniques have been used with very sensitive detection limits especially the recently reported uranyl-specific DNAzymes systems. However, to the best of our knowledge, few efficient detection methods have been reported for uranyl sensing in seawater. Herein, gold nanoclusters (AuNCs) are employed in an efficient spectroscopic method to detect uranyl ion (UO2 2+) with a detection limit of 1.86 ÎM. In the absence of UO2 2+, the BSA-stabilized AuNCs (BSA-AuNCs) showed an intrinsic peroxidase-like activity. In the presence of UO2 2+, this activity can be efficiently restrained. The preliminary quenching mechanism and selectivity of UO2 2+ was also investigated and compared with other ions. This design strategy could be useful in understanding the binding affinity of protein-stabilized AuNCs to UO2 2+ and consequently prompt the recycling of UO2 2+ from seawater.

  12. Multi-scale modelling of uranyl chloride solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Thanh-Nghi; Duvail, Magali, E-mail: magali.duvail@icsm.fr; Villard, Arnaud; Dufrêche, Jean-François, E-mail: jean-francois.dufreche@univ-montp2.fr [Institut de Chimie Séparative de Marcoule (ICSM), UMR 5257, CEA-CNRS-Université Montpellier 2-ENSCM, Site de Marcoule, Bâtiment 426, BP 17171, F-30207 Bagnols-sur-Cèze Cedex (France); Molina, John Jairo [Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103 (Japan); Guilbaud, Philippe [CEA/DEN/DRCP/SMCS/LILA, Marcoule, F-30207 Bagnols-sur-Cèze Cedex (France)

    2015-01-14

    Classical molecular dynamics simulations with explicit polarization have been successfully used to determine the structural and thermodynamic properties of binary aqueous solutions of uranyl chloride (UO{sub 2}Cl{sub 2}). Concentrated aqueous solutions of uranyl chloride have been studied to determine the hydration properties and the ion-ion interactions. The bond distances and the coordination number of the hydrated uranyl are in good agreement with available experimental data. Two stable positions of chloride in the second hydration shell of uranyl have been identified. The UO{sub 2}{sup 2+}-Cl{sup −} association constants have also been calculated using a multi-scale approach. First, the ion-ion potential averaged over the solvent configurations at infinite dilution (McMillan-Mayer potential) was calculated to establish the dissociation/association processes of UO{sub 2}{sup 2+}-Cl{sup −} ion pairs in aqueous solution. Then, the association constant was calculated from this potential. The value we obtained for the association constant is in good agreement with the experimental result (K{sub UO{sub 2Cl{sup +}}} = 1.48 l mol{sup −1}), but the resulting activity coefficient appears to be too low at molar concentration.

  13. Structure and dynamics of aqueous solution of uranyl ions

    International Nuclear Information System (INIS)

    Chopra, Manish; Choudhury, Niharendu

    2014-01-01

    The present work describes a molecular dynamics simulation study of structure and dynamics of aqueous solution of uranyl ions in water. Structural properties of the system in terms of radial distribution functions and dynamical characteristics as obtained through velocity autocorrelation function and mean square displacements have been analyzed. The results for radial distribution functions show the oxygen of water to form the first solvation shell at 2.4 Å around the uranium atom, whereas the hydrogen atoms of water are distributed around the uranium atom with the major peak at around 3.0 Å. Analyses of transport behaviors of ions and water through MSD indicates that the diffusion of the uranyl ion is much less as compared to that of the water molecules. It is also observed that the dynamical behavior of water molecules gets modified due to the presence of uranyl ion. The effect of increase in concentration of uranyl ions on the structure and dynamics of water molecules is also studied

  14. Synthesis and characterization of heterometallic uranyl pyridinedicarboxylate compounds

    Science.gov (United States)

    Jayasinghe, Ashini S.; Payne, Maurice K.; Forbes, Tori Z.

    2017-10-01

    The incorporation of transition metals into hybrid uranyl materials can result in more diverse structural topologies and variations in physical and chemical properties. To explore the impact of transition metals on the uranyl cation, five uranium containing bimetallic chain compounds, [(UO2)M(PDC)2(H2O)4]·4(H2O) (PDC = 2,6 pyridinedicarboxylate; M = Ni2+, Co2+, Fe2+, Zn2+, and Cu2+) were synthesized by evaporation of aqueous solutions at room temperature. The uranyl cation is complex by two PDC ligands and the transition metal cations bond to the complex to form a one-dimensional chain topology. The presence of the transition metal leads to the presence of a stronger uranyl oxo bonds as shown by the single-crystal X-ray diffraction data and the Raman spectra. Solid state diffuse reflectance UV/Visible spectra confirmed the presence of the transition metals in the structure by the broad bands that appeared at relevant wavelengths.

  15. Growth of uranyl hydroxide nanowires and nanotubes with electrodeposition method

    International Nuclear Information System (INIS)

    Wang Lin; Yuan Liyong; Chai Zhifang; Shi Weiqun

    2013-01-01

    Actinides nanomaterials have great potential applications in fabrication of novel nuclear fuel and spent fuel reprocessing in advanced nuclear energy system. However, the relative research so far still lacks systematic investigation on the synthetic methods for actinides nanomaterials. In this work, we use track-etched membranes as hard templates to synthesize uranium based nanomaterials with novel structures by electrodeposition method. Through electrochemical behavior investigations and subsequent product characterizations such as energy dispersive spectrometer (EDS), fourier transform infrared spectroscopy (FTIR), the chemical composition of deposition products have been confirmed as the uranyl hydroxide. More importantly, accurate control of morphology and structures (nanowires and nanotubes) could be achieved by carefully adjusting the growth parameters such as deposition time and deposition current density. It was found that the preferred morphology of electrodeposition products is nanowire when a low current density was applied, whereas nanotubes could be formed only under conditions of high current density and the short deposition time. The mechanism for the formation of nanowires in track-etched membranes is based on the precipitation of uranyl hydroxide from uranyl nitrate solution, according to the previous researches about obtaining nanostructures of hydroxides from nitrate salt solutions. And we have concluded that the formation of nanotubes is attributed to the hydrogen bubbles generated by water electrolysis under the condition of over-potential electro-reduction. The conveying of hydrogen bubbles plays the role of dynamic template which can prevent the complete filling of uranyl hydroxide in the channels. Additionally, we transform the chemical composition of deposition products from uranyl hydroxide to triuranium octoxide by calcining them at 500 and 800 degree centigrade, respectively, and SEM results show the morphologies of nanowires and

  16. Uptake of selenate on hydrated and degraded cement: batch and dynamic experiments

    International Nuclear Information System (INIS)

    Rojo, I.; Rovira, I.; Marti, V.; Pablo, J. de; Duro, L.; Gaona, X.; Colas, E.; Grive, M.

    2009-01-01

    The evaluation of selenate sorption and retardation in batch and dynamic experiments on hydrated and degraded cement has been studied. Desorption studies have also been carried in order to assess the reversibility of the sorption process. Sorption data onto degraded cement have been treated assuming the formation of surface complexes, whereas sorption kinetics has been fitted by using a pseudo-first order kinetic equation. Dynamic flow experiments have also been modelled. (authors)

  17. Preparation of CIGS thin films by HiPIMS or DC sputtering and various selenization processes

    Czech Academy of Sciences Publication Activity Database

    Olejníček, Jiří; Hubička, Zdeněk; Kšírová, Petra; Kment, Štěpán; Brunclíková, Michaela; Kohout, Michal; Čada, Martin; Darveau, S.A.; Exstrom, C.L.

    2013-01-01

    Roč. 16, č. 2 (2013), s. 314-319 ISSN 1203-8407 R&D Projects: GA MŠk LH12045 Institutional support: RVO:68378271 Keywords : CIGS * HIPIMS * selenization * nanocrystals * solar energy * sputtering * thin films Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 1.106, year: 2013 http://www.ingentaconnect.com/content/stn/jaots/2013/00000016/00000002/art00015

  18. Optimization of selenizing conditions for Seleno-Lentinan and its characteristics.

    Science.gov (United States)

    Ren, Guangming; Li, Koukou; Hu, Yang; Yu, Min; Qu, Juanjuan; Xu, Xiuhong

    2015-11-01

    Lentinan was successfully modified with nitric acid-sodium selenite method based on L9(3(4)) orthogonal experiments. The optimum selenizing conditions were obtained according to selenium conversion rate as follows: Lentinan of 1.0g, pH of 4.5, temperature of 70°C and sodium selenite of 1.50g. The antioxidant activity assays in vitro (DPPH, reducing power, superoxide radicals and hydroxyl radicals) proved that Lentinan had stronger antioxidant activity after selenizing. The elevations of serum alanine aminotransferase and aspartate aminotransferase, as well as the abnormal hepatic architecture, verified that oral administration of Seleno-Lentinan (SL2-1) markedly alleviated oxidative damage in the liver of mice induced by D-gal. In addition, SL2-1 significantly increased total antioxidant capacity, activities and protein expressions of catalase and glutathione peroxidase and lowered malondialdehyde levels in serum and liver. Fourier transform infrared spectroscopy analysis indicated that selenium of SL2-1 was mostly existed as the formations of OSeO, SeO and SeOC. Scanning electron microscope coupled with energy dispersive X-ray spectroscopy analysis revealed that the surface structure and elemental components of Lentinan significantly changed after selenizing. The results are instructive for the development of organic selenium-supplement resource. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. The intensity of tyrosine nitration is associated with selenite and selenate toxicity in Brassica juncea L.

    Science.gov (United States)

    Molnár, Árpád; Feigl, Gábor; Trifán, Vanda; Ördög, Attila; Szőllősi, Réka; Erdei, László; Kolbert, Zsuzsanna

    2018-01-01

    Selenium phytotoxicity involves processes like reactive nitrogen species overproduction and nitrosative protein modifications. This study evaluates the toxicity of two selenium forms (selenite and selenate at 0µM, 20µM, 50µM and 100µM concentrations) and its correlation with protein tyrosine nitration in the organs of hydroponically grown Indian mustard (Brassica juncea L.). Selenate treatment resulted in large selenium accumulation in both Brassica organs, while selenite showed slight root-to-shoot translocation resulting in a much lower selenium accumulation in the shoot. Shoot and root growth inhibition and cell viability loss revealed that Brassica tolerates selenate better than selenite. Results also show that relative high amounts of selenium are able to accumulate in Brassica leaves without obvious visible symptoms such as chlorosis or necrosis. The more severe phytotoxicity of selenite was accompanied by more intense protein tyrosine nitration as well as alterations in nitration pattern suggesting a correlation between the degree of Se forms-induced toxicities and nitroproteome size, composition in Brassica organs. These results imply the possibility of considering protein tyrosine nitration as novel biomarker of selenium phytotoxicity, which could help the evaluation of asymptomatic selenium stress of plants. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Novel in situ resistance measurement for the investigation of CIGS growth in a selenization process

    International Nuclear Information System (INIS)

    Liu Wei; He Qing; Li Fengyan; Li Changjian; Sun Yun; Tian Jianguo; Li Zubin

    2009-01-01

    During the selenization process of CIGS thin films, the relation between the element loss rate and the precursor depositions are analyzed. The growth of the CIGS thin films during the selenization process is investigated by the novel in situ resistance measurement, by which the formation of compound semiconductors can be observed directly and simultaneously. Their structures, phase evolutions and element losses are analyzed by XRD and XRF. Based on the experimental results, it can be concluded that the phase transforms have nothing to do with the deposition sequences of precursors, while the element loss rates are related to the deposition sequences in this process. In addition, element loss mechanisms of CIGS thin films prepared by the selenization process are analyzed by the phase evolutions and chemical combined path in the In, Ga–Se reaction processes. Moreover it is verified that the element losses are depressed by increasing the ramping-up rate finally. The results provide effective methods to fabricate high-quality CIGS thin films with low element losses

  1. Novel in situ resistance measurement for the investigation of CIGS growth in a selenization process

    Science.gov (United States)

    Liu, Wei; Tian, Jian-Guo; Li, Zu-Bin; He, Qing; Li, Feng-Yan; Li, Chang-Jian; Sun, Yun

    2009-03-01

    During the selenization process of CIGS thin films, the relation between the element loss rate and the precursor depositions are analyzed. The growth of the CIGS thin films during the selenization process is investigated by the novel in situ resistance measurement, by which the formation of compound semiconductors can be observed directly and simultaneously. Their structures, phase evolutions and element losses are analyzed by XRD and XRF. Based on the experimental results, it can be concluded that the phase transforms have nothing to do with the deposition sequences of precursors, while the element loss rates are related to the deposition sequences in this process. In addition, element loss mechanisms of CIGS thin films prepared by the selenization process are analyzed by the phase evolutions and chemical combined path in the In, Ga-Se reaction processes. Moreover it is verified that the element losses are depressed by increasing the ramping-up rate finally. The results provide effective methods to fabricate high-quality CIGS thin films with low element losses.

  2. Subsurface structures in the northern Mare Imbrium measured by Chang'E-3 and SELENE

    Science.gov (United States)

    Kumamoto, A.; Ishiyama, K.; Feng, J.

    2016-12-01

    Subsurface structures in the northern Mare Imbrium measured by Chang'E-3 and SELENE have been compared. In Chang'E-3 mission, subsurface radar sounding at (19.51W, 44.12N) was performed by Lunar Penetrating Radar (LPR) onboard the Yutu rover. The LPR was pulse radar operated at two frequencies: 60 MHz and 500 MHz. During its operation period from December 2013 to January 2014, the LPR observed subsurface echoes along the rover's track with total distance of 114 m. From the observation in 60 MHz, the subsurface echoes from buried regolith layers at depths of 35, 50, 140, 240, and 360 m were reported (Xiao et al., 2015). In SELENE mission, global subsurface radar sounding of the moon was performed by Lunar Radar Sounder (LRS) onboard the SELENE (Kaguya) spacecraft from the polar orbit with an altitude of 100 km. The LRS was chirp radar operated in a frequency range from 4-6 MHz. So the range resolution of LRS was 75 m in vacuum. During operation period from December 2007 to September 2008, subsurface echoes from all areas of the Moon was observed with a lateral resolution of 76 m. From the global observation, the subsurface echoes from the buried regolith layers in the neraside maria including Mare Imbrium at depths of several hundred meters were reported (Ono et al., 2009).In the present study, we focus on SELENE/LRS data obtained at (19.50W, 44.12N) which is the nearest to the Chang'E-3 landing site. While clear and large-scale subsurface reflectors, as found in Ono et al. (2009), are not found in it, we can identify some echo components from the depths of 140 ( 2000 ns), 240 ( 4000 ns), and 360 m ( 6000 ns). Further analyses utilizing high-resolution data from Chang'E-3/LPR and large-scale data from SELENE/LRS, we will be able to determine the thickness and large-scale structures of the buried regolith layers found by the both radars, and discuss their formation processes in volcanic history of Mare Imbrium.

  3. Np Incorporation into Uranyl Alteration Phases: A Quantum Mechanical Approach

    International Nuclear Information System (INIS)

    L.C. Huller; R.C. Win; U.Ecker

    2006-01-01

    Neptunium is a major contributor to the long-term radioactivity in a geologic repository for spent nuclear fuel (SNF) due to its long half-life (2.1 million years). The mobility of Np may be decreased by incorporation into the U 6+ phases that form during the corrosion of SNF. The ionic radii of Np (0.089nm) and U (0.087nm) are similar, as is their chemistry. Experimental studies have shown Np can be incorporated into uranyl phases at concentrations of ∼ 100 ppm. The low concentration of Np in the uranyl phases complicates experimental detection and presents a significant challenge for determining the incorporation mechanism. Therefore, we have used quantum mechanical calculations to investigate incorporation mechanisms and evaluate the energetics of Np substituting for U. CASTEP, a density functional theory based code that uses plane waves and pseudo-potentials, was used to calculate optimal H positions, relaxed geometry, and energy of different uranyl phases. The incorporation energy for Np in uranyl alteration phases was calculated for studtite, [(UO 2 )O 2 (H 2 O) 2 ](H 2 ) 2 , and boltwoodite, HK(UO 2 )(SiO 4 )* 1.5(H 2 O). Studtite is the rare case of a stable uranyl hydroxyl-peroxide mineral that forms in the presence of H 2 O 2 from the radiolysis of H 2 O. For studtite, two incorporation mechanisms were evaluated: (1) charge-balanced substitution of Np 5+ and H + for one U 6+ , and (2) direct substitution of Np 6+ for U 6+ . For boltwoodite, the H atomic positions prior to Np incorporation were determined, as well as the Np incorporation mechanisms and the corresponding substitution energies. The preferential incorporation of Np into different structure types of U 6+ minerals was also investigated. Quantum mechanical substitution energies have to be derived at Np concentrations higher than the ones found in experiments or expected in a repository. However, the quantum mechanical results are crucial for subsequent empirical force-field and Monte

  4. IR spectra and structure of uranyl pivaloyltrifluoroacetylacetonate isolated in argon matrix

    International Nuclear Information System (INIS)

    Belyaeva, A.A.; Dushin, R.B.; Sidorenko, G.V.; Suglobov, D.N.

    1985-01-01

    When studying IR absorption spectra of a number of isotopomers of uranyl pivaloyl trifluoroacetonate (UPTFA), isolated in the matrix of argon and dissolved in benzene, and comparing them with the spectra of uranyl hexafluoroacetylacetonate (UHFA) vapours, it has been ascertained, that UPTFA vapours consist of monomers and dimers, and UPTFA solution in benzene - of dimers.It is shown, that the dimers have T-shaped structure, at that, the bond inside the dimer is realized by yl-atom of oxygen of an uranyl ion, included in the equatorial coordination sphere of another uranyl ion. Proofs of the dimer T-like structure distortion in gaseous or matrix-isolated state, as a result of which the difference of the angles between uranyl axes from 90 deg is observed, are given. In the framework of approximated model of isolated uranyl-ion the force constants for all the compounds investigated are calaculted

  5. Probing uranyl(VI) speciation in the presence of amidoxime ligands using electrospray ionization mass spectrometry.

    Science.gov (United States)

    Mustapha, Adetayo M; Pasilis, Sofie P

    2013-10-15

    Extraction processes using poly(acrylamidoxime) resins are being developed to extract uranium from seawater. The main complexing agents in these resins are thought to be 2,6-dihydroxyiminopiperidine (DHIP) and N(1),N(5)-dihydroxypentanediimidamide (DHPD), which form strong complexes with uranyl(VI) at the pH of seawater. It is important to understand uranyl(VI) speciation in the presence of these and similar amidoxime ligands to understand factors affecting uranyl(VI) adsorption to the poly(acrylamidoxime) resins. Experiments were carried out in positive ion mode on a quadrupole ion trap mass spectrometer equipped with an electrospray ionization source. The ligands investigated were DHIP, DHPD, and N(1),N(2)-dihydroxyethanediimidamide (DHED). DHED and DHPD differ only in the number of carbons separating the oxime groups. The effects on the mass spectra of changes in uranyl(VI):ligand ratio, pH, and ligand type were examined. DHIP binds uranyl(VI) more effectively than DHPD or DHED in the pH range investigated, forming ions derived from solution-phase species with uranyl(VI):DHIP stoichiometries of 1:1, 1:2, and 2:3. The 2:3 uranyl(VI):DHIP complex appears to be a previously undescribed solution species. Ions related to uranyl(VI):DHPD complexes were detected in very low abundance. DHED is a more effective complexing agent for uranyl(VI) than DHPD, forming ions having uranyl(VI):DHED stoichiometries of 1:1, 1:2, 1:3, and 2:3. This study presents a first look at the solution chemistry of uranyl(VI)-amidoxime complexes using electrospray ionization mass spectrometry. The appearance of previously undescribed solution species suggests that the uranyl-amidoxime system is a rich and relatively complex one, requiring a more in-depth investigation. Copyright © 2013 John Wiley & Sons, Ltd.

  6. The state of uranyl ions in water-dioxane solvent mixtures

    International Nuclear Information System (INIS)

    Geipel, G.; Nebel, D.; Baraniak, L.

    1985-01-01

    A comparison of the spectra of uranyl ions in HCl and dioxane solutions leads to the conclusion that dioxane promotes complex formation. The investigation of spectra showed that taking into account the hydrolysis of uranyl ions in dioxane containing solutions, two successive equilibrium reactions take place. The formation constants were determined. Conductivity measurements confirmed the spectrophotometrically determined equilibria. In solutions containing up to 60 % dioxane there is no incorporation of dioxane in the solvating envelope of the uranyl ion. (author)

  7. Uranyl oxo activation and functionalization by metal cation coordination

    International Nuclear Information System (INIS)

    Arnold Polly, L.; Pecharman, A. F.; Hollis, E.; Parsons, S.; Love, J. B.; Yahia, A.; Maron, L.; Yahia, A.; Maron, L.

    2010-01-01

    The oxo groups in the uranyl ion [UO 2 ] 2+ - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

  8. Uranyl oxo activation and functionalization by metal cation coordination

    Energy Technology Data Exchange (ETDEWEB)

    Arnold Polly, L; Pecharman, A F; Hollis, E; Parsons, S; Love, J B [Univ Edinburgh, EaStCHEM Sch Chem, Edinburgh EH9 3JJ, Midlothian (United Kingdom); Yahia, A; Maron, L [Univ Toulouse 3, LPCNO, UMR 5215, INSA, CNRS, F-31077 Toulouse 4 (France); Yahia, A; Maron, L [Univ Montpellier 2, ENSCM, CNRS, ICSM, UMR 5257, CEA, Ctr Marcoule, F-30207 Bagnols Sur Ceze (France)

    2010-07-01

    The oxo groups in the uranyl ion [UO{sub 2}]{sup 2+} - one of many oxo cations formed by metals from across the periodic table - are particularly inert, which explains the dominance of this ion in the laboratory and its persistence as an environmental contaminant. In contrast, transition metal oxo (M=O) compounds can be highly reactive and carry out difficult reactions such as the oxygenation of hydrocarbons. Here we show how the sequential addition of a lithium metal base to the uranyl ion constrained in a 'Pacman' environment results in lithium coordination to the U=O bonds and single-electron reduction. This reaction depends on the nature and stoichiometry of the lithium reagent and suggests that competing reduction and C-H bond activation reactions are occurring. (authors)

  9. Investigation of uranyl phosphite interaction with some amides

    International Nuclear Information System (INIS)

    Avduevskaya, K.A.; Ragulina, N.B.; Rozanov, I.A.; Mukhajlov, Yu.N.; Kanishcheva, A.S.; Grevtseva, T.G.

    1981-01-01

    Uranyl (amide) phosphitocomplexes of [UO 2 HPO 3 H 2 OAA]xH 2 O, [UO 2 HPO 3 (AA) 2 ], [UO 2 HPO 3 H 2 O DMC], [UO 2 HPO 3 H 2 ODMFA], [UO 2 HPO 3 DAMA] and UO 2 HPO 3 x2FAxH 2 O compositions, where AA-acetamide; DMC-N, N-dimetyl carbamide, DMFA-dimetyl formamide; DAMA-diamide of malonic acid; FA-formamide, are separated, identified and investigated. Derivatives of mono substituted uranyl phosphite of UO 2 (H 2 PO 3 ) 2 x2FA and [UO 2 (H 2 PO 3 ) 2 H 2 O]x2TMC composition (where TMC-tetramethyl carbamide), are synthesized. Structures of complexes with DAMA, TMC, DMFA and acid dimethyl-ammonium diphosphitouranylate-(CH 3 ] 2 NH 2 x[UO 2 (HPO 3 ) 3 (H 2 PO 3 )] are investigated [ru

  10. Investigation of uranyl nitrate complexes with trialkylphosphine oxides

    International Nuclear Information System (INIS)

    Kobets, L.V.; Kopashova, I.M.; Dik, T.A.; Volodin, I.A.; Kovalenko, M.A.; Semenij, V.Ya.

    1982-01-01

    Using the methods of vibrational spectroscopy and thermal analysis a number of uranyl complexes with trialkylphosphine oxides of the general formula UO 2 (NO 3 ) 2 x2R 3 PO, where R-C 2 H 5 -C 10 H 21 have been studied. Infrared and Raman spectra are interpreted according to vibration types. Comparison of vibrational spectra of the complexes in solid phase and solutions of organic solvents permitted to find the differences in position and amount of acids responsible for complexing. It is detected that in the series of complexes investigated the strength of uranyl bond with phosphoryl group oxygen practically remains stable, whereas degree of covalence of nitrate groups is observed. The pointed out peculiarities are interpreted proceeding from the presence of bridge nitrate groups in the structure of the complexes. Thermal stability of the complexes is studied, chemism of their decomposition being suggested

  11. New chemistry of the uranyl ion in non aqueous media

    International Nuclear Information System (INIS)

    Siffredi, G.

    2008-12-01

    This work deals with new aspects of the chemistry of the uranyl(VI) ion {UO 2 } 2+ in anhydrous polar organic solvents such as the activation of the reputedly inert U-O yl bond and the controlled reduction of this species which represent a particularly active field of research that attracts much attention for both its fundamental aspects and applications. Treatment of uranyl(VI) compounds UO 2 X' 2 (X' = I, OTf, Cl) with Me 3 SiX (X = Cl, Br, I) reagents, in various anhydrous polar organic solvents, has been first considered. In most cases, reduction into tetravalent species with complete de-oxygenation of the uranyl {UO 2 } 2+ ion is observed. The reaction is particularly efficient in acetonitrile where the tetravalent [UX 4 (MeCN) 4 ] complexes, which are useful precursors in uranium chemistry, are isolated. In the course of these reactions, the influence of the solvent, the nature of X' and X in the UO 2 X' 2 precursor and the Me 3 SiX reagent are pointed out. Reaction of the uranyl(VI) UO 2 X 2 (X = I, Cl, OTf, NO 3 ) precursors with the anionic MC 5 R 5 (M = K, R = H, Me; M= Li, R = Me; M= Tl, R = H) reagents did not lead to the organometallic [(η 5 -C 5 R 5 ) n UO 2 X 2-n ] species (n = 1, 2) but to pentavalent uranyl(V) complexes. This method is a facile and rapid route towards the formation of stable pentavalent uranyl which offers promising sources for further U(V) chemical developments and for fundamental and applied interests. Their structure is strongly dependent on the nature of the solvent, the additional ligands X and of the M + cation. In pyridine, the {UO 2 (py) 5 } + ion appears to be an ubiquitous and a quite stable entity. The coordinating properties of the basic oxo groups, which coordinate easily to M + ions (M= Li, K, Tl), favour structural diversity with formation of hetero-polymetallic complexes such as [{UO 2 (py) 5 }{MX(py) 2 }] (M= Li, X I), [{UO 2 (py) 5 }{MX 2 (py) 2 }] ∞ (M= K, Tl, X= OTf; M= K, X= I), [{UO 2 (py) 5 }(M 2 X 3 )]

  12. Critical experiments on low enriched uranyl nitrate solution with STACY

    International Nuclear Information System (INIS)

    Miyoshi, Yoshinori

    1996-01-01

    As the STACY started steady operations, systematic criticality data on low enriched uranyl nitrate solution system could be accumulated. Main experimental parameters for the cylindrical tank of 60 cm in diameter were uranium concentration and the reflector condition. Basic data on a simple geometry will be helpful for the validation of the standard criticality safety codes, and for evaluating the safety margin included in the criticality designs. Experiments on the reactivity effects of structural materials such as borated concrete and polyethylene are on schedule next year as the second series of experiments using 10 wt% enriched uranyl solution. Furthermore, neutron interacting experiments with two slab tanks will be performed to investigate the fundamental properties of neutron interaction effects between core tanks. These data will be useful for making more reasonable calculation models and for evaluating the safety margin in the criticality designs for the multiple unit system. (J.P.N.)

  13. Uranyl(VI) luminescence spectroscopy at elevated temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Steudtner, Robin; Franzen, Carola; Brendler, Vinzenz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Surface Processes; Haubitz, Toni [Brandenburg Univ. of Technology, Cottbus-Senftenberg (Germany)

    2016-07-01

    We studied the influence of temperature and ionic strength on the luminescence characteristics (band position, decay time and intensity) of the free uranyl ion (UO{sub 2}{sup 2+}) in acidic aqueous solution. Under the chosen conditions an increasing temperature reduced both intensity and luminescence decay time of the UO{sub 2}{sup 2+} luminescence, but the individual U(VI) emission bands did not change.

  14. Electrochemical behavior of uranyl in anhydrous polar organic media

    Energy Technology Data Exchange (ETDEWEB)

    Burn, Adam G.; Nash, Kenneth L. [Washington State Univ., Pullmann, WA (United States). Dept. of Chemistry

    2017-09-01

    Weak complexes between pentavalent and hexavalent actinyl cations have been reported to exist in acidic, non-complexing high ionic strength aqueous media. Such ''cation-cation complexes'' were first identified in the context of actinide-actinide redox reactions in acidic aqueous media relevant to solvent extraction-based separation systems, hence their characterization is of potential interest for advanced nuclear fuel reprocessing. This chemistry could be relevant to efforts to develop advanced actinide separations based on the upper oxidation states of americium, which are of current interest. In the present study, the chemical behavior of pentavalent uranyl was examined in non-aqueous, aprotic polar organic solvents (propylene carbonate and acetonitrile) to determine whether UO{sub 2}{sup +} cations generated at the reducing working electrode surface would interact with the UO{sub 2}{sup 2+} cations in the bulk phase to form cation-cation complexes in such media. In magnesium perchlorate media, the electrolyte adsorbed onto the working electrode surface and interfered with the uranyl reduction/diffusion process through an ECE (electron transfer/chemical reaction/electron transfer) mechanism. In parallel studies of uranyl redox behavior in tetrabutylammonium hexafluorophosphate solutions, an EC (electron transfer/chemical reaction) mechanism was observed in the cyclic voltammograms. Ultimately, no conclusive electrochemical evidence demonstrated uranyl cation-cation interactions in the non-aqueous, aprotic polar organic solvent solutions, though the results reported do not completely rule out the presence of UO{sub 2}{sup +}.UO{sub 2}{sup 2+} complexes.

  15. Tritium gettering from air with hydrogen uranyl phosphate

    International Nuclear Information System (INIS)

    Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, R.T.

    1985-01-01

    Hydrogen uranyl phosphate (HUP), a solid proton electrolyte, getters tritium gas and water vapor from air by DC electrical action. We have reduced the formation of residual tritiated water to less than 2%, and demonstrated that HUP can clean a 5.5 m 3 working glove box. Data are presented to illustrate the parameters of the gettering and a model is derived. Two other tritium gettering electrolytes have been discovered. 9 refs., 5 figs., 3 tabs

  16. Tritium gettering from air with hydrogen uranyl phosphate. Revision 1

    International Nuclear Information System (INIS)

    Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, R.T.

    1985-01-01

    Hydrogen uranyl phosphate (HUP), a solid proton electrolyte, getters tritium gas and water vapor from air by DC electrical action. We have reduced the formation of residual tritiated water to less than 2%, and demonstrated that HUP can clean a 5.5 m 3 working glove box. Data are presented to illustrate the parameters of the gettering and a model is derived. Two other tritium gettering electrolytes have been discovered. 9 refs., 5 figs., 3 tabs

  17. Structural determination of some uranyl compounds by vibrational spectroscopy

    International Nuclear Information System (INIS)

    Rodriguez S, A.; Martinez Q, E.

    1990-07-01

    The vibrational spectra of different uranyl compounds has been studied and of it spectral information has been used the fundamental asymmetric vibrational frequency, to determine the length and constant bond force U=O by means of the combination of the concept of absorbed energy and the mathematical expression of Badger modified by Jones. It is intended a factor that simplifies the mathematical treatment and the results are compared with the values obtained for other methods. (Author)

  18. Crystal structure of the uranyl-oxide mineral rameauite

    Czech Academy of Sciences Publication Activity Database

    Plášil, Jakub; Škoda, R.; Čejka, J.; Bourgoin, V.; Boulliard, J.C.

    2016-01-01

    Roč. 28, č. 5 (2016), s. 959-967 ISSN 0935-1221 R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : rameauite * uranyl-oxide hydroxy-hydrate * crystal structure * Raman spectrum Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.362, year: 2016

  19. Structure, vibrations and quantum chemical investigations of hydrogen bonded complex of bis(1-hydroxy-2-methylpropan-2-aminium)selenate

    Science.gov (United States)

    Thirunarayanan, S.; Arjunan, V.; Marchewka, M. K.; Mohan, S.

    2017-04-01

    The hydrogen bonded molecular complex bis(1-hydroxy-2-methylpropan-2-aminium)selenate (C8H24N2O6Se) has been prepared by the reaction of 2-amino-2-methyl propanol and selenic acid. The X-ray diffraction analysis revealed that the intermolecular proton transfer from selenic acid (SeO4H2) to 2-amino-2-methylpropanol results in the formation of bis(1-hydroxy-2-methylpropan-2-aminium)selenate (HMPAS) salt and the fragments are connected through H-bonding and ion pairing. The N-H⋯O and O-H⋯O interactions between 2-amino-2-methylpropanol and selenic acid determine the supramolecular arrangement in three-dimensional space. The salt crystallises in the space group P121/n1 of monoclinic system. The complete vibrational assignments of HMPAS have been performed by FTIR and FT-Raman spectroscopy. The experimental data are correlated with the structural properties namely the energy, thermodynamic parameters, atomic charges, hybridization concepts and vibrational frequencies determined by quantum chemical studies performed with B3LYP method using 6-311++G*, 6-31+G* and 6-31G** basis sets.

  20. Preparation and thermogravimetric study of some uranyl phosphates

    International Nuclear Information System (INIS)

    Schaekers, J.M.

    1970-10-01

    The preparation of uranyl ammonium phosphate trihydrate (UAP = UO 2 NH 4 PO 4 .3H 2 O), acid uranyl phosphate tetrahydrate(AUP = UO 2 HPO 4 .4H 2 O) and neutral uranyl phosphate tetrahydrate (NUPT = (UO 2 ) 3 (PO 4 ) 2 .4H 2 O) was investigated during the data from the literature. The thermal decomposition in different atmospheres, such as air, oxygen, nitrogen and argon, was studied in the temperature range 25-1000 0 C. It was found that the pyrophosphate U 2 O 3 P 2 O 7 is a stable decomposition product of UAP as well as of AUP. A mixture of U 3 O 8 and U 2 O 3 P 2 O 7 is obtained when the NUPT is decomposed in an oxygen-free atmosphere. NUPT however is stable in an oxidising atmosphere. Hydrogen and carbon reductions were also carried out, and UO 2 or (UO) 2 P 2 O 7 as well as mixtures of these two products can be obtained, depending on the starting material and the reduction temperature. The different reduction and decomposition reactions were studied by means of thermogravimetric analysis, and activation energies were calculated where possible. I.R. spectral analysis was also used to identify various products with the same composition [af

  1. Safe use and waste disposal of uranyl acetate

    International Nuclear Information System (INIS)

    Sanchez, A.; Calvo, S.; Caparros, G.; Gallego, E.; Rascon, J.; Valladares, M.C.

    2006-01-01

    Radioactive labelled molecules are widely used in Biological Research Centres. The most common radioisotopes are: 32 P, 33 P, 35 S, 3 H, 14 C, 125 I and 45 Ca.Due to the inherent risk in the manipulation of these radiation unsealed sources, in these radioactive installations there are established radiological protection programs to reduce this potential risk and the professional exposure in the manipulation and in the radioactive waste generated. In these Biological Research Centres we used techniques with other radioactive products less used, that we must to control. It is the case of the use of uranyl acetate. Uranyl acetate is a uranium salt used in the preparation of samples for analysis in the electron microscope. Although the amounts used are relatively small, both the chemical and radiological toxicities of these compounds are significant and require working whit that some cautions, with the main emphasis on avoiding the possibility of inhalation of fine particulates or vapours. Due to changes in the Spanish regulations for this product, it was necessary to establish a specific control program in its manipulation. The purpose of this work is the accomplishment of specific protocols for the acquisition, manipulation, contamination measurements, inspections of the work zone and waste management, in order to minimize the risks in the manipulation of uranyl acetate,as well as apply the knowledge and use of specific norms for working with this product. (authors)

  2. Safe use and waste disposal of uranyl acetate

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez, A.; Calvo, S.; Caparros, G.; Gallego, E.; Rascon, J.; Valladares, M.C. [Centro de Biologia Molecular, Madrid (Spain)

    2006-07-01

    Radioactive labelled molecules are widely used in Biological Research Centres. The most common radioisotopes are: {sup 32}P,{sup 33}P, {sup 35}S,{sup 3}H,{sup 14}C,{sup 125}I and {sup 45}Ca.Due to the inherent risk in the manipulation of these radiation unsealed sources, in these radioactive installations there are established radiological protection programs to reduce this potential risk and the professional exposure in the manipulation and in the radioactive waste generated. In these Biological Research Centres we used techniques with other radioactive products less used, that we must to control. It is the case of the use of uranyl acetate. Uranyl acetate is a uranium salt used in the preparation of samples for analysis in the electron microscope. Although the amounts used are relatively small, both the chemical and radiological toxicities of these compounds are significant and require working whit that some cautions, with the main emphasis on avoiding the possibility of inhalation of fine particulates or vapours. Due to changes in the Spanish regulations for this product, it was necessary to establish a specific control program in its manipulation. The purpose of this work is the accomplishment of specific protocols for the acquisition, manipulation, contamination measurements, inspections of the work zone and waste management, in order to minimize the risks in the manipulation of uranyl acetate,as well as apply the knowledge and use of specific norms for working with this product. (authors)

  3. Design of one evaporation system for uranyl nitrate solution

    International Nuclear Information System (INIS)

    Mancilla Romero, R.J.

    1975-01-01

    The authors propose an instant evaporation system with recirculation of the concentrated solution to raise the concentration from 50 to 1500 g of uranium per litre of solution. The capacity of the plant is to be 14.1 kg of uranium per hour. The main equipment used in the system is as follows: 1. Ring-type heat exchanger, for increasing the temperature of the mixture of fresh and recirculated solution from 80 to 115 0 C; 2. Separation tank, in which instant evaporation is carried out. The absolute pressure inside the tank will be 500 mmHg, with steam separation from a concentrated (78.5 wt.%) uranyl nitrate solution; 3. Desuperheater-condenser of horizontal tubular type for condensing water vapour and recovering any uranyl nitrate that may have been entrained; 4. Storage tank for the concentrate, with a capacity for one day's normal operation, and a heating coil to prevent crystallization of the concentrated solution; 5. Two storage tanks for feed and condensate with capacity for one day's normal operation; 6. Supporting structure for the above components. Virtually all equipment in contact with the uranyl nitrate solution will be made of 304 stainless steel. Saturated steam at 143.3 0 C will be required. The cost of the proposed system is $543 030.00. (author)

  4. Photochemistry and exciplex of the uranyl ion in aqueous solution

    International Nuclear Information System (INIS)

    Marcantonatos, M.D.

    1980-01-01

    The effects of acidity, temperature, self-quenching and H-donor concentration on the luminescent state of the aqua-uranyl(VI) ion have been studied in aqueous acidic nitrate and perchlorate solution. The detailed results cannot be explained by any single simple mechanism such as radiative, non-radiative or spontaneous collisional quenching, or irreversible hydrogen abstraction from water. Quantitative analysis of the results shows a far more complex mechanism, involving the adiabatic formation of the species *UO 2 H 2+ and *U 2 O 4 H 4+ , as already proposed by the author. This mechanism is supported by state and m.o. correlations. The abstraction of hydrogen from water is shown to take place by H atom transfer in a *uranyl-water complex intermediate, rather than by attack of H + on the fully occupied πsub(u) orbitals of uranium(V) in a well-defined uranyl water complex with strong charge transfer character. A qualitative description of the exciplex *U 2 O 4 H 4+ is shown to be possible in a v.b. formalism and the origin of its radiative properties is discussed on this basis. (author)

  5. Variable Denticity in Carboxylate Binding to the Uranyl Coordination Complexes

    International Nuclear Information System (INIS)

    Groenewold, G.S.; De Jong, Wibe A.; Oomens, Jos; Van Stipdonk, Michael J.

    2010-01-01

    Tris-carboxylate complexes of the uranyl (UO2)2+ cation with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transformion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetatouranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric -CO2 stretches of both the monodentate and bidentate acetate, CH3 bending and umbrella vibrations, and a uranyl O-U-O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate, and two bidentate benzoate ligands.

  6. Contribution of SELENE-2 geodetic measurements to constrain the lunar internal structure

    Science.gov (United States)

    Matsumoto, K.; Kikuchi, F.; Yamada, R.; Iwata, T.; Kono, Y.; Tsuruta, S.; Hanada, H.; Goossens, S. J.; Ishihara, Y.; Kamata, S.; Sasaki, S.

    2012-12-01

    Internal structure and composition of the Moon provide important clue and constraints on theories for how the Moon formed and evolved. The Apollo seismic network has contributed to the internal structure modeling. Efforts have been made to detect the lunar core from the noisy Apollo data (e.g., [1], [2]), but there is scant information about the structure below the deepest moonquakes at about 1000 km depth. On the other hand, there have been geodetic studies to infer the deep structure of the Moon. For example, LLR (Lunar Laser Ranging) data analyses detected a displacement of the lunar pole of rotation, indicating that dissipation is acting on the rotation arising from a fluid core [3]. Bayesian inversion using geodetic data (such as mass, moments of inertia, tidal Love numbers k2 and h2, and quality factor Q) also suggests a fluid core and partial melt in the lower mantle region [4]. Further improvements in determining the second-degree gravity coefficients (which will lead to better estimates of moments of inertia) and the Love number k2 will help us to better constrain the lunar internal structure. Differential VLBI (Very Long Baseline Interferometry) technique, which was used in the Japanese lunar exploration mission SELENE (Sept. 2007 - June 2009), is expected to contribute to better determining the second-degree potential Love number k2 and low-degree gravity coefficients. SELENE will be followed by the future lunar mission SELENE-2 which will carry both a lander and an orbiter. We propose to put the SELENE-type radio sources on these spacecraft in order to accurately estimate k2 and the low-degree gravity coefficients. By using the same-beam VLBI tracking technique, these parameters will be retrieved through precision orbit determination of the orbiter with respect to the lander which serves as a reference. The VLBI mission with the radio sources is currently one of the mission candidates for SELENE-2. We have conducted a preliminary simulation study on the

  7. Uptake and speciation of selenium in garlic cultivated in soil amended with symbiotic fungi (mycorrhiza) and selenate

    DEFF Research Database (Denmark)

    Larsen, Erik Huusfeldt; Lobinski, R.; Burger-Meyer, K.

    2006-01-01

    The scope of the work was to investigate the influence of selenate fertilisation and the addition of symbiotic fungi (mycorrhiza) to soil on selenium and selenium species concentrations in garlic. The selenium species were extracted from garlic cultivated in experimental plots by proteolytic...... in garlic. The selenium content in garlic, which was analysed by ICP-MS, showed that addition of mycorrhiza to the natural soil increased the selenium uptake by garlic tenfold to 15 mu g g(-1) (dry mass). Fertilisation with selenate and addition of mycorrhiza strongly increased the selenium content...... of soil by mycorrhiza and/or by selenate increased the content of selenium but not the distribution of detected selenium species in garlic. Finally, the use of two-dimensional HPLC (size exclusion followed by reversed-phase) allowed the structural characterisation of gamma...

  8. Determination of selenite and selenate in human urine by ion chromatography and inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Gammelgaard, Bente; Jons, O.

    2000-01-01

    The selenium species selenite, selenate and selenomethionine were separated in aqueous solution by ion chromatography. The separation was performed on an IonPac AG11 in series with an AS11 anion exchange column by elution with 25 mM sodium hydroxide in 2% methanol. The Se-78 and Se-82 isotopes were...... monitored in the inductively coupled plasma mass spectrometry (ICP-MS) detector. When the chromatographic system was applied to analysis of urine samples diluted 1 + 1, the selenomethionine signal appeared in the front together with other unresolved selenium species, while the selenite and selenate signals...... and selenate, respectively, corresponding to absolute amounts of 8 and 16 pg, respectively. Calculations were based on peak height measurements of the Se-82 isotope. In 23 analysed urine samples, the concentration of selenite was in the range selenium...

  9. Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

    Science.gov (United States)

    Kassem, M. E.; Hamed, A. E.; Abulnasr, L.; Abboudy, S.

    1994-11-01

    Isotopic effects in pure and γ-irradiated triglycine selenate crystals were investigated using the specific heat ( Cp) technique. The obtained results showed an interesting dependence of the critical behavior of Cp on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order (γ-type) to a first order transition. After γ-irradiation, the behavior of Cp around the phase transition region was essentially affected. The transition temperature, Tc, decreased and Δ Cp depressed, and the transition became broad. It was noted that the effect of γ-irradiation is opposite to the isotopic effect.

  10. Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

    International Nuclear Information System (INIS)

    Kassem, M.E.; Hamed, A.E.; Abulnasr, L.; Abboudy, S.

    1994-01-01

    Isotopic effects in pure and γ-irradiated triglycine selenate crystals were investigated using the specific heat (C p ) technique. The obtained results showed an interesting dependence of the critical behavior of C p on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order (λ-type) to a first order transition. After γ-irradiation, the behavior of C p around the phase transition region was essentially affected. The transition temperature, T c , decreased and ΔC p depressed, and the transition became broad. It was noted that the effect of γ-irradiation is opposite to the isotopic effect. (author)

  11. Influence of selenite and selenate supplementation on the chromium uptake and translocation in Allium cepa

    International Nuclear Information System (INIS)

    Karuna Shanker; Setia, Seema; Srivastava, Shalini; Dass, Sahab; Srivastava, Rohit; Satya Prakash; Srivastava, M.M.

    1997-01-01

    Pot experiments were conducted on onion plant to study the effects of selenite and selenate treatments (0.5-6.0) μg ml -1 on the uptake and translocation of root absorbed chromium irrigated with 2 and 5 μg ml -1 of chromium in sand and soil. Both the form of selenium (SeO 3 2- , and SeO 4 2- ) were found equally effective in reducing the chromium burden of the plant. No significant difference (p>0.05) in dry matter yields among various selenium treatments exist suggesting no salt injury occurred in the plants under prevailing conditions. (author). 10 refs., 1 tab

  12. Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

    International Nuclear Information System (INIS)

    Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

    2012-01-01

    Highlights: ► The stability of peroxide in uranyl peroxo carbonato complex solutions with different temperatures was characterized. ► The decomposition rate of uranyl peroxo carbonato complex ion to uranyl tris-carbonato complex ion was observed to increase with temperature ► The decomposition kinetics of uranyl peroxo carbonato complex ions was evaluated by absorption and Raman spectroscopies. ► A precipitate of uranyl peroxo carbonato complex solution was evaluated with XRD. - Abstract: This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144 × 10 3 J mol −1 . The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.

  13. Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Kwang-Wook, E-mail: nkwkim@kaeri.re.kr [Korea Atomic Energy Research Institute, 1045 Daedeok daero, Yuseong, Daejeon 305-353 (Korea, Republic of); Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon [Korea Atomic Energy Research Institute, 1045 Daedeok daero, Yuseong, Daejeon 305-353 (Korea, Republic of); Shin, Dong-Woo [Gyeongsang National University, 900 Gajwa, Jinju 660-701 (Korea, Republic of)

    2012-09-30

    Highlights: Black-Right-Pointing-Pointer The stability of peroxide in uranyl peroxo carbonato complex solutions with different temperatures was characterized. Black-Right-Pointing-Pointer The decomposition rate of uranyl peroxo carbonato complex ion to uranyl tris-carbonato complex ion was observed to increase with temperature Black-Right-Pointing-Pointer The decomposition kinetics of uranyl peroxo carbonato complex ions was evaluated by absorption and Raman spectroscopies. Black-Right-Pointing-Pointer A precipitate of uranyl peroxo carbonato complex solution was evaluated with XRD. - Abstract: This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144 Multiplication-Sign 10{sup 3} J mol{sup -1}. The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.

  14. Effect of selenization conditions on the growth and properties of Cu2ZnSn(S,Se)4 thin films

    OpenAIRE

    Ranjbar, Samaneh; Rajesh Menon, M.R.; Fernandes, P.A.; da Cunha, A.F.

    2015-01-01

    The opto-electronic properties of copper zinc tin sulfide can be tuned to achieve better cell efficiencies by controlled incorporation of selenium. In this paper we report the growth of Cu2ZnSn(S,Se)4 (CZTSSe) using a hybrid process involving the sequential evaporation of Zn and sputtering of the sulfide precursors of Cu and Sn, followed by a selenization step. Two approaches for selenization were followed, one using a tubular furnace and the other using a rapid thermal processor. The effects...

  15. Separation of selenium compounds by CE-ICP-MS in dynamically coated capillaries applied to selenized yeast samples

    DEFF Research Database (Denmark)

    Bendahl, Lars; Gammelgaard, Bente

    2004-01-01

    The selenium species in nutritional supplement tablets, based on selenized yeast, were separated by capillary zone electrophoresis using capillaries coated dynamically with poly(vinyl sulfonate) and detected by ICP-MS. Sample pre-treatment consisted of cold-water extraction by sonication and subs......The selenium species in nutritional supplement tablets, based on selenized yeast, were separated by capillary zone electrophoresis using capillaries coated dynamically with poly(vinyl sulfonate) and detected by ICP-MS. Sample pre-treatment consisted of cold-water extraction by sonication...

  16. Energy transfer and quenching processes of excited uranyl ion and lanthanide ions in solutions

    International Nuclear Information System (INIS)

    Yamamura, Tomoo; Tomiyasu, Hiroshi

    1995-01-01

    Deactivation processes of photoexcited uranyl ion by various lanthanide ions in aqueous solution were studied. Each lanthanide ions show different interaction with excited uranyl ion depending on its lowest excited energy level, the number of 4f electrons and the acid concentration of the solution. (author)

  17. A surface structural model for ferrihydrite II: Adsorption of uranyl and carbonate

    NARCIS (Netherlands)

    Hiemstra, T.; Riemsdijk, van W.H.; Rossberg, A.; Ulrich, K.

    2009-01-01

    The adsorption of uranyl (UO22+) on ferrihydrite has been evaluated with the charge distribution (CD) model for systems covering a very large range of conditions, i.e. pH, ionic strength, CO2 pressure, U(VI) concentration, and loading. Modeling suggests that uranyl forms bidentate inner sphere

  18. A protein engineered to bind uranyl selectively and with femtomolar affinity

    Science.gov (United States)

    Zhou, Lu; Bosscher, Mike; Zhang, Changsheng; Özçubukçu, Salih; Zhang, Liang; Zhang, Wen; Li, Charles J.; Liu, Jianzhao; Jensen, Mark P.; Lai, Luhua; He, Chuan

    2014-03-01

    Uranyl (UO22+), the predominant aerobic form of uranium, is present in the ocean at a concentration of ~3.2 parts per 109 (13.7 nM) however, the successful enrichment of uranyl from this vast resource has been limited by the high concentrations of metal ions of similar size and charge, which makes it difficult to design a binding motif that is selective for uranyl. Here we report the design and rational development of a uranyl-binding protein using a computational screening process in the initial search for potential uranyl-binding sites. The engineered protein is thermally stable and offers very high affinity and selectivity for uranyl with a Kd of 7.4 femtomolar (fM) and >10,000-fold selectivity over other metal ions. We also demonstrated that the uranyl-binding protein can repeatedly sequester 30-60% of the uranyl in synthetic sea water. The chemical strategy employed here may be applied to engineer other selective metal-binding proteins for biotechnology and remediation applications.

  19. Production and Characterization of Desmalonichrome Relative Binding Affinity for Uranyl Ions in Relation to Other Siderophores

    Energy Technology Data Exchange (ETDEWEB)

    Mo, Kai-For; Dai, Ziyu; Wunschel, David S.

    2016-06-24

    Siderophores are Fe binding secondary metabolites that have been investigated for their uranium binding properties. Much of the previous work has focused on characterizing hydroxamate types of siderophores, such as desferrioxamine B, for their uranyl binding affinity. Carboxylate forms of these metabolites hold potential to be more efficient chelators of uranyl, yet they have not been widely studied and are more difficult to obtain. Desmalonichrome is a carboxylate siderophore which is not commercially available and so was obtained from the ascomycete fungus Fusarium oxysporum cultivated under Fe depleted conditions. The relative affinity for uranyl binding of desmalonichrome was investigated using a competitive analysis of binding affinities between uranyl acetate and different concentrations of iron(III) chloride using electrospray ionization mass spectrometry (ESI-MS). In addition to desmalonichrome, three other siderophores, including two hydroxamates (desferrioxamine B and desferrichrome) and one carboxylate (desferrichrome A) were studied to understand their relative affinities for the uranyl ion at two pH values. The binding affinities of hydroxymate siderophores to uranyl ion were found to decrease to a greater degree at lower pH as the concentration of Fe (III) ion increases. On the other hand, lowering pH has little impact on the binding affinities between carboxylate siderophores and uranyl ion. Desmalonichrome was shown to have the greatest relative affinity for uranyl at any pH and Fe(III) concentration. These results suggest that acidic functional groups in the ligands are critical for strong chelation with uranium at lower pH.

  20. Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

    International Nuclear Information System (INIS)

    Maroun, E.B.; Hagege, A.; Asfari, Z.; Basset, CH.; Quemeneur, E.; Vidaud, C.

    2009-01-01

    With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

  1. Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

    Energy Technology Data Exchange (ETDEWEB)

    Maroun, E.B.; Hagege, A.; Asfari, Z. [Laboratoire de Chimie Analytique et Minerale, UMR 7178 ULP/CNRS/IN2P3 LC4, ECPM, Strasbourg Cedex (France); Basset, CH.; Quemeneur, E.; Vidaud, C. [CEA IBEB, SBTN, Centre de Marcoule, Bagnols-sur-Ceze (France)

    2009-07-01

    With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

  2. Quantification of uranyl in presence of citric acid; Cuantificacion de uranilo en presencia de acido citrico

    Energy Technology Data Exchange (ETDEWEB)

    Garcia G, N.; Barrera D, C.E. [UAEM, Facultad de Quimica, 50000 Toluca, Estado de Mexico (Mexico); Ordonez R, E. [ININ, 52750 La Marquesa, Estado de Mexico (Mexico)]. e-mail: nidgg@yahoo.com.mx

    2007-07-01

    To determine the influence that has the organic matter of the soil on the uranyl sorption on some solids is necessary to have a detection technique and quantification of uranyl that it is reliable and sufficiently quick in the obtaining of results. For that in this work, it intends to carry out the uranyl quantification in presence of citric acid modifying the Fluorescence induced by UV-Vis radiation technique. Since the uranyl ion is very sensitive to the medium that contains it, (speciation, pH, ionic forces, etc.) it was necessary to develop an analysis technique that stands out the fluorescence of uranyl ion avoiding the out one that produce the organic acids. (Author)

  3. Selen og vitamin E til søer og pattegrise

    DEFF Research Database (Denmark)

    Nielsen, H. E.; Danielsen, V.; Simesen, M. G.

    1977-01-01

    Formålet med dette forsøg var at undersøge virkningen af foderets selen- og vitamin E indhold på søernes frugtbarhed og pattegrisenes levedygtighed og vækst. Endvidere at undersøge koncentrationen af selen (Se) og vitamin E i råmælk, somælk og blod i relation til foderet. Der forekom enkelte...... dødsfald blandt grisene, som kunne sættes i forbindelse med enten lavt Se-indhold eller lavt vitamin E indhold i foderet. Der blev desuden konstateret flere brunst- og drægtighedsproblemer hos søer, derfik foder med det lave indhold af vitamin E end hos søer i de andre grupper. En forøgelse af Se......-indholdet fra 30 til 60 µg pr. kg foder gav en fordobling af indholdet i råmælk og i somælk. En forøgelse af vitamin E indholdet i foderet fra ca. 20 mg til ca. 45 mg pr. kg foder gav 4 gange forøgelse i råmælk og somælk. Der blev konstateret tilsvarende virkninger af Se og vitamin E i foderet på indholdet i...

  4. Combination cancer treatment through photothermally controlled release of selenous acid from gold nanocages.

    Science.gov (United States)

    Cheng, Haoyan; Huo, Da; Zhu, Chunlei; Shen, Song; Wang, Wenxia; Li, Haoxuan; Zhu, Zhihong; Xia, Younan

    2018-04-03

    Selenite, one of the inorganic forms of selenium, is emerging as an attractive chemotherapeutic agent owing to its selectivity in eradicating cancer cells. Here we demonstrate a new formulation of nanomedicine based on selenous acid, which is mixed with lauric acid (a phase-change material with a melting point around 43 °C) and then loaded into the cavities of Au nanocages. The Au nanocages can serve as a carrier during cell endocytosis and then as a photothermal agent to melt the lauric acid upon the irradiation with a near-infrared laser, triggering the swift release of selenous acid. The photothermal and chemo therapies can also work synergistically, leading to enhanced destruction of cancer cells relative to normal cells. Our systematic study suggests that the impaired mitochondrial function arising from the ROS generated through combination treatment is responsible for the cell death. This study offers an appealing candidate that holds great promise for synergistic cancer treatment. Published by Elsevier Ltd.

  5. From zinc selenate to zinc selenide nano structures synthesized by reduction process

    International Nuclear Information System (INIS)

    Hutagalung, S.D.; Eng, S.T.; Ahmad, Z.A.; Ishak Mat; Yussof Wahab

    2009-01-01

    One-dimensional nano structure materials are very attractive because of their electronic and optical properties depending on their size. It is well known that properties of material can be tuned by reducing size to nano scale because at the small sizes, that they behave differently with its bulk materials and the band gap will control by the size. The tunability of the band gap makes nano structured materials useful for many applications. As one of the wide band gaps semiconductor compounds, zinc selenide (ZnSe) nano structures (nanoparticles, nano wires, nano rods) have received much attention for the application in optoelectronic devices, such as blue laser diode, light emitting diodes, solar cells and IR optical windows. In this study, ZnSe nano structures have been synthesized by reduction process of zinc selenate using hydrazine hydrate (N 2 H 4 .2H 2 O). The reductive agent of hydrazine hydrate was added to the starting materials of zinc selenate were heat treated at 500 degree Celsius for 1 hour under argon flow to form one-dimensional nano structures. The SEM and TEM images show the formation of nano composite-like structure, which some small nano bar and nano pellets stick to the rod. The x-ray diffraction and elemental composition analysis confirm the formation of mixture zinc oxide and zinc selenide phases. (author)

  6. Comparative study of uranyl(VI) and -(V) carbonato complexes in an aqueous solution.

    Science.gov (United States)

    Ikeda, Atsushi; Hennig, Christoph; Tsushima, Satoru; Takao, Koichiro; Ikeda, Yasuhisa; Scheinost, Andreas C; Bernhard, Gert

    2007-05-14

    Electrochemical, complexation, and electronic properties of uranyl(VI) and -(V) carbonato complexes in an aqueous Na2CO3 solution have been investigated to define the appropriate conditions for preparing pure uranyl(V) samples and to understand the difference in coordination character between UO22+ and UO2+. Cyclic voltammetry using three different working electrodes of platinum, gold, and glassy carbon has suggested that the electrochemical reaction of uranyl(VI) carbonate species proceeds quasi-reversibly. Electrolysis of UO22+ has been performed in Na2CO3 solutions of more than 0.8 M with a limited pH range of 11.7 < pH < 12.0 using a platinum mesh electrode. It produces a high purity of the uranyl(V) carbonate solution, which has been confirmed to be stable for at least 2 weeks in a sealed glass cuvette. Extended X-ray absorption fine structure (EXAFS) measurements revealed the structural arrangement of uranyl(VI) and -(V) tricarbonato complexes, [UO2(CO3)3]n- [n = 4 for uranyl(VI), 5 for uranyl(V)]. The bond distances of U-Oax, U-Oeq, U-C, and U-Odist are determined to be 1.81, 2.44, 2.92, and 4.17 A for the uranyl(VI) complex and 1.91, 2.50, 2.93, and 4.23 A for the uranyl(V) complex, respectively. The validity of the structural parameters obtained from EXAFS has been supported by quantum chemical calculations for the uranyl(VI) complex. The uranium LI- and LIII-edge X-ray absorption near-edge structure spectra have been interpreted in terms of electron transitions and multiple-scattering features.

  7. Comparing uranyl sorption complexes on soil and reference clays

    International Nuclear Information System (INIS)

    Chisholm-Brause, C.J.; Berg, J.M.; Conradson, S.D.; Morris, D.E.; McKinley, J.P.; Zachara, J.M.

    1993-01-01

    Clay minerals and other components in natural soils may play a key role in limiting the mobility of uranium in the environment through the formation of sorption complexes. Reference clays are frequently used as models to study sorption processes because they have well-known chemical and physical properties, but they may differ chemically and morphologically from clays derived from natural soils. Therefore, inferences based on reference clay data have been questioned. The authors have used luminescence and x-ray absorption spectroscopies to characterize the sorption complexes of aqueous uranyl (UO 2 2+ ) species on two soil smectites from the Kenoma and Ringold formations, and compared these results to those obtained on reference smectite clays. The pH dependence of uptake suggests that the ratio of sorption on amphoteric edge sites is greater for the soil smectites than for reference clays such as Wyoming montmorillonite (SWy-1). The luminescence spectra for uranyl sorbed to the soil clays are very similar to those for uranyl sorbed principally to the edge sites of SWy-1. This observation supports the solution data suggesting that adsorption to amphoteric sites is a more important mechanism for soil clays. However, the spectral data indicate that the sorption complexes on natural and reference clays are quite similar. Furthermore, as with the reference clays, the authors have found that the chemistry of the solution plays a greater role in defining the sorption complex than does the clay matrix. Thus, if differences in surface properties are adequately taken into account, the reference clays may serve as useful analogs for soil clays in investigations of metal-ion sorption

  8. Determination of free nitric acid in uranyl nitrate solution

    International Nuclear Information System (INIS)

    Mayankutty, P.C.; Ravi, S.; Nadkarni, M.N.

    1981-01-01

    Potentiometric titration of uranyl nitrate solution with sodium hydroxide exhibits two peaks. The first peak characterises the following reaction, UO 2 (C 2 O 4 )+NaOH Na[UO 2 (C 2 O 4 )(OH)]. This reaction, indicating the partial hydrolysis of uranyl oxalate complex, appears to be complete at pH9. If the titration is carried out to this end-point pH, the total alkali consumed can be equated to the sum of uranium content and the free acidity present in the sample volume. Based on this, a method was standardised to determine the free acidity in uranyl nitrate solution. The sample, taken in a solution of potassium oxalate previously adjusted to pH9, is titrated to this pH with standard sodium hydroxide. The free acidity in the sample can be computed by subtracting the alkali reacted with uranium from the total alkali consumed. Analyses of several synthetic samples containing uranium and nitric acid in a wide range of combinations indicate that the free acidity can be accurately determined by this method, if uranium concentration in the sample is known. The results are compared to those obtained by two other widely used methods, viz., (i) titration of pH7 in the presence of neutral potassium oxalate to suppress hydrolysis and (ii) separation of hydrolyzable ions on a cationic resin and alkali titration of the free acid released. The advantages of and the precision obtained with the present method over the above two methods are discussed. (author)

  9. Study of diamagnetism in uranyl complexes of some Schiff bases

    International Nuclear Information System (INIS)

    Dodwad, S.S.; Sawant, A.S.

    1992-01-01

    Uranyl complexes of Schiff bases obtained by condensing salicylaldehyde with aromatic amines have been isolated and characterised. The complexes have the formula M (LH) 2 (NO 3 ) 2 where M = UO 2 and LH = Schiff base. The magnetic susceptibilities of these complexes have been measured on a Gouy balance. These values have been compared with the computed ones. The percentage deviation between the observed and computed values of molar magnetic susceptibilities clearly show that they are outside experimental error and therefore significant. These deviations have been discussed in the light of VanVleck's, equation for molar susceptibility of polyatomic molecule. (author). 3 refs., 1 tab

  10. Acute toxicity of uranium hexafluoride, uranyl fluoride and hydrogen fluoride

    International Nuclear Information System (INIS)

    Just, R.A.

    1988-01-01

    Uranium hexafluoride (UF 6 ) released into the atmosphere will react rapidly with moisture in the air to form the hydrolysis products uranyl fluoride (UO 2 F 2 ) and hydrogen fluoride (HF). Uranium compounds such as UF 6 and UO 2 F 2 exhibit both chemical toxicity and radiological effects, while HF exhibits only chemical toxicity. This paper describes the development of a methodology for assessing the human health consequences of a known acute exposure to a mixture of UF 6 , UO 2 F 2 , and HF. 4 refs., 2 figs., 5 tabs

  11. Biosolubilization of uranyl ions in uranium ores by hydrophyte plants

    International Nuclear Information System (INIS)

    Cecal, Alexandru; Calmoi, Rodica; Melniciuc-Puica, Nicoleta

    2006-01-01

    This paper investigated the bioleaching of uranyl ions from uranium ores, in aqueous medium by hydrophyte plants: Lemna minor, Azolla caroliniana and Elodea canadensis under different experimental conditions. The oxidation of U(IV) to U(VI) species was done by the atomic oxygen generated in the photosynthesis process by the aquatic plants in the solution above uranium ores. Under identical experimental conditions, the capacity of bioleaching of uranium ores decreases according to the following series: Lemna minor > Elodea canadensis > Azolla caroliniana. The results of IR spectra suggest the possible use of Lemna minor and Elodea canadensis as a biological decontaminant of uranium containing wastewaters. (author)

  12. Detection of over 100 selenium metabolites in selenized yeast by liquid chromatography electrospray time-of-flight mass spectrometry.

    Science.gov (United States)

    Gilbert-López, Bienvenida; Dernovics, Mihaly; Moreno-González, David; Molina-Díaz, Antonio; García-Reyes, Juan F

    2017-08-15

    The characterization of the selenometabolome of Selenized(Se)-yeast, that is the fraction of water soluble low-molecular weight Se-metabolites produced in Se-yeast is of paramount interest to expand the knowledge on the composition of this food supplement. In this work, we have applied liquid chromatography electrospray time-of-flight mass spectrometry (LC-TOFMS) to search for Se-species from the low molecular weight range fraction of the selenized yeast used for food supplements. Prior to LC-TOFMS, sample treatment consisted of ultrasound assisted water extraction followed by size exclusion fractionation assisted with off-line inductively coupled plasma mass spectrometry detection of isotope 82 Se. The fraction corresponding to low-molecular weight species was subjected to LC-TOFMS using electrospray ionization in the positive ion mode. The detection of the suspected selenized species has been based on the information obtained from accurate mass measurements of both the protonated molecules and fragments from in-source CID fragmentation; along with the characteristic isotope pattern exhibited by the presence of Se. The approach enables the detection of 103 selenized species, most of them not previously reported, in the range from ca. 300-650Da. Besides the detection of selenium species, related sulphur derivate metabolites were detected based on the accurate mass shift due to the substitution of sulphur and selenium. Copyright © 2017. Published by Elsevier B.V.

  13. Uptake and specification of selenium in garlic cultivated in soil amended with symbiotic fungi (mycorrhiza) and selenate

    NARCIS (Netherlands)

    Larsen, E.H.; Lobinski, R.; Burger-Meijer, K.; Hansen, M.; Ruzik, R.; Mazurowska, L.; Rasmussen, P.H.; Sloth, J.J.; Scholten, O.E.; Kik, C.

    2006-01-01

    The scope of the work was to investigate the influence of selenate fertilisation and the addition of symbiotic fungi (mycorrhiza) to soil on selenium and selenium species concentrations in garlic. The selenium species were extracted from garlic cultivated in experimental plots by proteolytic

  14. Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures.

    Science.gov (United States)

    Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

    2012-09-30

    This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144×10(3) J mol(-1). The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Influence of uranyl dibutylphosphate on the UV/VIS spectrophotometric online monitoring of uranium in tributylphosphate/hydrocarbon solvent

    International Nuclear Information System (INIS)

    Creech, E.T.; Rutenberg, A.C.; Smithwick, R.W.; Seals, R.D.

    1984-01-01

    In the uranium recovery process at the Y-12 Plant uranium is recovered from aqueous uranyl solutions by extraction into a solvent consisting of 30% tributylphosphate (TBP) and 70% hydrocarbon solvent. Within this process the uranium is continuously monitored by a UV/VIS absorbance measurement of the uranyl/tributylphosphate complex in the organic phase. The uranium is then further extracted from the organic phase to a final water phase. Dibutylphosphate (DBP), which is a decomposition product of TBP, builds up in the organic solvent. A very strong complex of uranyl/dibutylphosphate is formed which cannot be extracted into the aqueous phase. Prior to this work the uranyl/dibutylphosphate complex absorbance was assumed to be the same as the uranyl tributylphosphate complex. To determine the effect of the presence of uranyl/dibutylphosphate on the continuous UV/VIS monitor required (a) the purification of commercial dibutylphosphate, (b) the synthesis, and (c) the characterization of uranyl/dibutylphosphate

  16. Investigation into the dehydration of selenate doped Na2M(SO4)2·2H2O (M = Mn, Fe, Co and Ni): Stabilisation of the high Na content alluaudite phases Na3M1.5(SO4)3-1.5x(SeO4)1.5x (M = Mn, Co and Ni) through selenate incorporation

    Science.gov (United States)

    Driscoll, L. L.; Kendrick, E.; Knight, K. S.; Wright, A. J.; Slater, P. R.

    2018-02-01

    In this paper we report an investigation into the phases formed on dehydration of Na2M(SO4)2-x(SeO4)x·2H2O (0 ≤ x ≤ 1; M = Mn, Fe, Co and Ni). For the Fe series, all attempts to dehydrate the samples doped with selenate resulted in amorphous products, and it is suspected that a side redox reaction involving the Fe and selenate may be occurring leading to phase decomposition and hence the lack of a crystalline product on dehydration. For M = Mn, Co, Ni, the structure observed was shown to depend upon the transition metal cation and level of selenate doping. An alluaudite phase, Na3M1.5(SO4)3-1.5x(SeO4)1.5x, was observed for the selenate doped compositions, with this phase forming as a single phase for x ≥ 0.5 M = Co, and x = 1.0 M = Ni. For M = Mn, the alluaudite structure is obtained across the series, albeit with small impurities for lower selenate content samples. Although the alluaudite-type phases Na2+2y(Mn/Co)2-y(SO4)3 have recently been reported [1,2], doping with selenate appears to increase the maximum sodium content within the structure. Moreover, the selenate doped Ni based samples reported here are the first examples of a Ni sulfate/selenate containing system exhibiting the alluaudite structure.

  17. Microporous uranyl chromates successively formed by evaporation from acidic solution

    Energy Technology Data Exchange (ETDEWEB)

    Siidra, Oleg I.; Nazarchuk, Evgeny V.; Bocharov, Sergey N.; Kayukov, Roman A. [St. Petersburg State Univ. (Russian Federation). Dept. of Crystallography; Depmeier, Wulf [Kiel Univ. (Germany). Inst. fuer Geowissenschaften

    2018-04-01

    The first microporous framework structures containing uranium and chromium have been synthesized and characterized. Rb{sub 2}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 3}(H{sub 2}O){sub 2}](H{sub 2}O){sub 3} (1) was crystallized from uranyl chromate solution by evaporation. Further evaporation led to increased viscosity of the solution and overgrowing of Rb{sub 2}[(UO{sub 2}){sub 2}(CrO{sub 4}){sub 3}(H{sub 2}O)](H{sub 2}O) (2) on the crystals of 1. With respect to 1, the framework of 2 is partially dehydrated. Both frameworks differ compositionally by only one water molecule, but this seemingly small difference affects significantly the pore size and overall structural topology of the frameworks, which present very different flexibility of the U-O-Cr links. These are rigid in the pillared framework of 1, in contrast to 2 where the U-O-Cr angles range from 126.3 to 168.2 , reflecting the substantial flexibility of Cr-O-U connections which make them comparable to the corresponding Mo-O-U links in uranyl molybdates.

  18. SEPARATION OF BARIUM VALUES FROM URANYL NITRATE SOLUTIONS

    Science.gov (United States)

    Tompkins, E.R.

    1959-02-24

    The separation of radioactive barium values from a uranyl nitrate solution of neutron-irradiated uranium is described. The 10 to 20% uranyl nitrate solution is passed through a flrst column of a cation exchange resin under conditions favoring the adsorption of barium and certain other cations. The loaded resin is first washed with dilute sulfuric acid to remove a portion of the other cations, and then wash with a citric acid solution at pH of 5 to 7 to recover the barium along with a lesser amount of the other cations. The PH of the resulting eluate is adjusted to about 2.3 to 3.5 and diluted prior to passing through a smaller second column of exchange resin. The loaded resin is first washed with a citric acid solution at a pH of 3 to elute undesired cations and then with citric acid solution at a pH of 6 to eluts the barium, which is substantially free of undesired cations.

  19. Preparation and physicochemical characterization of anionic uranyl. beta. -ketoenolates

    Energy Technology Data Exchange (ETDEWEB)

    Marangoni, G; Paolucci, G [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Graziani, R; Celon, E

    1978-01-01

    New classes of anionic uranyl ..beta..-ketoenolates of formula (UO/sub 2/L/sub 2/X)/sup -/ (where L = 1,3-diphenylpropane-1,3-dionate (dppd), 4,4,4-trifluoro-1-phenylbutane-1,3-dionate (tfpbd), or 1-phenylbutane-1,3-dionate (pbd); X = Cl/sup -/, Br/sup -/, I/sup -/, (NO/sub 3/)/sup -/, (O/sub 2/CMe)/sup -/, or (NCS)/sup -/) and (L/sub 2/O/sub 2/U(..mu..-X) UO/sub 2/L/sub 2/)/sup -/ (where X = F/sup -/, and also Cl/sup -/ only in the case of L = dppd) have been synthesized and characterized by a number of physical measurements. The different ability of the various anionic ligands to enter into the co-ordination sphere of the uranyl ion, their potentially different bonding modes, and the possible correlations between physical parameters and the nature of either the chelate substituents or the anionic ligand are discussed.

  20. Bases for DOT exemption uranyl nitrate solution shipments

    International Nuclear Information System (INIS)

    Moyer, R.A.

    1982-07-01

    Uranyl nitrate solutions from a Savannah River Plant reprocessing facility have been transported in cargo tank trailers for more than 20 years without incident during transit. The solution is shipped to Oak Ridge for further processing and returned to SRP in a solid metal form for recycle. This solution, called uranyl nitrate hexahydrate (UNH) solution in Department of Transportation (DOT) regulations, is currently diluted about 2-fold to comply with DOT concentration limits (10% of low specific activity levels) specified for bulk low specific activity (LSA) liquid shipments. Dilution of the process solution increases the number of shipments, the cost of transportation, the cost of shipper preparations, the cost of further reprocessing in the receiving facility to first evaporate the added water, and the total risk to the population along the route of travel. However, the radiological risk remains about the same. Therefore, obtaining an exemption from DOT regulations to permit shipment of undiluted UNH solution, which is normally about two times the present limit, is prudent and more economical. The radiological and nonradiological risks from shipping a unit load of undiluted solution are summarized for the probable route. Data and calculations are presented on a per load or per shipment basis throughout this memorandum to keep it unclassified

  1. Modulation of the unpaired spin localization in Pentavalent Uranyl Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Vetere, V.; Maldivi, P.; Mazzanti, M. [CEA Grenoble, INAC, SCIB, laboratoire de reconnaissance ionique et chimie de coordination, 38 (France); Vetere, V. [UMR5626, laboratoire de chimie et physique quantique, universite de Toulouse, 31 - Toulouse (France)

    2010-06-15

    The electronic structure of various complexes of pentavalent uranyl species, namely UO{sub 2}{sup +}, is described, using DFT methods, with the aim of understanding how the structure of the ligands may influence the localisation of the unpaired 5f electron of uranium (V) and, finally, the stability of such complexes towards oxidation. Six complexes have been inspected: [UO{sub 2}py{sub 5}]{sup +} (1), [(UO{sub 2}py{sub 5})KI{sub 2}] (2), [UO{sub 2}(salan-{sup t}Bu{sub 2})(py)K] (3), [UO{sub 2}(salophen-{sup t}Bu{sub 2})(thf)K] (4), [UO{sub 2}(salen-{sup t}Bu{sub 2})(py)K] (5), [and UO{sub 2}-cyclo[6]pyrrole]{sup 1-} (6), chosen to explore various ligands. In the five first complexes, the UO{sub 2}{sup +} species is well identified with the unpaired electron localized on the 5f uranium orbital. Additionally, for the salan, salen and salophen ligands, some covalent interactions have been observed, resulting from the presence of both donor and acceptor binding sites. In contrast, the last complex is best described by a UO{sub 2}{sup 2+} uranyl (VI) coordinated by the anionic radical cyclo-pyrrole, the highly delocalized p orbitals set stabilizing the radical behaviour of this ligand. (authors)

  2. Photophysics of the excited uranyl ion in aqueous solutions

    International Nuclear Information System (INIS)

    Formosinho, S.J.; Miguel, M. da G.M.

    1985-01-01

    The effect of the micelles of Triton X-100 on the biexponential decay of (UO 2 2+ )* has been investigated. Data are analysed in terms of a reversible crossing mechanism for the decay. Azulene fluorescence quenching and 13 C n.m.r. studies strongly suggest that uranyl ions are able to penetrate deep inside the micelle core. Micelle quenching for the reversible decay of (UO 2 2+ )* occurs in the interior (ksub(q) = 3 x 10 10 dm 3 mol -1 s -1 ) and at the surface (Ksub(q) = 1.5 x 10 9 mol -1 dm 3 s -1 ) of the micelles. The latter process has a rate virtually identical to that for the free surfactant molecules. Penetration of (UO 2 2+ )* inside the non-polar regions of the micelle core increases solvent exchange rates by ca. two orders of magnitude. Uranyl-ion excimers are formed in occupied micelles. The quenching processes decrease strongly for these species because excimers do not penetrate the micelles. (author)

  3. Enhanced Adsorption and Recovery of Uranyl Ions by NikR Mutant-Displaying Yeast

    Directory of Open Access Journals (Sweden)

    Kouichi Kuroda

    2014-04-01

    Full Text Available Uranium is one of the most important metal resources, and the technology for the recovery of uranyl ions (UO22+ from aqueous solutions is required to ensure a semi-permanent supply of uranium. The NikR protein is a Ni2+-dependent transcriptional repressor of the nickel-ion uptake system in Escherichia coli, but its mutant protein (NikRm is able to selectively bind uranyl ions in the interface of the two monomers. In this study, NikRm protein with ability to adsorb uranyl ions was displayed on the cell surface of Saccharomyces cerevisiae. To perform the binding of metal ions in the interface of the two monomers, two metal-binding domains (MBDs of NikRm were tandemly fused via linker peptides and displayed on the yeast cell surface by fusion with the cell wall-anchoring domain of yeast α-agglutinin. The NikRm-MBD-displaying yeast cells with particular linker lengths showed the enhanced adsorption of uranyl ions in comparison to the control strain. By treating cells with citrate buffer (pH 4.3, the uranyl ions adsorbed on the cell surface were recovered. Our results indicate that the adsorption system by yeast cells displaying tandemly fused MBDs of NikRm is effective for simple and concentrated recovery of uranyl ions, as well as adsorption of uranyl ions.

  4. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sang-Won; Leckie, J.O. [Stanford Univ., CA (United States); Siegel, M.D. [Sandia National Labs., Albuquerque, NM (United States)

    1995-09-01

    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption.

  5. Influence of Acidity on Uranyl Nitrate Association in Aqueous Solutions: A Molecular Dynamics Simulation Study

    International Nuclear Information System (INIS)

    de Almeida, Valmor F.; Cui, Shengting; Khomami, Bamin; Ye, Xianggui; Smith, Rodney Bryan

    2010-01-01

    Uranyl ion complexation with water and nitrate is a key aspect of the uranium/plutonium extraction process. We have carried out a molecular dynamics simulation study to investigate this complexation process, including the molecular composition of the various complex species, the corresponding structure, and the equilibrium distribution of the complexes. The observed structures of the complexes suggest that in aqueous solution, uranyls are generally hydrated by 5 water molecules in the equatorial plane. When associating with nitrate ions, a water molecule is replaced by a nitrate ion, preserving the five-fold coordination and planar symmetry. Analysis of the pair correlation function between uranyl and nitrate suggests that nitrates bind to uranyl in aqueous solution mainly in a monodentate mode, although a small portion of bidentates occur. Dynamic association and dissociation between uranyls and nitrates take place in aqueous solution with a substantial amount of fluctuation in the number of various uranyl nitrate species. The average number of the uranyl mononitrate complexes shows a dependence on acid concentration consistent with equilibrium-constant analysis, namely, the concentration of [UO2NO3]+ increases with nitric acid concentration.

  6. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    International Nuclear Information System (INIS)

    Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

    1995-09-01

    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption

  7. Use of uranyl nitrate as a shift reagent in polar and inert solvents

    International Nuclear Information System (INIS)

    Nosov, B.P.

    1988-01-01

    This work examines the effect of uranyl nitrate as a shift reagent on the PMR spectra of different organic molecules in polar and inert solvents. In order to identify the coordination site of the uranyl ion, its effect on the spectra of amino acids and acetic or propionic acids in water was compared. It was found that the induced shifts of the protons in the corresponding positions of the different acids after addition of uranyl nitrate agreed to within ±0.01 ppm. When nitrogenous bases such as diethylamine and pyridine were added to solutions of the carboxylic acids with uranyl nitrate, an increase in the induced chemical shift of the resonance signals occurred. These facts suggest the coordination of the uranyl ion with the carboxyl oxygen both for acetic and propionic acids and for amino acids. The authors established that the addition of uranyl nitrate to solutions of organic compounds caused different downfield shifts of the resonance signals from the protons. In polar solvents shifts induced by uranyl nitrate in the PMR spectra of carboxylic acids occur only when nitrogenous bases are added

  8. Spectroscopic studies of 2-thenoyltrifluoro acetonate of uranyl salts doped with europium

    International Nuclear Information System (INIS)

    Nakagawa, F.T.; Luiz, J.E.M. de Sa; Felinto, M.C.F.C.; Brito, H.F.; Teotonio, E.E.S.

    2006-01-01

    Uranyl compounds present a great potential as luminescence materials. Some examples of applications are: in laser technology, cathode ray tube, X-rays diagnostic. In this work it was studied the synthesis, characterization and spectroscopic properties study of uranyl 2-thenoyl trifluoroacetonate and uranyl 2- thenoyl trifluoroacetonate doped with europium. The compounds were synthesized and characterized by infrared absorption spectroscopy, thermal analysis, scanning electronic microscopy, and electronic spectroscopy of emission and excitation. The Eu 3+ ion acted as an effective luminescent probe, however the process of energy transfer from UO 2 2+ to Eu 3+ ion has not been efficient. (author)

  9. Unusual case of a polar copper(II) uranyl phosphonate that fluoresces

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A.G.D.; Albrecht-Schmitt, Th.E. [Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, Indiana (United States)

    2010-06-15

    A polar Cu(II) uranyl diphosphonate, Cu(H{sub 2}O){sub 4}(UO{sub 2}){sub 3}(H{sub 2}O){sub 2}[CH{sub 2}(PO{sub 3}){sub 2}]{sub 2}.5H{sub 2}O, has been prepared under mild hydrothermal conditions. This compound has direct linkages between the oxo atoms of the uranyl moieties and the Cu(II) centers. Despite the presence of Cu(II) in the structure, vibronically-coupled emission is still observed, most likely because there are two crystallographically unique uranyl moieties, only one of which bonds to Cu(II). (authors)

  10. Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives

    International Nuclear Information System (INIS)

    Schoendorff, George E.; Windus, Theresa L.; De Jong, Wibe A.

    2009-01-01

    The coordination of nitrile (acetonitrile, propionitrile, and benzonitrile) and carbonyl (formaldehyde, ethanal, and acetone) ligands to the uranyl dication (UO22+) has been examined using density functional theory (DFT) utilizing relativistic effective core potentials (RECPs). Complexes containing up to six ligands have been modeled for all ligands except formaldehyde, for which no minimum could be found. A comparison of relative binding energies indicates that five coordinate complexes are predominant while a six coordinate complex involving propionitrile ligands might be possible. Additionally, the relative binding energy and the weakening of the uranyl bond is related to the size of the ligand and, in general, nitriles bind more strongly to uranyl than carbonyls.

  11. Removal of uranyl ions from residual waters using some algae types

    International Nuclear Information System (INIS)

    Cecal, A.; Palamaru, I.; Humelnicu, D.; Popa, K.; Salaru, V.V.; Rudic, V.; Gulea, A.

    1999-01-01

    This paper deals with a study on the bioaccumulation of uranyl ions resulted from residual effluents by means of some microbiological collectors: Scenedesmus quadricauda, Anabaena karakumica, Calothrix brevissima, Penicillinium sp, as well as the Glucid extract of Porphyridium cruentum, under various experimental conditions. The retaining degree of the bioaccumulated uranyl ions, as well as the leaching degree, in HCl and H 2 O media, of the same ions previously retained on algae were established. The retaining degree decreases in the series: Scenedesmus quadricauda > Anabaena karakumica > Penicillinium sp > Calothrix brevissima. The leaching effect of bioaccumulated uranyl ions is higher in hydrochloric acid than in water. (author)

  12. Mass-spectrometric study of volatile uranyl β-diketonates and their adducts

    International Nuclear Information System (INIS)

    Adamov, V.M.; Belyaev, B.N.; Berezinskij, S.O.; Sidorenko, G.V.; Suglobov, D.N.

    1985-01-01

    The mass spectra of a number of uranyl β-diketonates containing methyl, trifluoromethyl and tert-butyl substituents in β-diketonate anion, and their adducts are measured. The form of the unsolvated β-diketonates and their adducts in gas phase is studied. The ways of fragmentation of uranyl β-diketonates and their adducts are investigated. The data concerning the thermal and chemical side reactions proceeding with uranyl β-diketonates and their addicts in an ion source are obtained. The mass spectra of the samples of neptunyl and plutonyl β-diketonate adducts synthesized for the first time are measured

  13. Removal of uranyl ions from residual waters using some algae types

    International Nuclear Information System (INIS)

    Cecal, Al.; Rudic, V.; Gulea, A.; Palamaru, I.; Humelnicu, D.; Salaru, V.V.; Popa, K.

    1997-01-01

    This paper deals with a study on the bioaccumulation of uranyl ions resulted from residual effluents, by means of some microbiological collectors: Scenedesmus quadricauda, Anabaena karakumica, Calothrix brevissima, Penicillium sp, as well as the Glucide extract of Porphyridium cruentum, in several experimental conditions. The retaining degree of the bioaccumulated uranyl ions, as well as the leaching degree, in HCl and H 2 O media, of the same ions previously retained on algae, were karakumica >Penicillium sp> Calothrix brevissima. The leaching effect of bioaccumulated uranyl ions is higher in hydrochloric acid then in water. (authors)

  14. Sorption mechanisms of selenium species (selenite and selenate) on copper-based minerals

    International Nuclear Information System (INIS)

    Devoy, J.

    2001-09-01

    The sorption of radionuclides on the surface of minerals represents a process capable to delay the migration of the elements from a spent fuel deep repository towards the biosphere. In the framework of a deep underground repository, an engineered clay barrier has a high trapping capacity for cationic radio-elements, in particular because of the negative charge of clay surfaces. However, anionic radioelements like selenium species, would be only weakly retained by chemical processes. In order to optimize the trapping capacity of a clay barrier with respect to anionic species, prospective studies are carried out in order to find and evaluate some minerals with specific chemical trapping functions. Among radionuclides, the case of selenium has to be considered because its isotope 79 Se is present in radioactive wastes and has a half life time of 6.5 10 4 years. It is also judicious to find a mineral capable of trapping simultaneously several anionic radio-elements. Copper oxides and sulfides (Cu 2 O, CuO, Cu 2 S, CuS, CuFeS 2 and Cu 5 FeS 4 ) are good adsorbents with respect to selenium species (selenite and selenate). These minerals, with their selenium retention properties, could be used also for the decontamination of soils and waters or to process industrial effluents. The sorption mechanisms have been studied in details for copper oxides (Cu 2 O and CuO) with respect to selenite and selenate. Chalcomenite precipitates in acid pH conditions when selenite is added to a Cu 2 O and CuO suspension. Selenate, in contact with cuprite (Cu 2 O) leads also to a selenium-based precipitate in acid pH environment. For higher pH values, selenite and selenate are adsorbed on copper oxides (Cu 2 O and CuO) and lead to internal and external sphere complexes, respectively. In the case of a selenite/cuprite mixture in basic pH environment and at the equilibrium, a chemical reaction occurs between the oxidation product of cuprite, Cu(OH) 2 and HSeO 3 . A preliminary study of

  15. Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

    Energy Technology Data Exchange (ETDEWEB)

    Kassem, M.E.; Hamed, A.E.; Abulnasr, L.; Abboudy, S. [Alexandria Univ. (Egypt). Dept. of Physics

    1994-11-01

    Isotopic effects in pure and {gamma}-irradiated triglycine selenate crystals were investigated using the specific heat (C{sub p}) technique. The obtained results showed an interesting dependence of the critical behavior of C{sub p} on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order ({lambda}-type) to a first order transition. After {gamma}-irradiation, the behavior of C{sub p} around the phase transition region was essentially affected. The transition temperature, T{sub c}, decreased and {Delta}C{sub p} depressed, and the transition became broad. It was noted that the effect of {gamma}-irradiation is opposite to the isotopic effect. (author).

  16. Rover exploration on the lunar surface; a science proposal for SELENE-B mission

    Science.gov (United States)

    Sasaki, S.; Kubota, T.; Akiyama, H.; Hirata, N.; Kunii, Y.; Matsumoto, K.; Okada, T.; Otake, M.; Saiki, K.; Sugihara, T.

    LUNARSURFACE:ASCIENCES. Sasaki (1), T. Kubota (2) , H. Akiyama (1) , N. Hirata (3), Y. Kunii (4), K. Matsumoto (5), T. Okada (2), M. Otake (3), K. Saiki (6), T. Sugihara (3) (1) Department of Earth and Planetary Science, Univ. Tokyo, (2) Institute of Space and Astronautical Sciences, (3) National Space Development Agency of Japan, (4) Department of Electrical and Electronic Engineering, Chuo Univ., (5) National Aerospace Laboratory of Japan, (6) Research Institute of Materials and Resources, Akita Univ. sho@eps.s.u -tokyo.ac.jp/Fax:+81-3-5841-4569 A new lunar landing mission (SELENE-B) is now in consideration in Japan. Scientific investigation plans using a rover are proposed. To clarify the origin and evolution of the moon, the early crustal formation and later mare volcanic processes are still unveiled. We proposed two geological investigation plans: exploration of a crater central peak to discover subsurface materials and exploration of dome-cone structures on young mare region. We propose multi-band macro/micro camera using AOTF, X-ray spectrometer/diffractometer and gamma ray spectrometer. Since observation of rock fragments in brecciaed rocks is necessary, the rover should have cutting or scraping mechanism of rocks. In our current scenario, landing should be performed about 500m from the main target (foot of a crater central peak or a cone/dome). After the spectral survey by multi-band camera on the lander, the rover should be deployed for geological investigation. The rover should make a short (a few tens meter) round trip at first, then it should perform traverse observation toward the main target. Some technological investigations on SELENE-B project will be also presented.

  17. Growth of Cu(In,Al)(Se,S)2 thin films by selenization and sulfurization for a wide bandgap absorber

    International Nuclear Information System (INIS)

    Fujiwara, C.; Kawasaki, Y.; Sato, T.; Sugiyama, M.; Chichibu, S.F.

    2010-01-01

    Full text : Chalcopyrite structure Cu(In 1 .xAlx)(S y Se 1 -y) 2 (CIASS) alloys are attracting attention as promising candidates for the light-absorbing medium of high conversion efficiency, low cost, and lightweight solar cells. In addition, according to the wide variation in the bandgap energy (1.0-3.5eV), multiple-junction or tandem solar cells able to be fabricated using CIASS films of different compositions, x and y. In fact, several research groups have recently fabricated Cu(In,Al)Se 2 -based solar cells, and a high μ of 16.9 percent has been demonstrated. The sulfurization following selenization of Cu(In,Ga)Se2 (CIGS) films is believed to be promising for bandgap engineering of absorber material. Furthermore, it has been reported that the controlled incorporation of sulfur into CIGS films reduces the carrier recombination in the space charge region due to the deep trap states. Therefore, the sulfurization following selenization is expected to be used as a method of growth of CIASS films. However, sulfurization condition following selenization for obtaining CIASS films has not been clarified. The crystal growth of CIASS must be studied for solar cell applications. In this study, the advantages of using sulfurization for the growth of CIASS will be presented. Cu-In-Al precursors were selenized using diethylselenide (DESe) at 515-570 degrees Celsium for 60- 90 min under atmospheric pressure. The flow rates of DESe and N 2 carrier gases were 35 imol/min and 2 L/min, respectively. The films were then sulfurized at 550 degrees Celsium using S vapor. These films were characterized by SEM, EDX, XRD, and PL measurements. Using the selenization and sulfurization technique, polycrystalline Cu(In,Al)Se 2 , CuIn(Se,S) 2 , CuInS 2 films with thickness of approximately 2.0 im were formed without additional annealing. The films adhered well to the Mo/SLG substrate, which was confirmed by the peeling test. Phase separations, i.e. distinct peaks corresponding to CuInSe 2

  18. The application of time-resolved luminescence spectroscopy to a remote uranyl sensor

    International Nuclear Information System (INIS)

    Varineau, P.T.; Duesing, R.; Wangen, L.E.

    1991-01-01

    Time resolved luminescence spectroscopy is an effective method for the determination of a wide range of uranyl concentrations in aqueous samples. We have applied this technique to the development of a remote sensing device using fiber optic cables coupled with a micro flow cell in order to probe for uranyl in aqueous samples. This sensor incorporates a Nafion membrane through which UO 2 2+ can diffuse in to a reaction/analysis chamber which holds phosphoric acid, a reagent which enhances the uranyl luminescence intensity and lifetime. With this device, anionic and fluorescing organic interferences could be eliminated, allowing for the determination of uranyl over a concentration range of 10 4 to 10 -9 M. 17 refs., 5 figs

  19. Aggregation-induced emission active tetraphenylethene-based sensor for uranyl ion detection.

    Science.gov (United States)

    Wen, Jun; Huang, Zeng; Hu, Sheng; Li, Shuo; Li, Weiyi; Wang, Xiaolin

    2016-11-15

    A novel tetraphenylethene-based fluorescent sensor, TPE-T, was developed for the detection of uranyl ions. The selective binding of TPE-T to uranyl ions resulted in a detectable signal owing to the quenching of its aggregation-induced emission. The developed sensor could be used to visually distinguish UO2(2+) from lanthanides, transition metals, and alkali metals under UV light; the presence of other metal ions did not interfere with the detection of uranyl ions. In addition, TPE-T was successfully used for the detection of uranyl ions in river water, illustrating its potential applications in environmental systems. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Uranyl determination using pyridylazoresorcinol as complexing active by adsorb voltametry technique with cathodic redissolution

    International Nuclear Information System (INIS)

    Ohara, A.K.; Farias, P.A.M.

    1990-01-01

    The development method for uranyl ion determination by the optimization of chemical reaction and instrumental parameters is shown. This method is based on preconcentration stage, where in adsorptive accumulation of metallic complex in a static electrode is presented. (author)

  1. The uranyl influence on a mutation process in germ and somatic cells of mice

    International Nuclear Information System (INIS)

    Kostrova, L.N.; Mosseh, I.B.; Molofej, V.P.

    2008-01-01

    The mutagenic effect of uranyl was revealed by the chromosome rearrangement test in germ and somatic cells of mice. The effect value depended on duration of substance administration into organism. (authors)

  2. Sorption rate of uranyl ions by hyphan cellulose exchangers and by hydrated titanium dioxide

    International Nuclear Information System (INIS)

    Ambe, F.; Burba, P.; Lieser, K.H.

    1979-01-01

    Sorption of uranyl ions by the cellulose exchanger Hyphan proceeds rather fast. Two steps are observed with half-times of the order of 10 s and 2 min. The majority of the uranyl ions is bound in 1 min. Sorption of uranyl ions by titanium dioxide is a very slow process. For particle sizes between 0,1 and 0,5 mm the half-time is about 3 h and equilibrium is attained in about 1 day. The effect of stirring suspensions of inorganic sorbents like titanium dioxide in solution is investigated in detail. Sorption of uranyl ions by titanium dioxide and change in pH in solution are measured simultaneously as a function of time. (orig.) [de

  3. Giant regular polyhedra from calixarene carboxylates and uranyl

    Science.gov (United States)

    Pasquale, Sara; Sattin, Sara; Escudero-Adán, Eduardo C.; Martínez-Belmonte, Marta; de Mendoza, Javier

    2012-01-01

    Self-assembly of large multi-component systems is a common strategy for the bottom-up construction of discrete, well-defined, nanoscopic-sized cages. Icosahedral or pseudospherical viral capsids, built up from hundreds of identical proteins, constitute typical examples of the complexity attained by biological self-assembly. Chemical versions of the so-called 5 Platonic regular or 13 Archimedean semi-regular polyhedra are usually assembled combining molecular platforms with metals with commensurate coordination spheres. Here we report novel, self-assembled cages, using the conical-shaped carboxylic acid derivatives of calix[4]arene and calix[5]arene as ligands, and the uranyl cation UO22+ as a metallic counterpart, which coordinates with three carboxylates at the equatorial plane, giving rise to hexagonal bipyramidal architectures. As a result, octahedral and icosahedral anionic metallocages of nanoscopic dimensions are formed with an unusually small number of components. PMID:22510690

  4. Effect of temperature on internal structure of uranyl gels

    International Nuclear Information System (INIS)

    Landspersky, H.; Urbanek, V.

    1983-01-01

    Tempering freshly prepared uranyl gel serves the homogenization of the volume of the individual spheres and the whole volume of the processed material. Tempering is carried out at a temperature of 90 degC in a special countercurrent through-flow column. The tempered gel particles were analyzed for specific surface and porosity using different methods, subjected to phase analysis, and the crystallite mean size was determined. It was found that the quality of the final gel depends on the residence time in the tempering column. Gel recrystallization probably takes place during tempering leading to stress and cracks which in the final stage lead to the disintegration of the xerogel. Maximum permissible gel residence time in the tempering column is 15 mins. (M.D.)

  5. Process control for a continuous uranyl nitrate evaporator

    International Nuclear Information System (INIS)

    Peterson, S.F.; MacIntyre, L.P.

    1984-07-01

    A continuous uranyl nitrate evaporator at the Savannah River Plant (SRP) in Aiken, South Carolina ws the subject of this work. A rigorous mathematical model of the evaporator was developed. A difference equation form of the model was then constructed and used for control studies. Relative gain analysis was done on the system in order to identify any promising multivariable control schemes. Several alternate control schemes were modeled, tuned, and compared against the scheme presently in use at SRP. As the pneumatic specific gravity instrumentation at SRP is very noisy, the noise was simulated and used in the second phase of the control study. In this phase, alternate tuning methods and filters were invesigated and compared. The control studies showed that the control algorithm now in use at SRP is the simplest and best available. 10 references, 53 figures, 22 tables

  6. Pilot scale for preparation of ammonium uranyl carbonate

    International Nuclear Information System (INIS)

    Santos, L.R. dos.

    1989-01-01

    The procedure adopted for obtaining Ammonium Uranyl Carbonate (AUC) from uranium hexafluoride (UF sub(6)) or aqueous solutions of uranylnitrate (UO sub(2)(NO sub(3)) sub(2)) is described in the present work. This procedure involves the precipitation of AUC in a chemical reactor by the addition of gaseous UF sub(6) or solutions of uranylnitrate to NH sub(3) and CO sub(2) gases in a solution containing ammonium bicarbonate, where pH and temperature are controlled. Details regarding the characterization and quality control methods in the preparation of AUC are presented along with their physical and chemical properties. Some informations about effluents generated during the process are presented too. An attempt is made to correlate the parameters involved in the precipitation process of AUC and their characteristics. (author)

  7. Cutaneous contamination after a uranyl nitrate skin burn: incident report

    International Nuclear Information System (INIS)

    Berard, P.; Chalabreysse, J.; Quesne, B.; Auriol, B.

    1994-01-01

    The authors review the circumstances of a handburn incident by a mixture of dilute nitric acid and uranyl nitrate. The burn was localised on the thumb and three fingers of the left hand. After abundant washing, external direct measurements revealed the presence of uranium on the fingers. The injured employee was maintained under observation for ten days, and therapy was performed until all the activity disappeared. External monitoring with various detectors, and measurements of the bandages and skin showed a rapid decrease of uranium fixation. All urine was collected throughout the duration of the treatment. The study shows that all the activity was retained on the burnt skin, with very little systemic uptake. Rapid peeling eliminated the cutaneous retention. Internal and external dose assessments were calculated and the committed effective dose equivalent and the committed dose equivalent for the skin and bone surfaces were low. (author)

  8. Complex formation between uranyl and various thiosemicarbazide derivatives

    International Nuclear Information System (INIS)

    Chuguryan, D.G.; Dzyubenko, V.I.

    1987-01-01

    Complex formation between hexavalent uranium and salicylaldehyde thiosemicarbazone (H 2 L), salicylaldehyde S-methyl-isothiosemicarbazone (H 2 Q), S-methyl-N 1 ,N 4 -bis(salicylidene)isothiosemicarbazide(H 2 Z), and thiosemicarbazidodiacetic acid (H 2 R) has been studied spectrophotometrically in solution. Stability constants for complexes having the composition UO 2 A have been calculated. Solid uranyl derivatives having the composition UO 2 L x 2H 2 O, UO 2 Q x 2H 2 O, UO 2 Z x 2H 2 O, and UO 2 R x 2H 2 O have been obtained. These derivatives were isolated and their IR spectroscopic behavior and thermal properties were investigated

  9. Hydrothermal syntheses and characterization of uranyl tungstates with electro-neutral structural units

    Energy Technology Data Exchange (ETDEWEB)

    Balboni, Enrica; Burns, Peter C. [Univ. of Notre Dame, IN (United States). Dept. of Civil and Enviromental Engineering and Earth Sciences; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry

    2015-11-01

    Two uranyl tungstates, (UO{sub 2})(W{sub 2}O{sub 7})(H{sub 2}O){sub 3} (1) and (UO{sub 2}){sub 3}(W{sub 2}O{sub 8})F{sub 2}(H{sub 2}O){sub 3} (2), were synthesized under hydrothermal conditions at 220 C and were structurally, chemically, and spectroscopically characterized. 1 Crystallizes in space group Pbcm, a = 6.673(5) Aa, b = 12.601(11) Aa, c = 11.552 Aa; 2 is in C2/m, a = 13.648(1) Aa, b = 16.852(1) Aa, c = 9.832(1) Aa, β = 125.980(1) {sup circle}. In 1 the U(VI) cations are present as (UO{sub 2}){sup 2+} uranyl ions that are coordinated by five oxygen atoms to give pentagonal bipyramids. These share two edges with two tungstate octahedra and single vertices with four additional octahedra, resulting in a sheet with the iriginite-type anion topology. Only water molecules are located in the interlayer. The structural units of 2 consist of (UO{sub 2}){sup 2+} uranyl oxy-fluoride pentagonal bipyramids present as either [UO{sub 2}F{sub 2}O{sub 3}]{sup -6} or [UO{sub 2}FO{sub 4}]{sup -5}, and strongly distorted tungstate octahedra. The linkage of uranyl pentagonal bipyramids and tungstate octahedra gives a unique sheet anion topology consisting of pentagons, squares and triangles. In 2, the uranyl tungstates sheets are connected into a novel electro-neutral three-dimensional framework through dimers of uranyl pentagonal bipyramids. These dimers connecting the sheets share an edge defined by F anions. 2 is the first example of a uranyl tungstate oxy-fluoride, and 1 and 2 are rare examples of uranyl compounds containing electro-neutral structural units.

  10. Ligand exchange in uranyl complexes in non-aqueous solutions: equilibrium properties

    International Nuclear Information System (INIS)

    Egozy, Y.; Weiss, S.

    1976-01-01

    The systems uranyl nitrate, tributylphosphate and 8-hydroxyquinoline or diphenylcarbazone were studied in chloroform, carbon tetrachloride and 1,2-dichloroethane at a number of temperatures. The nature of the complexes formed was determined and the equilibrium constants and several thermodynamic functions were measured. 8-hydroxyquinoline and diphenylcarbazone will be valuable as indicators for uranyl in kinetic studies. They are also interesting since they participate, along with tributylphosphate, in formation of synergistic complexes. (author)

  11. Investigation of uranyl sorbed to Wyoming montmorillonite at amphoteric and exchange sites by optical spectroscopy

    International Nuclear Information System (INIS)

    Morris, D.E.; Chisholm-Brause, C.J.; Berg, J.M.; McKinley, J.P.; Zachara, J.M.; Smith, S.C.

    1993-01-01

    Using optical spectroscopy, the authors have characterized aqueous uranyl (UO 2 2+ ) sorption complexes on a sodium-saturated Wyoming montmorillonite (SWy-1) at low and high ionic strength (IS, as NaClO 4 . McKinley et al. (1193), ACS Spring Meeting) have shown that uranyl uptake is suppressed at high IS at these pH values, reflecting increased cation competition for exchange sites, and an increase in the ratio of uranyl species sorbed on amphoteric edge sites to those in exchange sites. At higher pH, sorption is less dependent on IS, with complexation by amphoteric edge sites becoming dominant as pH increases. At low pH, emission spectra for uranyl sorbed to SWy-1 from solutions with high IS ([Na]/[U] > 1000) are distinct from those at low IS ([Na]/[U] < 10). The low IS spectra are dominanted by a short lifetime component (τ∼0.5μs), and have low integrated intensities (normalized for uranium concentration). However, gated detection clearly resolves an additional, longer-loved component. The high IS spectra have significant contributions form 2-3 longer-lived components (5<τ120μs), and have much stronger intensities. Based on comparison to solution data, these results suggest that the uranyl moiety in the exchange sites is strikingly similar to the fully aquated uranyl monomer in solution, whereas the uranyl species occupying the edge sites are structurally more similar to hydrolyzed uranyl species in solution. At higher pH values, the emission spectra represent composites of at least the two distinct spectra identified at lower pH. However, the ratios of the different components and thus the overall emission spectra vary as a function of ionic strength. These results demonstrate that several spectroscopically (and therefore structurally) distinct sorption complexes exist in exchange and edges of SWy-1

  12. High-affinity uranyl-specific antibodies suitable for cellular imaging

    Energy Technology Data Exchange (ETDEWEB)

    Reisser-Rubrecht, L.; Torne-Celer, C.; Renier, W.; Averseng, O.; Plantevin, S.; Quemeneur, E.; Bellanger, L.; Vidaud, C. [CEA Valrho, DSV, IBEB, Serv Biochim et Toxicol Nucl, F-30207 Bagnols Sur Ceze (France)

    2008-07-01

    Monoclonal antibodies (mAbs) have proved to be valuable models for the study of protein-metal interactions, and previous reports have described very specific antibodies to chelated metal ions, including uranyl. We raised specific mAbs against UO{sub 2}{sup 2+}-DCP-BSA (DCP, 1, 10-phenanthroline-2,9-dicarboxylic acid) to generate new sets of antibodies that might cross-react with various complexed forms of uranyl in different environments for further application in the field of toxicology. Using counter-screening with UO{sub 2}{sup 2+}-DCP-casein, we selected two highly specific mAbs against uranyl-DCP (K{sub D} = 10-100 pM): U04S and U08S. Competitive assays in the presence of different metal ions (UO{sub 2}{sup 2+}, Fe{sup 3+}, Zn{sup 2+}, Cu{sup 2+}, and Ca{sup 2+}) showed that uranyl in solution can act as a good competitor, suggesting some antibody ability to cross-react with chelating groups other than DCP in the UO{sub 2}{sup 2+} equatorial coordination plane. Interestingly, one of the antibodies could be used for revealing uranyl cations in cell samples. Fluorescence activated cell sorting analyses after immuno-labeling revealed the interaction of uranyl with human kidney cells HK2. The intracellular accumulation of uranyl could be directly visualized by metal-immunostaining using fluorescent-labeled mAb. Our results suggest that U04S mAb epitopes mostly include the uranyl fraction and its para-topes can accommodate a wide variety of chelating groups. (authors)

  13. Nephrotoxicity of uranyl acetate: effect on rat kidney brush border membrane vesicles

    International Nuclear Information System (INIS)

    Goldman, M.; Yaari, A.; Moran, A.; Doshnitzki, Z.; Cohen-Luria, R.

    2006-01-01

    Since the Gulf war exposure to depleted uranium, a known nephrotoxic agent, there is a renewed interest in the toxic effects of uranium in general and its mechanism of nephrotoxicity which is still largely unknown in particular. In order to investigate the mechanism responsible for uranium nephrotoxicity and the therapeutic effect of urine alkalization, we utilized rat renal brush border membrane vesicles (BBMV). Uranyl acetate (UA) caused a decrease in glucose transport in BBMV. The apparent K i of uranyl was 139±30 μg uranyl/mg protein of BBMV. Uranyl at 140 μg/mg protein of BBMV reduced the maximal capacity of the system to transport glucose [V max 2.2±0.2 and 0.96±0.16 nmol/mg protein for control and uranyl treated BBMV (P m (1.54±0.33 and 1.54±0.51 mM for control, and uranyl treated BBMV, respectively). This reduction in V max is at least partially due to a decrease in the number of sodium-coupled glucose transporters as apparent from the reduction in phlorizin binding to the uranyl treated membranes, V max was reduced from 247±13 pmol/mg protein in control BBMV to 119±3 pmol/mg protein in treated vesicles (P<0.001). The pH of the medium has a profound effect on the toxicity of UA on sodium-coupled glucose transport in BBMV: higher toxicity at neutral pH (around pH 7.0), and practically no toxicity at alkaline pH (7.6). This is the first report showing a direct inhibitory dose and pH dependent effect of uranyl on the glucose transport system in isolated apical membrane from kidney cortex. (orig.)

  14. High-affinity uranyl-specific antibodies suitable for cellular imaging

    International Nuclear Information System (INIS)

    Reisser-Rubrecht, L.; Torne-Celer, C.; Renier, W.; Averseng, O.; Plantevin, S.; Quemeneur, E.; Bellanger, L.; Vidaud, C.

    2008-01-01

    Monoclonal antibodies (mAbs) have proved to be valuable models for the study of protein-metal interactions, and previous reports have described very specific antibodies to chelated metal ions, including uranyl. We raised specific mAbs against UO 2 2+ -DCP-BSA (DCP, 1, 10-phenanthroline-2,9-dicarboxylic acid) to generate new sets of antibodies that might cross-react with various complexed forms of uranyl in different environments for further application in the field of toxicology. Using counter-screening with UO 2 2+ -DCP-casein, we selected two highly specific mAbs against uranyl-DCP (K D = 10-100 pM): U04S and U08S. Competitive assays in the presence of different metal ions (UO 2 2+ , Fe 3+ , Zn 2+ , Cu 2+ , and Ca 2+ ) showed that uranyl in solution can act as a good competitor, suggesting some antibody ability to cross-react with chelating groups other than DCP in the UO 2 2+ equatorial coordination plane. Interestingly, one of the antibodies could be used for revealing uranyl cations in cell samples. Fluorescence activated cell sorting analyses after immuno-labeling revealed the interaction of uranyl with human kidney cells HK2. The intracellular accumulation of uranyl could be directly visualized by metal-immunostaining using fluorescent-labeled mAb. Our results suggest that U04S mAb epitopes mostly include the uranyl fraction and its para-topes can accommodate a wide variety of chelating groups. (authors)

  15. A study of precipitation from pure solutions of uranyl nitrate; Etude de la precipitaion de solutions pures de nitrate d'uranyle

    Energy Technology Data Exchange (ETDEWEB)

    Decrop, J; Holder, J; Sauteron, J [Commissariat a l' Energie Atomique, Usine du Bouchet, Service des Lab. de Recherches et de Controle, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    After its purification by extraction of the uranyl nitrate from the organic solvent, uranium has to be converted into solid form again: uranium trioxide (UO{sub 3}). It can be done either by thermal decomposition of uranyl nitrate or by precipitation of uranium, followed by filtration and calcination. Only the second method has been studied for now at the Bouchet plant. This paper reports the bench-scale and pilot-scale experiments of the studies of the precipitation of pure solutions of uranyl nitrate using ammonia (gaseous or in solution) or ammonium carbonate. These have been carried out at the Bouchet plant. It investigates the chemical aspect (pH, precipitates chemical composition) and the technical aspect of the different ways of precipitation (conditions of precipitation, decantation and filtration of precipitates). (M.P.)

  16. Temperature and pH driven association in uranyl aqueous solutions

    Directory of Open Access Journals (Sweden)

    M. Druchok

    2012-12-01

    Full Text Available An association behavior of uranyl ions in aqueous solutions is explored. For this purpose a set of all-atom molecular dynamics simulations is performed. During the simulation, the fractions of uranyl ions involved in dimer and trimer formations were monitored. To accompany the fraction statistics one also collected distributions characterizing average times of the dimer and trimer associates. Two factors effecting the uranyl association were considered: temperature and pH. As one can expect, an increase of the temperature decreases an uranyl capability of forming the associates, thus lowering bound fractions/times and vice versa. The effect of pH was modeled by adding H+ or OH- ions to a "neutral" solution. The addition of hydroxide ions OH- favors the formation of the associates, thus increasing bound times and fractions. The extra H+ ions in a solution produce an opposite effect, thus lowering the uranyl association capability. We also made a structural analysis for all the observed associates to reveal the mutual orientation of the uranyl ions.

  17. Aggregation-induced emission active tetraphenylethene-based sensor for uranyl ion detection

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Jun; Huang, Zeng; Hu, Sheng [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, 621900, Sichuan Province (China); Li, Shuo, E-mail: lishuo@cqut.edu.cn [School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054 (China); Li, Weiyi, E-mail: weiyili@mail.xhu.edu.cn [School of Science, Xihua University, Chengdu, Sichuan, 610065 (China); Wang, Xiaolin, E-mail: xlwang@caep.cn [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, 621900, Sichuan Province (China)

    2016-11-15

    Highlights: • A novel AIE fluorescent sensor for the detection of uranyl has been developed. • TPE-T is capable of visually distinguish UO{sub 2}{sup 2+} among many metals owing to the AIE phenomenon. • TPE-T showed a wide effective pH range, high selectivity and good anti-interference qualities. • TPE-T showed good accuracy in the determination of uranyl in river water. - Abstract: A novel tetraphenylethene-based fluorescent sensor, TPE-T, was developed for the detection of uranyl ions. The selective binding of TPE-T to uranyl ions resulted in a detectable signal owing to the quenching of its aggregation-induced emission. The developed sensor could be used to visually distinguish UO{sub 2}{sup 2+} from lanthanides, transition metals, and alkali metals under UV light; the presence of other metal ions did not interfere with the detection of uranyl ions. In addition, TPE-T was successfully used for the detection of uranyl ions in river water, illustrating its potential applications in environmental systems.

  18. Theoretical insights into the uranyl adsorption behavior on vanadium carbide MXene

    Science.gov (United States)

    Zhang, Yu-Juan; Zhou, Zhang-Jian; Lan, Jian-Hui; Ge, Chang-Chun; Chai, Zhi-Fang; Zhang, Peihong; Shi, Wei-Qun

    2017-12-01

    Remediation of the contamination by long-lived actinide wastes is extremely important but also challenging. Adsorption based techniques have attracted much research attention for their potential as low-cost and effective methods to reduce the radioactive waste from solution. In this work, we have investigated the adsorption behavior of uranyl species [with the general form UO2(L1)x(L2)y(L3)z, where L1, L2 and L3 stand for ligands H2O, OH and CO3, respectively] on hydroxylated vanadium carbide V2C(OH)2 MXene nanosheets using density functional theory based simulation methods We find that all studied uranyl species can stably bond to hydroxylated MXene with binding energies ranging from -3.3 to -4.6 eV, suggesting that MXenes could be effective adsorbers for uranyl ions. The strong adsorption is achieved by forming two Usbnd O bonds with the hydroxylated Mxene. In addition, the axial oxygen atoms from the uranyl ions form hydrogen bonds with the hydroxylated V2C, further strengthening the adsorption. We have also investigated the effects of F termination on the uranyl adsorption properties of V2C nanosheets. Usbnd F bonds are in general weaker than Usbnd O bonds on the adsorption site, suggesting that F terminated Mexne is less favorable for uranyl adsorption applications.

  19. Raman spectral titration method: an informative technique for studying the complexation of uranyl with uranyl(vi)-DPA/oxalate systems as examples.

    Science.gov (United States)

    Liu, Qian; Zhang, Qianci; Yang, Suliang; Zhu, Haiqiao; Liu, Quanwei; Tian, Guoxin

    2017-10-10

    The Raman band at about 870 cm -1 originating from the symmetric stretch vibration (ν 1 ) of uranyl, UO 2 2+ , has proven to be very informative for investigating the complexation of uranyl using perchlorate or nitrate of known concentration as internal standards. The concentration of uranyl can be conveniently calculated by using the ratio of the directly read band intensities of uranyl and the added reference, ClO 4 - , with a factor of 1.72. While with NO 3 - of concentration lower than 1.8 M as the reference, a factor of 0.85 should be used. Furthermore, with added internal standards, the linear relationship between the Raman intensity and the concentration of the corresponding species is illustrated by the spectral titration of U(vi) with a very strong ligand, dipicolinic acid (DPA); and the application of a spectral titration method with Raman spectroscopy in studying the complexation of uranyl is demonstrated by the titration of U(vi) with oxalate. The stepwise changes in the Raman shift of 18, 17, and 6 cm -1 , corresponding to the three oxalate anions successively bonding to UO 2 2+ , imply that the coordination modes are different. In the 1 : 1 and 1 : 2 ratios of metal to ligand complexes, the oxalate anions bond to the uranyl ion in side-on bidentate mode, but in the 1 : 3 complex the third oxalate bonds in head-on mode, which is much weaker than the first two.

  20. Contribution to the study of uranyl salts in butyl phosphate solutions; Contribution a l'etude des solutions de sels d'uranyle dans les phosphates butyliques

    Energy Technology Data Exchange (ETDEWEB)

    Coulon, A [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1965-06-01

    A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from {approx} 1270 cm{sup -1} to {approx} 1180 cm{sup -1}. A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [French] Une etude spectroscopique dans l'infrarouge moyen portant sur les associations: - phosphates trialcoyliques (tributylique - triethylique - trimethylique) - sels d'uranyle (nitrate, chlorure, acetate) a confirme l'existence d'une interaction entre le groupement phosphoryle et l'atome d'uranium, se manifestant par un deplacement de la bande d'absorption de la vibration de valence P = 0 de {approx} 1270 cm{sup -1} a {approx} 1180 cm{sup -1}. Une etude preparative, analytique et spectroscopique des solides obtenus par precipitation de sels d'uranyle par les phosphates butyliques acides a ete effectuee. La spectrophotomerie infrarouge met en evidence l'association, anterieure a toute introduction d'uranium, des phosphates tributylique et dibutylique dans des diluants non polaires. L'extraction de sels d'uranyle, d'une solution aqueuse acide par un melange dilue de phosphates tributylique et dibutylique, s'effectue suivant des processus differents a la nature de l'anion (nitrate ou chlorure). (auteur)

  1. Uptake and speciation of selenium in garlic cultivated in soil amended with symbiotic fungi (mycorrhiza) and selenate

    Energy Technology Data Exchange (ETDEWEB)

    Larsen, Erik H.; Hansen, Marianne; Rasmussen, Peter Have; Sloth, Jens J. [Danish Institute for Food and Veterinary Research, Department of Food Chemistry, Soeborg (Denmark); Lobinski, Ryszard; Ruzik, Rafal; Mazurowska, Lena [CNRS UMR 5034, Pau (France); Warsaw University of Technology, Department of Analytical Chemistry, Warsaw (Poland); Burger-Meyer, Karin; Scholten, Olga [Wageningen University and Research Centre, Plant Research International (PRI), P.O. Box 16, Wageningen (Netherlands); Kik, Chris [Wageningen University and Research Centre, Plant Research International (PRI), P.O. Box 16, Wageningen (Netherlands); Wageningen University and Research Centre, Centre for Genetic Resources, The Netherlands (CGN), P.O. Box 16, Wageningen (Netherlands)

    2006-07-15

    The scope of the work was to investigate the influence of selenate fertilisation and the addition of symbiotic fungi (mycorrhiza) to soil on selenium and selenium species concentrations in garlic. The selenium species were extracted from garlic cultivated in experimental plots by proteolytic enzymes, which ensured liberation of selenium species contained in peptides or proteins. Separate extractions using an aqueous solution of enzyme-deactivating hydroxylamine hydrochloride counteracted the possible degradation of labile selenium species by enzymes (such as alliinase) that occur naturally in garlic. The selenium content in garlic, which was analysed by ICP-MS, showed that addition of mycorrhiza to the natural soil increased the selenium uptake by garlic tenfold to 15 {mu}g g{sup -1} (dry mass). Fertilisation with selenate and addition of mycorrhiza strongly increased the selenium content in garlic to around one part per thousand. The parallel analysis of the sample extracts by cation exchange and reversed-phase HPLC with ICP-MS detection showed that {gamma}-glutamyl-Se-methyl-selenocysteine amounted to 2/3, whereas methylselenocysteine, selenomethionine and selenate each amounted to a few percent of the total chromatographed selenium in all garlic samples. Se-allyl-selenocysteine and Se-propyl-selenocysteine, which are selenium analogues of biologically active sulfur-containing amino acids known to occur in garlic, were searched for but not detected in any of the extracts. The amendment of soil by mycorrhiza and/or by selenate increased the content of selenium but not the distribution of detected selenium species in garlic. Finally, the use of two-dimensional HPLC (size exclusion followed by reversed-phase) allowed the structural characterisation of {gamma}-glutamyl-Se-methyl-selenocysteine and {gamma}-glutamyl-Se-methyl-selenomethionine in isolated chromatographic fractions by quadrupole time-of-flight mass spectrometry. (orig.)

  2. Identifying the Impact of E-Selen on the Sterile Medfly Ceratitis capitata at the Genomic Level Using DNA Profile

    International Nuclear Information System (INIS)

    Zaghloul, Y.S.

    2014-01-01

    The antioxidant E-Selen is an exogenous antioxidant containing both selenium and vitamin E. It was added to the larval artificial diets of the Mediterranean fruit fly, Ceratitis capitata in various concentrations (0.1, 0.3, 0.5 and 1.5 mg) prior to irradiation in order to obtain fully competent males. The produced full grown pupae were exposed to gamma rays at a dose rate of 90 Gy. Biological assessment of two E-Selen concentrations 0.3 and 0.5 mg were found to ameliorate the fitness of the sterile insects as well as to increase significantly most of their amino acids content. The study of the PCR patterns of normal and irradiated C. capitata undertaken or not different doses of E-Selen prior to irradiation and contained in the larval diets induced some modifications to the DNA profiles. The appearance of some new bands and disappearance of others were frequently encountered during this investigation. The appearance of bands was attributed to a repair mechanism that occurs in the irradiated DNA. However, the similarity in the DNA patterns of the homogenate pupal of C. capitata was due to the irradiation-induced damage may be in genome regions other than the regions of study

  3. Optical and structural properties of FeSe2 thin films obtained by selenization of sprayed amorphous iron oxide films

    International Nuclear Information System (INIS)

    Ouertani, B.; Ouerfelli, J.; Saadoun, M.; Zribi, M.; Rabha, M.Ben; Bessais, B.; Ezzaouia, H.

    2006-01-01

    We report in this work the optical and structural properties of iron diselenide films (FeSe 2 ) obtained by selenization under vacuum of amorphous iron oxide films predeposited by spray pyrolysis. The structure of the FeSe 2 films was investigated by scanning electron microscopy (SEM), microprobe analyses, atomic force microscopy (AFM) and X-ray diffraction (XRD). XRD and micro-probe analyses showed that FeSe 2 as well as FeSe 2-x phases begin to appear at a selenization temperature of 500 deg. C. As the selenization temperature rises, the iron diselenide films become more stoichiometric with a dominance of the FeSe 2 phase. At 550 deg. C, a single FeSe 2 phase having good crystallinity was obtained. At 600 deg. C, two phases were detected: the major one corresponds to Fe 3 O 4 , and the minor one to FeSe 2 . SEM surface views show that FeSe 2 films have granular structure with small spherical crystallites. However, layered and clustered FeSe 2 films were found, respectively, at 550 deg. C and 600 deg. C. Absorption measurements show that iron diselenide films have a direct and an indirect gaps of about 1.03 eV and 0.3 eV, which were suggested to be due to the stoichiometric FeSe 2 phase and to a Fe-rich non-stoichiometric phase, respectively

  4. Rapid fabrication of self-ordered porous alumina with 10-/sub-10-nm-scale nanostructures by selenic acid anodizing

    Science.gov (United States)

    Nishinaga, Osamu; Kikuchi, Tatsuya; Natsui, Shungo; Suzuki, Ryosuke O.

    2013-01-01

    Anodic porous alumina has been widely investigated and used as a nanostructure template in various nanoapplications. The porous structure consists of numerous hexagonal cells perpendicular to the aluminum substrate and each cell has several tens or hundreds of nanoscale pores at its center. Because the nanomorphology of anodic porous alumina is limited by the electrolyte during anodizing, the discovery of additional electrolytes would expand the applicability of porous alumina. In this study, we report a new self-ordered nanoporous alumina formed by selenic acid (H2SeO4) anodizing. By optimizing the anodizing conditions, anodic alumina possessing 10-nm-scale pores was rapidly assembled (within 1 h) during selenic acid anodizing without any special electrochemical equipment. Novel sub-10-nm-scale spacing can also be achieved by selenic acid anodizing and metal sputter deposition. Our new nanoporous alumina can be used as a nanotemplate for various nanostructures in 10-/sub-10-nm-scale manufacturing. PMID:24067318

  5. Uranium (VI) chemistry at the interface solution/minerals (quartz and aluminium hydroxide): experiments and spectroscopic investigations of the uranyl surface species

    International Nuclear Information System (INIS)

    Froideval, A.

    2004-09-01

    This study deals with the understanding of the uranyl chemistry at the 0.1 M NaNO 3 solution/mineral (quartz and aluminium hydroxide) interface. The aims are:(i) to identify and to characterize the different uranyl surface species (mononuclear, polynuclear complexes and/or precipitates...), i.e. the coordination environments of sorbed/precipitated uranyl ions, by using X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) and time-resolved laser-induced fluorescence spectroscopy (TRLFS), and;(ii) to investigate the influence of pH, initial uranyl aqueous concentration and hydroxyl ligand concentration on the uranyl surface speciation. Our study on the speciation of uranyl ions at the quartz surface (i) confirms the formation of uranyl polynuclear/oligomers on quartz from moderate (1 μmol/m 2 ) to high (26 μmol/m 2 ) uranyl surface concentrations and (ii) show that theses polynuclear species coexist with uranyl mononuclear surface species over a pH range ≅ 5-8.5 and a wide range of initial uranyl concentration o f the solutions (10-100 μM). The uranyl concentration of these surface species depends on pH and on the initial uranyl aqueous concentration. Hydrate (surface-) precipitates and/or adsorbed polynuclear species and monomeric uranyl surface complexes are formed on aluminium hydroxide. Uranyl mononuclear complexes are predominant at acidic pH, as well as uranyl in solution or on the surface. Besides mononuclear species, precipitates and/or adsorbed polynuclear species are predominantly formed at neutral pH values on aluminium hydroxide. A main contribution of our investigations is that precipitation and/or adsorption of polynuclear species seem to occur at low uranyl surface concentrations (0.01-0.4 μmol/m 2 ). The uranyl surface speciation is mainly dependent on the pH and the aluminol ligand concentration. (author)

  6. Sorption of uranyl species on zircon and zirconia

    International Nuclear Information System (INIS)

    Lomenech, C.; Drot, R.; Simoni, E.; Ehrhardt, J.J.; Mielczarski, J.

    2002-01-01

    The safety of a long-term storage of radioactive waste in deep geological repositories would be strongly affected by the migration properties of radionuclides through the different barriers to the surface of the earth. Since the main process involved in the retention of radioactive ions is their sorption at the water/ mineral interface, a quantitative description of the sorption reactions is needed. Macroscopic data have for a long time been the only source of information used to propose a modelling of sorption equilibria, although they bring no direct information on the nature of the sorbed species; a microscopic structural investigation of the surface complexes is difficult indeed, because of the small amount of matter sorbed. Thus, in this study, parallel to the macroscopic measurements, different complementary spectroscopic techniques have been used in order to determine the nature of the surface species. As the final purpose of such a study is the simulation of the experimental retention data, the precise structural identification of the sorption equilibria will then be very useful to constrain the data simulation code. In this work, we present the results of both macroscopic and microscopic studies of the sorption of uranyl species on zircon and zirconia. The first part of our macroscopic approach was the surface characterisation of the non-sorbed materials by the determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, while the second part aimed at obtaining the sorption isotherms (percentage of sorption versus pH), which was performed using alpha spectrometry, for different uranyl concentrations, media (NaClO 4 or KNO 3 ) and ionic strengths. The spectroscopic identification of the different surface complexes and sorption sites has been carried out using four different spectroscopies. Whereas tune-resolved laser spectro-fluorimetry gave a direct answer concerning the number of surface species (only for a

  7. 1H chemically induced dynamic nuclear polarization in the photodecomposition of uranyl carboxylates

    International Nuclear Information System (INIS)

    Rykov, S.V.; Khudyakov, I.V.; Skakovsky, E.D.; Burrows, H.D.; Formosinho, S.J.; Miguel, M. da G.M.

    1991-01-01

    Chemically induced dynamic nuclear polarization ( 1 H CIDNP) has been observed during photolysis of uranyl salts of pivalic, propionic, and acetic acids in D 2 O solution, [ 2 H 6 ]acetone, [ 2 H 4 ]methanol, or in some other solvent. The multiplet polarization of isobutene and isobutane protons has been found under photolysis of deoxygenated pivalate solution. The polarized compounds are formed in the triplet pairs of tert-butyl free radicals. 1 H Emission of the tert-butylperoxyl group and emission of 1 H from isobutene have been recorded under photolysis of air-saturated pivalate solutions. The CIDNP of butane protons stays as a multiplet. Such changes in the presence of air/oxygen have arisen apparently because of the formation of tert-butylperoxyl free radical and its reaction with tert-butyl radical products, i.e. hydroperoxide (peroxide) and isobutene. Isobutene probably forms a complex with molecular oxygen which has a very short proton relaxation time. During the photolysis of uranyl pivalate in the presence of p-benzoquinone (5 x 10 -2 -0.1 mol dm -3 ) we have not observed any CIDNP, whereas under p-benzoquinone concentrations of 10 -3 -10 -2 mol dm -3 the CIDNP from both hydroquinone and p-benzoquinone has been followed. Photolysis of uranyl propionate has led to CIDNP from butane protons. An emission from methyl group protons of a compound with an ethylperoxyl fragment in the presence of air/oxygen has been observed. The same polarization picture has arisen under interaction of photoexcited uranyl with propionic acid. During the photolysis of uranyl acetate at relatively low concentrations (10 -2 mol dm -3 ) a CIDNP very similar to that registered for uranyl propionate was recorded. The ethyl fragment is probably obtained in reactions for two methyl radicals formed from acetate with the parent uranyl acetate, namely hydrogen-atom abstraction and addition reactions. (author)

  8. Crystal structure of the uranyl-oxide mineral rameauite

    Energy Technology Data Exchange (ETDEWEB)

    Plasil, Jakub [ASCR, Prague (Czech Republic). Inst. of Physics; Skoda, Radek [Masaryk Univ., Brno (Czech Republic). Dept. of Geological Sciences; Cejka, Jiri [National Museum, Prague (Czech Republic). Dept. of Mineralogy and Petrology; Bourgoin, Vincent; Boulliard, Jean-Claude [Pierre et Marie Curie Univ., Paris (France). Association Jean Wyart, Collection des Mineraux de Jussieu

    2016-12-15

    Rameauite is a rare supergene uranyl-oxide hydroxy-hydrate mineral that forms during hydration-oxidation weathering of uraninite. On the basis of single-crystal X-ray diffraction data collected on a microfocus source, rameauite is monoclinic, space group Cc, with a = 13.9458(19), b = 14.3105(19), c = 13.8959(18) Aa, β = 118.477(14) , V = 2437.7(6) Aa{sup 3} and Z = 4, with D{sub calc} = 5.467 g cm{sup -3}. The structure of rameauite (R = 0.060 for 1698 unique observed reflections) contains sheets of the β-U{sub 3}O{sub 8} topology, with both UO{sub 6} and UO{sub 7} bipyramids, which is similar to the sheets found in spriggite, ianthinite and wyartite. The sheets alternate with the interlayer, which contains K{sup +}, Ca{sup 2+} and H{sub 2}O molecules. Interstitial cations are linked into infinite chains that extend along [10-1]. Adjacent sheets are linked through K-O, Ca-O and H-bonds. The structural formula of rameauite is K{sub 2} Ca(H{sub 2}{sup [3]}O){sub 1}(H{sub 2}{sup [5]}O){sub 4}[(UO{sub 2}) {sub 6}O{sub 6}(OH){sub 4}](H{sub 2}{sup [4]}O){sub 1}. The empirical formula obtained from the average of eight electron-microprobe analyses is (on the basi s of 6 U p.f.u.) K{sub 1.87}(Ca{sub 1.10}Sr{sub 0.04}){sub Σ1.14}[(UO 2){sub 6}O{sub 6}(OH){sub 4.15}].6H{sub 2}O. The Raman spectrum is dominate d by U.O and O.H vibrations. A discussion of related uranyl-oxide minerals is given.

  9. Synthesis, characterization and thermal decomposition of tetramethylammonium rare earth double selenates

    Science.gov (United States)

    Divekar, Sandesh K.; Achary, S. Nagabhusan; Ajgaonkar, Vishnu R.

    2018-06-01

    A series of double selenates, as (CH3)4NLn(SeO4)2rad 4H2O (Ln = Rare earth ion like La, Pr, Nd, Sm, Gd, Tb, Dy) was crystallized from mixed solution and characterized in detail for their structure, vibrational and optical properties as well as thermal stabilities. The crystal structure of the praseodymium compound was obtained by single crystal X-ray diffraction (XRD) and revealed a monoclinic (C2/c) lattice with chains formed by PrO8 and SeO4 units. The chains with compositions [Pr(SeO4)4(H2O)4]- are stacked in three dimensions and the (CH3)4N+ ions located in between them provide charge neutrality to the structure. The characterization of other compounds were carried out from powder XRD data and revealed that they all are isostructural to Pr-compound. All the functional groups were identified by Raman and IR spectroscopic studies. Solid state 77Se NMR revealed noticeable changes in selenium environment in these compounds. The optical absorption studies on the compounds show strong band edge absorptions in UV region. Thermal stabilities of the compounds, as investigated by simultaneous TG-DTA techniques indicate their sequential decompositions due to loss of H2O, (CH3)4N+ group, SeO2 and finally leaving their corresponding rare earth oxides.

  10. Abiotic pyrite reactivity versus nitrate, selenate and selenite using chemical and electrochemical methods

    International Nuclear Information System (INIS)

    Ignatiadis, I.; Betelu, S.; Gaucher, E.; Tournassat, C.; Chainet, F.

    2010-01-01

    Document available in extended abstract form only. This work is part of ReCosy European project (www.recosy.eu), whose main objectives are the sound understanding of redox phenomena controlling the long-term release/retention of radionuclides in nuclear waste disposal and providing tools to apply the results to performance assessment/safety case. Redox is one of the main factor affecting speciation and mobility of redox-sensitive radionuclides. Thus, it is of a great importance to investigate the redox reactivity of the host radioactive waste formations, particularly when exposed to redox perturbations. Callovo-Oxfordian formation (COx), a clay rock known as an anoxic and reducing system, was selected in France as the most suitable location to store nuclear waste. Iron (II) sulfide, mostly constituted of pyrite (FeS 2 ), iron (II) carbonate, iron(II) bearing clays and organic matter are considered to account almost entirely for the total reducing capacity of the rock. We report here the redox reactivity of pyrite upon exposure to nitrate (N(V)), selenate (Se(VI)) and selenite (Se(IV)) that possibly occur in the nuclear storage. Both, chemical and electrochemical kinetic approaches were simultaneously conducted such as to (i) determine the kinetics parameters of the reactions and (ii) understand the kinetic mechanisms. In order to reach similar conditions that are encountered in the storage system, all experiments were realised in NaCl 0.1 M, near neutral pH solutions, and an abiotic glove box (O 2 less than 10 -8 M). Chemical approach has consisted to set in contact pyrite in grains with solutions containing respectively nitrate, selenate and selenite. Reactants and products chemical analyses, conducted at different contact times, allowed us to assess the kinetics of oxidant reduction. Electrochemical approach has consisted in the continuous or semi-continuous analysis of large surface pyrite electrodes immersed in solutions with or without oxidant (nitrate

  11. Syntheses, characterizations and crystal structures of three new organically templated or organically bonded zinc selenates

    International Nuclear Information System (INIS)

    Feng Meiling; Mao Jianggao; Song Junling

    2004-01-01

    Three new organically templated or organically bonded zinc selenates, namely, {H 2 bipy}Zn(SeO 4 ) 2 (H 2 O) 2 1 (bipy=4,4'-bipyridine), {H 2 pip}{Zn(SeO 4 ) 2 (H 2 O) 4 }·2H 2 O 2 (pip=piprazine), and Zn(SeO 4 )(phen)(H 2 O) 2 3 (phen=1,10-phenanthroline) have been synthesized by hydrothermal reactions. The structure of compound 1 features a 1D chain composed of [Zn(SeO 4 ) 2 (H 2 O) 2 ] 2- anions. Compound 2 has a 2D layer structure built from {Zn(SeO 4 ) 2 (H 2 O) 4 } 2- anions that are cross-linked by doubly protonated piperazine cations via N-H···O hydrogen bonds. The structure of compound 3 contains a 1D chain of Zn(SeO 4 )(phen)(H 2 O) 2 , such chains are further interlinked by hydrogen bonds and π···π interactions to form a layer. The different roles the templates played have also been discussed

  12. Deletion of thioredoxin reductase and effects of selenite and selenate toxicity in Caenorhabditis elegans.

    Directory of Open Access Journals (Sweden)

    Christopher J Boehler

    Full Text Available Thioredoxin reductase-1 (TRXR-1 is the sole selenoprotein in C. elegans, and selenite is a substrate for thioredoxin reductase, so TRXR-1 may play a role in metabolism of selenium (Se to toxic forms. To study the role of TRXR in Se toxicity, we cultured C. elegans with deletions of trxr-1, trxr-2, and both in axenic media with increasing concentrations of inorganic Se. Wild-type C. elegans cultured for 12 days in Se-deficient axenic media grow and reproduce equivalent to Se-supplemented media. Supplementation with 0-2 mM Se as selenite results in inverse, sigmoidal response curves with an LC50 of 0.20 mM Se, due to impaired growth rather than reproduction. Deletion of trxr-1, trxr-2 or both does not modulate growth or Se toxicity in C. elegans grown axenically, and (75Se labeling showed that TRXR-1 arises from the trxr-1 gene and not from bacterial genes. Se response curves for selenide (LC50 0.23 mM Se were identical to selenite, but selenate was 1/4(th as toxic (LC50 0.95 mM Se as selenite and not modulated by TRXR deletion. These nutritional and genetic studies in axenic media show that Se and TRXR are not essential for C. elegans, and that TRXR alone is not essential for metabolism of inorganic Se to toxic species.

  13. Ultrastructural and metabolic changes in osteoblasts exposed to uranyl nitrate

    International Nuclear Information System (INIS)

    Tasat, D.R.; Orona, N.S.; Mandalunis, P.M.; Cabrini, R.L.; Ubios, A.M.

    2007-01-01

    Exposure to uranium is an occupational hazard to workers who continually handle uranium and an environmental risk to the population at large. Since the cellular and molecular pathways of uranium toxicity in osteoblast cells are still unknown, the aim of the present work was to evaluate the adverse effects of uranyl nitrate (UN) on osteoblasts both in vivo and in vitro. Herein we studied the osteoblastic ultrastructural changes induced by UN in vivo and analyzed cell proliferation, generation of reactive oxygen species (ROS), apoptosis, and alkaline phosphatase (APh) activity in osteoblasts exposed to various UN concentrations (0.1, 1, 10, and 100 μM) in vitro. Cell proliferation was quantified by means of the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, ROS was determined using the nitro blue tetrazolium test, apoptosis was morphologically determined using Hoechst 3332 and APh activity was assayed spectrophotometrically. Electron microscopy revealed that the ultrastructure of active and inactive osteoblasts exposed to uranium presented cytoplasmic and nuclear alterations. In vitro, 1-100 μM UN failed to modify cell proliferation ratio and to induce apoptosis. ROS generation increased in a dose-dependent manner in all tested doses. APh activity was found to decrease in 1-100 μM UN-treated cells vs. controls. Our results show that UN modifies osteoblast cell metabolism by increasing ROS generation and reducing APh activity, suggesting that ROS may play a more complex role in cell physiology than simply causing oxidative damage. (orig.)

  14. Reversible uranyl fluoride nephrotoxicity in the Long Evans rat

    International Nuclear Information System (INIS)

    Diamond, G.L.; Morrow, P.E.; Panner, B.J.; Gelein, R.M.; Baggs, R.B.

    1989-01-01

    Severity and duration of renal injury produced by low levels of uranyl fluoride (UO2F2) were examined in the rat. Rats received multiple ip injections of UO2F2 (cumulative dose: 0.66 or 1.32 mg U/kg body wt). Renal injury was characterized histologically by cellular and tubular necrosis of pars recta of proximal tubule (S2 and S3), with less severe cellular injury to thick ascending limb of loop of Henle and collecting tubule. Injury was evident when renal uranium levels were between 0.7 and 1.4 micrograms U/g wet kidney and was most severe when renal uranium burden was between 3.4 and 5.6 micrograms U/g. Repair of injury was rapid, with complete restoration within 35 days after exposure. Associated with injury were abnormalities in renal function, including impaired tubular reabsorption, proteinuria, and enzymuria, which appeared temporally related, to variable degrees, to progression of renal injury. Thus, reversible renal injury occurs in the rat at levels of uranium in kidney below the present Nuclear Regulatory Commission standard of 3 micrograms U/g kidney for renal injury in humans

  15. Adsorption of uranyl in SiO2 porous glass

    International Nuclear Information System (INIS)

    Benedetto, F. E.; Prado, M. O.

    2013-01-01

    Vitreous SiO 2 porous matrices can be used in many applications involving the uptake of chemical species on its solid surface. In this work, vitreous silica sponges were prepared from a sodium borosilicate glass manufactured in our laboratory. The product obtained was then separated into phases with subsequent leaching of the soluble phase rich in B and Na. The resulting porous matrices have a specific surface of 35 m2/gr. Adsorption of uranyl ions onto the SiO 2 porous surface was studied to evaluate the use of this material as a filter for treatment of uranium containing water. The effects of contact time, adsorbent mass and equilibrium concentration of solution were studied. The porous adsorbent exhibits a pseudo-second-order kinetic behavior. The sponges with adsorbed uranium were thermally sealed as a way of U immobilization. Retention of uranium was confirmed during the matrix sealing by TGA. Uranium concentration before and after adsorption tests were made by means of ICP-OES. For uranium concentration of 800 ppm, 72 hours contact time and pH of 3.5, the amount of uranium adsorbed was 21.06 ± 0.02 mg U per gram of vitreous porous SiO 2 . (author)

  16. Tritium gettering from air with hydrogen uranyl phosphate

    International Nuclear Information System (INIS)

    Souers, P.C.; Uribe, F.S.; Stevens, C.G.; Tsugawa, T.T.

    1985-08-01

    The managers of all tritium facilities now worry about their emissions into the atmosphere. The only method for cleaning tritium out of air is to catalyze the formation of tritiated water which is adsorbed, along with the overwhelming bulk of naturally occurring water vapor, on a zeolite molecular sieve. This method generally costs several million dollars for a small system, because of the necessary steel ducting, compressors and holding tanks. We have long had the dream of finding another getter that might be cheaper to use and would, hopefully, not make tritiated water (HTO). In a previous paper, we discovered that hydrogen uranyl phosphate (HUP, with the formula HUO 2 PO 4 x 4H 2 O) getters 1 ppM of tritium gas out of moist air. This makes HUP the first known ''direct'' tritium getter to work in air. However, the tritium enters a hydroxyl network within the HUP, so that it is effectively still in ''water'' form within the HUP. Worse yet, we found up to 10% tritiated water formed during the previous gettering experiments. HUP is unusual in possessing the exceptionally low vapor pressure of 0.6 torr water vapor at 298 0 K. This allows HUP to be used in fairly dry environments. 14 refs., 3 figs., 2 tabs

  17. Synthesis of uranyl ion imprinted polymer and its application in analysis

    International Nuclear Information System (INIS)

    Xiao Jingshui; Liu Huijun; Xiao Xilin; Huang Shengli

    2011-01-01

    Uranyl ion imprinted polymer beads were prepared by the copolymerization of styrene monomer and divinyl benzene as crosslinking agent in methanol solution,with the UO 2 2+ -o-dihydroxybenzene-4-vinyl pyridine ternary complex as template, the 2, 2'-azo-bis-isobutyronitrile as initiator and UO 2 2+ as the imprinting ion. The uranyl ions were removed from the polymer beads by treating with 6 mol/L HCl, leaving behind cavities that match uranyl ion in size. The treated polymer beads can preconcentrate uranyl ions from dilute aqueous solutions. The adsorption efficiency can reach 99% or above with good selectivity when pH is in the range of 5-7 and the adsorption time is more than 20 min. The elution rate can reach above 99% under the conditions of concentration of HCl being above 1.0 mol/L, elution time more than 20 min and the elution Janume more than 5 times the Janume of ion imprinted polymer. The uranyl ion imprinted polymer beads have been successfully applied to determine micro-uranium in brine samples. The results are satisfactory compared with NBS method.(authors)

  18. Electron spectra and mechanism of complexing of uranyl nitrate in water-acetone solutions

    International Nuclear Information System (INIS)

    Zazhogin, A.A.; Zazhogin, A.P.; Komyak, A.I.; Serafimovich, A.I.

    2003-01-01

    Based on the analysis of the luminescence and electronic absorption spectra, the processes of complexing in an aqueous solution of UO 2 (NO 3 ) 2 ·6H 2 O with small additions of acetone have been studied. In a pure aqueous solution, uranyl exists as the complex UO 2 ·5H 2 O. It is shown that the addition of acetone to the solution leads to the displacement of some water molecules out of the first coordination sphere of uranyl and the formation of the uranyl nitrate dihydrate complexes UO 2 (NO 3 ) 2 ·2H 2 O. It has been established that the stability of these complexes is determined by the decrease in the water activity and in the degree of hydration of uranyl and nitrate, which is the result of the local increase in the concentration of acetone molecules (due to their hydrophobicity) in the regions of the solution where uranyl and nitrate ions are found. The experimental facts supported the mechanism proposed are presented. (authors)

  19. Structural contributions to the third-law entropy of uranyl phases

    International Nuclear Information System (INIS)

    Chen, F.; Ewing, R.C.

    1999-01-01

    Entropies that are used in geochemical calculations are usually based on calorimetric measurements. However, because of the contributions of neglected residual entropies which cannot be determined by calorimetric measurements, the true third-law entropies for many phases may be quite different from those derived from thermal data. The residual entropies are caused by site-mixing, structural disorder and magnetic spin disorder and may result in a considerable contribution to the third-law entropy of solid phases. Magnetic spin-configurational entropy is not expected to be significant in uranyl phases. However, because most uranyl phases are based on sheet or chain structures and usually contain several molecular water groups, site-mixing, vacancies, as well as disorder in the orientation of hydrogen bonds and the polar H 2 O molecules may occur. Calculations of the ideal site-mixing configurational entropy for some uranyl phases indicate that the residual contributions that arise from substitution and vacancies to the third-law entropies of uranyl phases may be large. A brief examination of the crystal chemistry of water molecules in uranyl phases suggests that considerable residual entropy may be caused by the disorder of hydrogen bonds associated with interstitial H 2 O groups

  20. Time-resolved luminescence studies in hydrogen uranyl phosphate intercalated with amines

    Energy Technology Data Exchange (ETDEWEB)

    Novo, Joao Batista Marques [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil)]. E-mail: jbmnovo@quimica.ufpr.br; Batista, Fabio Roberto [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Cunha, Carlos Jorge da [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Dias, Lauro Camargo Jr. [Departamento de Quimica, Universidade Federal do Parana, CP 19081, 81531-990 Curitiba-PR (Brazil); Teixeira Pessine, Francisco Benedito [Instituto de Quimica, Universidade Estadual de Campinas, CP 6154, 13084-971 Campinas-SP (Brazil)

    2007-05-15

    Time-resolved luminescence decays of intercalated compounds of hydrogen uranyl phosphate (HUP) with p-toluidinium (HUPPT), benzylaminium (HUPBZ), {alpha}-methylbenzylaminium (HUPMBZ) and hydroxylaminium (HUPHAM) were studied. The prepared compounds belong to the tetragonal P4/ncc space group and showed 00 l reflections shifted to lower angles relative to HUP, indicating that the intercalation increases the c parameter of the unit cell. The luminescence decays of the compounds with 100% of intercalation ratio (HUPHAM and HUPBZ) were analyzed by Global Analysis, assuming Lianos' stretched exponential as the model function, which can be applied to compounds with restricted geometry and mobile donor and quencher molecules. It was remarkable that the luminescence decays showed that the quenching of the emission of the uranyl ions by the intercalated protonated amines is not restricted by low dimensionality of the host uranyl phosphate, and that a diffusion mechanism occurs. Benzylaminium cation efficiently quenches the excited energy of the uranyl ions at close distance, but the long-range and long-lifetime quenching is hindered. A different situation is found in the case of the small hydroxylaminium cation, where the long distance diffusion of the species is fast, playing an important role in the quenching of the excited uranyl ions at longer times.

  1. Time-resolved luminescence studies in hydrogen uranyl phosphate intercalated with amines

    International Nuclear Information System (INIS)

    Novo, Joao Batista Marques; Batista, Fabio Roberto; Cunha, Carlos Jorge da; Dias, Lauro Camargo Jr.; Teixeira Pessine, Francisco Benedito

    2007-01-01

    Time-resolved luminescence decays of intercalated compounds of hydrogen uranyl phosphate (HUP) with p-toluidinium (HUPPT), benzylaminium (HUPBZ), α-methylbenzylaminium (HUPMBZ) and hydroxylaminium (HUPHAM) were studied. The prepared compounds belong to the tetragonal P4/ncc space group and showed 00 l reflections shifted to lower angles relative to HUP, indicating that the intercalation increases the c parameter of the unit cell. The luminescence decays of the compounds with 100% of intercalation ratio (HUPHAM and HUPBZ) were analyzed by Global Analysis, assuming Lianos' stretched exponential as the model function, which can be applied to compounds with restricted geometry and mobile donor and quencher molecules. It was remarkable that the luminescence decays showed that the quenching of the emission of the uranyl ions by the intercalated protonated amines is not restricted by low dimensionality of the host uranyl phosphate, and that a diffusion mechanism occurs. Benzylaminium cation efficiently quenches the excited energy of the uranyl ions at close distance, but the long-range and long-lifetime quenching is hindered. A different situation is found in the case of the small hydroxylaminium cation, where the long distance diffusion of the species is fast, playing an important role in the quenching of the excited uranyl ions at longer times

  2. Kinetic studies of uranyl ion adsorption on acrylonitrile (AN) / polyethylene glycol (PEG) interpenetrating networks (IPN)

    International Nuclear Information System (INIS)

    Aycik, G.A.; Gurellier, R.

    2004-01-01

    The kinetics of the adsorption of uranyl ions on amidoximated acrylonitrile (AN)/ polyethylene glycol (PEG) interpenetrating network (IPNs) from aqueous solutions was studied as a function of time and temperature. Adsorption analyses were performed for definite uranyl ion concentrations of 1x10 -2 M and at four different temperatures as 290K, 298K, 308K and 318K. Adsorption time was increased from zero to 48 hours. Adsorption capacities of uranyl ions by PEG/AN IPNS were determined by gamma spectrometer. The results indicate that adsorption capacity increases linearly with increasing temperature. The max adsorption capacity was found as 602 mgu/g IPN at 308K. Adsorption rate was evaluated from the curve plotted of adsorption capacity versus time, for each temperature. Rate constants for uranyl ions adsorption on amidoximated ipns were calculated for 290K, 298K, 308K and 318K at the solution concentration of 1x10 -2 M . The results showed that as the temperature increases the rate constant increases exponentially too. The mean activation energy of uranyl ions adsorption was found as 34.6 kJ/mole by using arrhenius equation. (author)

  3. Effect of Sodium Selenate on Hippocampal Proteome of 3×Tg-AD Mice-Exploring the Antioxidant Dogma of Selenium against Alzheimer's Disease.

    Science.gov (United States)

    Iqbal, Javed; Zhang, Kaoyuan; Jin, Na; Zhao, Yuxi; Liu, Qiong; Ni, Jiazuan; Shen, Liming

    2018-04-19

    Selenium (Se), an antioxidant trace element, is an important nutrient for maintaining brain functions and is reported to be involved in Alzheimer's disease (AD) pathologies. The present study has been designed to elucidate the protein changes in hippocampus of 3×Tg-AD mice after supplementing sodium selenate as an inorganic source of selenium. By using iTRAQ proteomics technology, 113 differentially expressed proteins (DEPs) are found in AD/WT mice with 37 upregulated and 76 downregulated proteins. Similarly, in selenate-treated 3×Tg-AD (ADSe/AD) mice, 115 DEPs are found with 98 upregulated and 17 downregulated proteins. The third group of mice (ADSe/WT) showed 75 DEPs with 46 upregulated and 29 downregulated proteins. Among these results, 42 proteins (40 downregulated and 2 upregulated) in the diseased group showed reverse expression when treated with selenate. These DEPs are analyzed with different bioinformatics tools and are found associated with various AD pathologies and pathways. Based on their functions, selenate-reversed proteins are classified as structural proteins, metabolic proteins, calcium regulating proteins, synaptic proteins, signaling proteins, stress related proteins, and transport proteins. Six altered AD associated proteins are successfully validated by Western blot analysis. This study shows that sodium selenate has a profound effect on the hippocampus of the triple transgenic AD mice. This might be established as an effective therapeutic agent after further investigation.

  4. Changes in SeMSC, glucosinolates and sulforaphane levels, and in proteome profile in broccoli (Brassica oleracea var. Italica) fertilized with sodium selenate.

    Science.gov (United States)

    Sepúlveda, Ignacio; Barrientos, Herna; Mahn, Andrea; Moenne, Alejandra

    2013-05-07

    The aim of this work was to analyze the effect of sodium selenate fortification on the content of selenomethyl selenocysteine (SeMSC), total glucosinolates and sulforaphane, as well as the changes in protein profile of the inflorescences of broccoli (Brassica oleracea var. Italica). Two experimental groups were considered: plants treated with 100 μmol/L sodium selenate (final concentration in the pot) and control plants treated with water. Fortification began 2 weeks after transplantation and was repeated once a week during 10 weeks. Broccoli florets were harvested when they reached appropriate size. SeMSC content in broccoli florets increased significantly with sodium selenate fortification; but total glucosinolates and sulforaphane content as well as myrosinase activity were not affected. The protein profile of broccoli florets changed due to fortification with sodium selenate. Some proteins involved in general stress-responses were up-regulated, whereas down-regulated proteins were identified as proteins involved in protection against pathogens. This is the first attempt to evaluate the physiological effect of fortification with sodium selenate on broccoli at protein level. The results of this work will contribute to better understanding the metabolic processes related with selenium uptake and accumulation in broccoli.

  5. A Comprehensive Study of One-Step Selenization Process for Cu(In1-x Ga x )Se2 Thin Film Solar Cells.

    Science.gov (United States)

    Chen, Shih-Chen; Wang, Sheng-Wen; Kuo, Shou-Yi; Juang, Jenh-Yih; Lee, Po-Tsung; Luo, Chih Wei; Wu, Kaung-Hsiung; Kuo, Hao-Chung

    2017-12-01

    In this work, aiming at developing a rapid and environmental-friendly process for fabricating CuIn 1-x Ga x Se 2 (CIGS) solar cells, we demonstrated the one-step selenization process by using selenium vapor as the atmospheric gas instead of the commonly used H 2 Se gas. The photoluminescence (PL) characteristics indicate that there exists an optimal location with superior crystalline quality in the CIGS thin films obtained by one-step selenization. The energy dispersive spectroscopy (EDS) reveals that the Ga lateral distribution in the one-step selenized CIGS thin film is intimately correlated to the blue-shifted PL spectra. The surface morphologies examined by scanning electron microscope (SEM) further suggested that voids and binary phase commonly existing in CIGS films could be successfully eliminated by the present one-step selenization process. The agglomeration phenomenon attributable to the formation of MoSe 2 layer was also observed. Due to the significant microstructural improvement, the current-voltage (J-V) characteristics and external quantum efficiency (EQE) of the devices made of the present CIGS films have exhibited the remarkable carrier transportation characteristics and photon utilization at the optimal location, resulting in a high conversion efficiency of 11.28%. Correlations between the defect states and device performance of the one-step selenized CIGS thin film were convincingly delineated by femtosecond pump-probe spectroscopy.

  6. Changes in SeMSC, Glucosinolates and Sulforaphane Levels, and in Proteome Profile in Broccoli (Brassica oleracea var. Italica Fertilized with Sodium Selenate

    Directory of Open Access Journals (Sweden)

    Alejandra Moenne

    2013-05-01

    Full Text Available The aim of this work was to analyze the effect of sodium selenate fortification on the content of selenomethyl selenocysteine (SeMSC, total glucosinolates and sulforaphane, as well as the changes in protein profile of the inflorescences of broccoli (Brassica oleracea var. Italica. Two experimental groups were considered: plants treated with 100 mmol/L sodium selenate (final concentration in the pot and control plants treated with water. Fortification began 2 weeks after transplantation and was repeated once a week during 10 weeks. Broccoli florets were harvested when they reached appropriate size. SeMSC content in broccoli florets increased significantly with sodium selenate fortification; but total glucosinolates and sulforaphane content as well as myrosinase activity were not affected. The protein profile of broccoli florets changed due to fortification with sodium selenate. Some proteins involved in general stress-responses were up-regulated, whereas down-regulated proteins were identified as proteins involved in protection against pathogens. This is the first attempt to evaluate the physiological effect of fortification with sodium selenate on broccoli at protein level. The results of this work will contribute to better understanding the metabolic processes related with selenium uptake and accumulation in broccoli.

  7. Selenate reduction to elemental selenium by anaerobic bacteria in sediments and culture: biogeochemical significance of a novel, sulfate-independent respiration

    Science.gov (United States)

    Oremland, Ronald S.; Hollibaugh, James T.; Maest, Ann S.; Presser, Theresa S.; Miller, Laurence G.; Culbertson, Charles W.

    1989-01-01

    Interstitial water profiles of SeO42−, SeO32−, SO42−, and Cl− in anoxic sediments indicated removal of the seleno-oxyanions by a near-surface process unrelated to sulfate reduction. In sediment slurry experiments, a complete reductive removal of SeO42− occurred under anaerobic conditions, was more rapid with H2 or acetate, and was inhibited by O2, NO3−, MnO2, or autoclaving but not by SO42− or FeOOH. Oxidation of acetate in sediments could be coupled to selenate but not to molybdate. Reduction of selenate to elemental selenium was determined to be the mechanism for loss from solution. Selenate reduction was inhibited by tungstate and chromate but not by molybdate. A small quantity of the elemental selenium precipitated into sediments from solution could be resolublized by oxidation with either nitrate or FeOOH, but not with MnO2. A bacterium isolated from estuarine sediments demonstrated selenate-dependent growth on acetate, forming elemental selenium and carbon dioxide as respiratory end products. These results indicate that dissimilatory selenate reduction to elemental selenium is the major sink for selenium oxyanions in anoxic sediments. In addition, they suggest application as a treatment process for removing selenium oxyanions from wastewaters and also offer an explanation for the presence of selenite in oxic waters.

  8. Quenching of excited uranyl ion during its photochemical reduction with triphenyl-phosphine : Part IV - effect of heterocyclic molecules

    International Nuclear Information System (INIS)

    Sidhu, M.S.; Bhatia, P.V.K.

    1994-01-01

    The presence of heterocyclic compounds triggers off a competition between photophysical and photochemical annihilation of excited uranyl ion during its photochemical reduction with triphenylphosphine. This competition is used to measure Stern-Volmer constant using UV visible spectrophotometer for quenching the uranyl ion luminescence with a number of heterocyclic molecules viz., pyridine, thiophene bipyridyl, tetrahydrofuran and piperidine. (author). 7 refs., 2 figs., 1 tab

  9. Aqueous uranyl complexes. 3. Potentiometric measurements of the hydrolysis of uranyl(VI) ion at 25 degrees C

    International Nuclear Information System (INIS)

    Palmer, D.A.; Nguyen-Trung, C.

    1995-01-01

    Potentiometric titrations of uranyl(VI) solutions were conducted using a standard glass/calomel electrode combination over the pH range 3 to 12 at 0.1 mol-kg -1 ionic strength with tetramethylammonium trifluoromethanesulfonate as the supporting electrolyte. The electrodes were calibrated directly on the hydrogen ion concentration scale during the initial stage of each titration. The species, UO 2 2+ , (UO 2 ) 2 (OH) 2 2+ , (UO 2 ) 3 (OH) 5 + , (UO 2 ) 3 (OH) 7 - , (UO 2 ) 3 (OH) 8 2- , and (UO 2 ) 3 (OH) 10 4- identified in an earlier Raman study were compatible with the analysis of the titration data. Based on this analysis and application of the extended Debye-Hueckel treatment, the polynuclear species indicated above were assigned overall formation constants at 25 degrees C and at infinite dilution of -5.51±0.04, -15.3±0.1, -27.77±0.09, -37.65±0.14, and -62.4±0.3, respectively. The results are discussed in reference to hydrolysis quotients reported in the literature for the first three species. Formation quotients for the last two species have not been reported previously

  10. Decomposition of uranyl peroxo-carbonato complex ion in the presence of metal oxides in carbonate media

    International Nuclear Information System (INIS)

    Dong-Yong Chung; Min-Sung Park; Keun-Young Lee; Eil-Hee Lee; Kwang-Wook Kim; Jei-Kwon Moon

    2015-01-01

    Uranium oxide was dissolved in the form of the uranyl peroxo-carbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- in carbonate solutions with hydrogen peroxide. When UO 2 (O 2 )(CO 3 ) 2 4- ions lose their peroxide component, they become a stable species of uranyl tricarbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- . The uranyl peroxo-carbonato complex self-decomposed more rapidly into the uranyl tricarbonato complex ion in the presence of a metal oxide in the carbonate solution. In this study, decomposition of the uranyl peroxo-carbonato complex in a carbonate solution was investigated in the presence of several metal oxides using absorption spectroscopy. (author)

  11. Time-resolved luminescence spectroscopy of trace uranyl in wet sand

    International Nuclear Information System (INIS)

    Freed, D.

    1993-01-01

    The objective of the project was to develop a technique to observe and characterize the behaviour of uranium in unsaturated groundwater flow systems, particularly with regard to unstable ''fingered'' flow, which could drastically reduce time of travel. The actual experimental work described was a study of the feasibility of detecting uranyl at the parts-per-billion level in aqueous solution by means of its luminescence spectrum. A high-power UV laser was used to excite aqueous uranyl in a wet sand mixture; the characteristic green phosphorescence emitted in the decay transition was detected by a photomultiplier tube; and the amplified signal was sent to an oscilloscope in communication with Macintosh data acquisition software. At the time of the conference, a more sophisticated sample configuration for imaging the flow of uranyl was already under development. 5 refs., 3 figs

  12. Time-resolved luminescence spectroscopy of trace uranyl in wet sand

    Energy Technology Data Exchange (ETDEWEB)

    Freed, D [Massachusetts Inst. of Tech., Cambridge, MA (United States)

    1994-12-31

    The objective of the project was to develop a technique to observe and characterize the behaviour of uranium in unsaturated groundwater flow systems, particularly with regard to unstable ``fingered`` flow, which could drastically reduce time of travel. The actual experimental work described was a study of the feasibility of detecting uranyl at the parts-per-billion level in aqueous solution by means of its luminescence spectrum. A high-power UV laser was used to excite aqueous uranyl in a wet sand mixture; the characteristic green phosphorescence emitted in the decay transition was detected by a photomultiplier tube; and the amplified signal was sent to an oscilloscope in communication with Macintosh data acquisition software. At the time of the conference, a more sophisticated sample configuration for imaging the flow of uranyl was already under development. 5 refs., 3 figs.

  13. Expanding the Library of Uranyl Amide Derivatives: New Complexes Featuring the tert-Butyldimethylsilylamide Ligand.

    Science.gov (United States)

    Pattenaude, Scott A; Coughlin, Ezra J; Collins, Tyler S; Zeller, Matthias; Bart, Suzanne C

    2018-04-16

    New uranyl derivatives featuring the amide ligand, -N(SiHMe 2 ) t Bu, were synthesized and characterized by X-ray crystallography, multinuclear NMR spectroscopy, and absorption spectroscopies. Steric properties of these complexes were also quantified using the computational program Solid-G. The increased basicity of the free ligand -N(SiHMe 2 ) t Bu was demonstrated by direct comparison to -N(SiMe 3 ) 2 , a popular supporting ligand for uranyl. Substitutional lability on a uranyl center was also demonstrated by exchange with the -N(SiMe 3 ) 2 ligand. The increased basicity of this ligand and diverse characterization handles discussed here will make these compounds useful synthons for future reactivity.

  14. Contribution to the study of uranyl salts in butyl phosphate solutions

    International Nuclear Information System (INIS)

    Coulon, A.

    1965-06-01

    A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from ∼ 1270 cm -1 to ∼ 1180 cm -1 . A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [fr

  15. Synthesis, X-ray crystallography, thermal studies, spectroscopic and electrochemistry investigations of uranyl Schiff base complexes.

    Science.gov (United States)

    Asadi, Zahra; Shorkaei, Mohammad Ranjkesh

    2013-03-15

    Some tetradentate salen type Schiff bases and their uranyl complexes were synthesized and characterized by UV-Vis, NMR, IR, TG, C.H.N. and X-ray crystallographic studies. From these investigations it is confirmed that a solvent molecule occupied the fifth position of the equatorial plane of the distorted pentagonal bipyramidal structure. Also, the kinetics of complex decomposition by using thermo gravimetric methods (TG) was studied. The thermal decomposition reactions are first order for the studied complexes. To examine the properties of uranyl complexes according to the substitutional groups, we have carried out the electrochemical studies. The electrochemical reactions of uranyl Schiff base complexes in acetonitrile were reversible. Copyright © 2012 Elsevier B.V. All rights reserved.

  16. Uranyl adsorption kinetics within silica gel: dependence on flow velocity and concentration

    Science.gov (United States)

    Dodd, Brandon M.; Tepper, Gary

    2017-09-01

    Trace quantities of a uranyl dissolved in water were measured using a simple optical method. A dilute solution of uranium nitrate dissolved in water was forced through nanoporous silica gel at fixed and controlled water flow rates. The uranyl ions deposited and accumulated within the silica gel and the uranyl fluorescence within the silica gel was monitored as a function of time using a light emitting diode as the excitation source and a photomultiplier tube detector. It was shown that the response time of the fluorescence output signal at a particular volumetric flow rate or average liquid velocity through the silica gel can be used to quantify the concentration of uranium in water. The response time as a function of concentration decreased with increasing flow velocity.

  17. Studies of rubidium selenate with secondary phase of RbOH under humidified reducing atmosphere

    International Nuclear Information System (INIS)

    Beyribey, Berceste; Hallinder, Jonathan; Poulsen, Finn Willy; Bonanos, Nikolaos; Mogensen, Mogens

    2012-01-01

    Highlights: ► Degradation of Rb 2 SeO 3 and Rb 2 SeO 4 to form RbOH provide protonic conductivity. ► The conductivity increases by increasing temperature. ► The highest conductivity value of 2.01·10 −4 S cm −1 is observed at 317 °C. ► The work may state conductivity rise in solid acid electrolytes upon decomposition. - Abstract: The high temperature properties of Rb 2 SeO 4 have been studied by calorimetry, impedance spectroscopy and X-ray powder diffraction. As synthesized, Rb 2 SeO 4 includes a second phase of Rb 2 SeO 3 , which can be eliminated upon heating the compound. As expected, no conductivity is observed in dry (pH 2 O 2 O = 0.1 bar) air at 176 °C, the conductivity increases sharply from 8.6·10 −8 to 1.7·10 −6 S cm −1 . Under humidified (pH 2 O = 0.1 bar) reducing atmosphere (9%H 2 in N 2 ), the conductivity increases to 2.0·10 −4 S cm −1 at 317 °C. Degradation of Rb 2 SeO 3 and Rb 2 SeO 4 to form RbOH, which is known as a proton conductor, are thought to be responsible for the observed conductivity in humidified atmospheres. Our observations may explain the conductivity rise in other solid acid electrolytes, including sulfate and selenate groups, around their decomposition temperatures, in humidified atmospheres.

  18. The simulation of lunar gravity field recovery from D-VLBI of Chang’E-1 and SELENE lunar orbiters

    Science.gov (United States)

    Yan, Jianguo; Ping, Jingsong; Matsumoto, K.; Li, Fei

    2008-07-01

    The lunar gravity field is a foundation to study the lunar interior structure, and to recover the evolution history of the Moon. It is still an open and key topic for lunar science. For above mentioned reasons, it becomes one of the important scientific objectives of recent lunar missions, such as KAGUYA (SELENE) the Japanese lunar mission and Chang’E-1, the Chinese lunar mission. The Chang’E-1 and the SELENE were successfully launched in 2007. It is estimated that these two missions can fly around the Moon longer than 6 months simultaneously. In these two missions, the Chinese new VLBI (Very Long Baseline Interferometry) network will be applied for precise orbit determination (POD) by using a differential VLBI (D-VLBI) method during the mission period. The same-beam D-VLBI technique will contribute to recover the lunar gravity field together with other conventional observables, i.e. R&RR (Range and Range Rate) and multi-way Doppler. Taking VLBI tracking conditions into consideration and using the GEODYNII/SOVLE software of GSFC/NASA/USA [Rowlands, D.D., Marshall, J.A., Mccarthy, J., et al. GEODYN II System Description, vols. 1 5. Contractor Report, Hughes STX Corp. Greenbelt, MD, 1997; Ullman, R.E. SOLVE program: mathematical formulation and guide to user input, Hughes/STX Contractor Report, Contract NAS5-31760. NASA Goddard Space Flight Center, Greenbelt, Maryland, 1994], we simulated the lunar gravity field recovering ability with and without D-VLBI between the Chang’E-1 and SELENE main satellite. The cases of overlapped flying and tracking period of 30 days, 60 days and 90 days have been analyzed, respectively. The results show that D-VLBI tracking between two lunar satellites can improve the gravity field recovery remarkably. The results and methods introduced in this paper will benefit the actual missions.

  19. Behaviour of selenate in soils: experimental approach and modeling of hysteresis of sorption/desorption

    International Nuclear Information System (INIS)

    Loffredo, N.

    2010-01-01

    In the context of future storage of nuclear material in deep geological layers, the transfer of selenium-79 from groundwater to biosphere through irrigation is one of the scenarios considered by the ANDRA (National Agency for Radioactive Waste Management). So, the soil would act as an interface between the geosphere and biosphere. Actually the model adopted to evaluate the element mobility in soil is based on a simple representation of its distribution between the quantity adsorbed on the soil and the amount remaining in the solution (KD model). Such distribution is considered as instantaneous, reversible and linear with the concentration of contamination. This model has some inadequacies with respect to selenium because this latter can be present in different redox states that control its mobility and whose transformation kinetics among states are poorly known (Se(-II), Se(0), Se(IV) and Se(VI)). In order to improve predictions on the mobility of selenium in soil, selenate (Se(VI)) - which is the most mobile form - has been used to study its interactions with respect to two different soils (soil B and soil R). A kinetic model, alternative to the K d model, has been developed to describe the evolution of stocks of Se(VI) in solution. This model considers that a fraction of selenium is associated with soil in a reversibly way (potentially mobile) and a portion of it is stabilized in soil (pseudo-irreversibly fixed). This model integrates on one hand, in the soil, kinetics of biotic and abiotic stabilization and on the other hand, in solution, a reduction kinetic. With the goal of acquiring the parameters of the models, various experiments using dialysis bags have been effectuated, both in batch and with open-flow reactors. The parameter acquisition has allowed kinetic and K d models to be compared in different realistic scenarios of contamination (chronic or sequential) of a surface soil with 79 Se(VI). In addition, the sorption mechanisms of Se(VI) have been

  20. Engineering of specific uranyl-coordination sites in the calcium-binding motif of Calmodulin

    International Nuclear Information System (INIS)

    Beccia, M.; Pardoux, R.; Sauge-Merle, S.; Bremond, N.; Lemaire, D.; Berthomieu, C.; Delangle, P.; Guilbaud, P.

    2014-01-01

    Complete text of publication follows: Characterization of heavy metals interactions with proteins is fundamental for understanding the molecular factors and mechanisms governing ions toxicity and speciation in cells. This line of research will also help in developing new molecules able to selectively and efficiently bind toxic metal ions, which could find application for bio-detection or bioremediation purposes. We have used the regulatory calcium-binding protein Calmodulin (CaM) from A. thaliana as a structural model and, starting from it, we have designed various mutants by site-directed mutagenesis. We have analysed thermodynamics of uranyl ion binding to both sites I and II of CaM N-terminal domain and we have identified structural factors governing this interaction. Selectivity for uranyl ion has been tested by studying reactions of the investigated peptides with Ca 2+ , in the same conditions used for UO 2 2+ . Spectro-fluorimetric titrations and FTIR analysis have shown that the affinity for uranyl increases by phosphorylation of a threonine in site I, especially approaching the physiological pH, where the phospho-threonine side chain is deprotonated. Based on structural models obtained by Molecular Dynamics, we tested the effect of a two residues deletion on site I properties. We obtained an almost two orders of magnitude increase in affinity for uranyl, with a sub-nanomolar dissociation constant for the uranyl complex with the non phosphorylated peptide, and an improved uranyl/calcium selectivity. Allosteric effects depending on Ca 2+ and UO 2 2+ binding have been investigated by comparing thermodynamic parameters obtained for mutants having both sites I and II able to chelate metal ions with those of mutants consisting of just one active site

  1. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Univ. of California, Berkeley, CA (United States)

    2015-01-21

    The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  2. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    International Nuclear Information System (INIS)

    Arnold, John

    2015-01-01

    The uranyl cation (UO 2 2+ ) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  3. Background electrolytes and pH effects on selenate adsorption using iron-impregnated granular activated carbon and surface binding mechanisms.

    Science.gov (United States)

    Zhang, Ning; Gang, Daniel Dianchen; McDonald, Louis; Lin, Lian-Shin

    2018-03-01

    Iron-impregnated granular activated carbon (Fe-GAC) has been shown effective for selenite adsorptive removal from aqueous solutions, but similar effectiveness was not observed with selenate. This study examined the effects of background electrolytes and pH on selenate adsorption on to Fe-GAC, and surface bindings to elucidate the selenate adsorption mechanisms. The decrease magnitude of selenate adsorption capacity under three background electrolytes followed the order: LiCl > NaCl > KCl, as ionic strength increased from 0.01 to 0.1 M. Larger adsorption capacity differences among the three electrolytes were observed under the higher ionic strengths (0.05 and 0.1 M) than those under 0.01 M. Multiplet peak fittings of high resolution X-ray photoelectron spectra for O1s and Fe2p 3/2 indicated the presence of iron (III) on adsorbent surface. pH variations during the adsorbent preparation within 3-8 in NaCl solutions did not cause appreciable changes in the iron redox state and composition. Raman spectra showed the formation of both monodentate and bidentate inner sphere complexes under pHs adsorption under alkaline conditions. Mechanisms for monodentate and bidentate formations and a stable six-member ring structure were proposed. Two strategies were recommended for modifying Fe-GAC preparation procedure to enhance the selenate adsorption: (1) mixed-metal oxide coatings to increase the point of zero charge (pH zpc ); and (2) ferrous iron coating to initially reduce selenate followed by selenite adsorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Study of the Cupriavidus metallidurans CH34 resistance of selenite and selenate oxy-anions: accumulation, localisation and transformation of selenium

    International Nuclear Information System (INIS)

    Avoscan, L.

    2007-06-01

    Selenium is an essential trace element for the living organisms but it is very toxic at high concentration. Selenite and selenate oxides, soluble forms, highly toxic and bio-assimilable, are the most prevalent forms in the environment. Some soil micro-organisms play a dominant role and contribute to the natural cycle of selenium. Our study model, Cupriavidus (formerly Ralstonia) metallidurans CH34, a telluric bacterium characteristic of metal-contaminated biotopes, is known to resist selenite by reducing it into elemental selenium, an insoluble and less toxic form of selenium. In order to better understand the mechanisms of selenium reduction in the bacteria, three methods of speciation were combined (XAS (XANES and EXAFS), HPLC-ICP-MS and SDS-PAGEPIXE). They were completed by the direct quantification of selenium accumulated in the bacteria. Speciation analyses highlighted the existence of two mechanisms of reduction of selenium oxides in C. metallidurans CH34. Assimilation transforms selenite and selenate into organic selenium, identified as seleno-methionine and leads to its non-specific incorporation into bacterial proteins (presence of selenious proteins). Detoxication precipitates selenite in nano-particles of elemental selenium. This way of detoxication is not set up after an exposure to selenate although it is nevertheless possible to detect elemental selenium but in very small amount compared to the exposure of selenite. Seleno-diglutathion is detected in bacteria stressed by an exposure to selenate in medium limited in sulphate. Bacteria exposed to selenite accumulate 25 times more selenium than when they are exposed to selenate. The study of mutants resistant to selenite, which do not express the membrane protein DedA, showed that the accumulation of selenium after exposure to selenite is decreased compared with the wild strain meaning probable link between the transport of selenite and the DedA protein. Finally, selenate would use the sulphate permease

  5. Crystal field influence on vibration spectra: anhydrous uranyl chloride and dihydroxodiuranyl chloride tetrahydrate

    International Nuclear Information System (INIS)

    Perrin, Andre; Caillet, Paul

    1976-01-01

    Vibrational spectra of anhydrous uranyl chloride UO 2 Cl 2 and so called basic uranyl chloride: dihydroxodiuranyl chloride tetrahydrate /UO 2 (OH) 2 UO 2 /Cl 2 (H 2 O) 4 are reported. Factor group method analysis leads for the first time to complete and comprehensive interpretation of their spectra. Two extreme examples of crystal field influence on vibrational spectra are pointed out: for UO 2 Cl 2 , one is unable to explain spectra without taking into account all the elements of primitive crystalline cell, whilst for dihydroxodiuranyl dichloride tetrahydrate the crystal packing has very little effect on vibrational spectra [fr

  6. The treatment of uranyl nitrate from the AMOR process for VKTA Rossendorf

    International Nuclear Information System (INIS)

    Boessert, W.; Krempl, R.; Miller, J.W.

    2003-01-01

    The blending of uranyl nitrate solutions at VKTA and its subsequent treatment at BNFL-Sellafield is a significant step towards the safe and effective treatment of these enriched uranyl nitrate solutions. Overall the integration of the expertise of the international company BNFL/Westinghouse will lead to the achievement of a successful solution. This success has involved the integration of the project management and operational facilities of BNFL Sellafield with the local planning, design and manufacture capacities of Westinghouse Reaktor GmbH. (orig.)

  7. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    International Nuclear Information System (INIS)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

    2012-01-01

    Switching on uranium(V) reactivity: The silylated uranium(V) dioxo complex [(Me_3SiOUO)_2(L)_2] (A) is inert to oxidation, but after two-electron reduction to [(Me_3SiOUO)_2(L)]"2"- (1), it can be desilylated to form [OU(μ-O)_2UO(L)_2]"2"- (2) with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U"V"I"/"V couple in dioxygen reduction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    International Nuclear Information System (INIS)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B.

    2012-01-01

    The silylated uranium(V) dioxo complex [(Me_3SiOUO)_2(L)_2] is inert to oxidation, but after two-electron reduction to [(Me_3SiOUO)_2(L)]"2"-, it can be desilylated to form [OU(μ-O)_2UO(L)_2]"2"- with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U"V"I"/"V couple in dioxygen reduction. [de

  9. Kinetic analysis of laser induced phosphorescence in uranyl phosphate for improved analytical measurements

    International Nuclear Information System (INIS)

    Bushaw, B.A.

    1983-10-01

    Pulsed dye-laser excitation with multichannel scaler photon counting is used to obtain time resolved emission spectra of uranyl ions in aqueous solution. Kinetic analysis of this data corrects for matrix quenching and temperature effects which reduce the quantum yield of the uranyl ion luminescence. The method gives accurate measurements without separative prechemistry or the use of internal standards. Detection limits of one part-per-trillion (pptr) have been demonstrated, and in samples with concentrations greater than 100 pptr, relative standard deviations of less than 3% are achieved routinely

  10. Extraction of rare earth metals (3) from aqueous solutions containing thorium and uranyl nitrates

    International Nuclear Information System (INIS)

    Pyartman, A.K.; Kopyrin, A.A.; Berinskij, A.E.; Keskinov, V.A.

    2000-01-01

    Isotherms of extraction of rare earth metals (3) from aqueous solutions containing thorium and uranyl nitrates by solutions of tributylphosphate (TBP) and diisooctylmethylphosphonate (DIOMP) in kerosene at 298.15 Deg C and pH 1 are presented. Equations for description of interphase distribution of components of the systems considered are suggested. These equations describe distribution of components adequately in the systems of thorium nitrate (uranyl nitrate) - rare earth nitrates - (TBP, DIOMP) in the case of wide variation of phase compositions. Dependences of separation factors on composition of aqueous phase are considered [ru

  11. Removal of uranyl ions by p-hexasulfonated calyx[6]arene acid

    Energy Technology Data Exchange (ETDEWEB)

    Popescu, Ioana-Carmen [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Petru, Filip [“C.D. Nenitescu” Institute of Organic Chemistry, Splaiul Independentei 202B, Sector 6, Bucharest 71141 (Romania); Humelnicu, Ionel [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania); Mateescu, Marina [National R and D Institute for Chemistry and Petrochemistry, Splaiul Independenţei No. 202, Bucharest 060021 (Romania); Militaru, Ecaterina [R and D National Institute for Metals and Radioactive Resources–ICPMRR, B-dul Carol I No.70, Sector 2, Bucharest 020917 (Romania); Humelnicu, Doina, E-mail: doinah@uaic.ro [“Al.I. Cuza” University of Iasi, The Faculty of Chemistry, Bd. Carol-I No. 11, Iasi 700506 (Romania)

    2014-10-15

    Radioactive pollution is a significant threat for the people’s health. Therefore highly effective radioactive decontamination methods are required. Ion exchange, biotechnologies and phytoremediation in constructed wetlands have been used as radioactive decontamination technologies for uranium contaminated soil and water remediation. Recently, beside those classical methods the calix[n]arenic derivatives’ utilization as radioactive decontaminators has jogged attention. The present work aims to present the preliminary research results of uranyl ion sorption studies on the p-hexasulfonated calyx[6]arenic acid. The effect of temperature, contact time, sorbent amount and uranyl concentration variation on sorption efficiency was investigated. Isotherm models revealed that the sorption process fit better Langmuir isotherm.

  12. Investigation of regularities of uranyl salts complexing with neutral bases in nonaqueous media

    International Nuclear Information System (INIS)

    Kobets, L.V.; Buchikhin, E.P.

    1986-01-01

    Anhydrous uranyl chloride complexing with neutral oxygen-containing organic bases (sulfoxides, organic phosphates, phosphinates, phosphinoxides, N-oxides) in the acetone medium depending on the donor capacity of neutral molecules is discussed. The constants of 1:1 complexes dissociation are shown to detect no correlation with the donor capacity of neutral bases. At the same time stability constants of complexes increase as the donor capacity of ligands grows. But the dependence is of a complex character and is determined by the nature of neutral molecules. Estimation of uranyl chloride and 0-donor contributions into the values of stability constants and complex formation heats is given

  13. Ultrastructure changes produced by the action of uranyl acetate on the human erythrocyte in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Wyatt, J H

    1975-06-01

    Human erythrocytes exposed in vitro to low concentrations of uranyl ions are immediately changed in shape to stomatocytes. Electron microscope examination demonstrates that cellular damage is confined to the plasma membrane. Endocytosis of the cell membrane produces groups of inside out membrane-lined vesicles within the cell; lipid from the membrane enters the cell, giving rise to intracellular myelin figures, and breaks are seen in the cell membrane. It is proposed that the lipid fraction of the cell membrane is the primary target for damage by uranyl ions.

  14. Determination of uranium in uranyl nitrate solutions of nuclear grade quality - Gravimetric method

    International Nuclear Information System (INIS)

    1990-01-01

    This international Standard specifies a precise and accurate gravimetric method for determining the uranium content in uranyl nitrate product solutions of nuclear grade quality at concentrations above 100 g/l of uranium. Non-volatile impurities influence the accuracy of the method. Uranyl nitrate is converted into uranium octoxide (U 3 O 8 ) by ignition in air to constant mass at 900 deg. C ± 10 deg. C. Calculation of the uranium content in the sample using a gravimetric conversion factor which depends on the isotopic composition of the uranium. The isotopic composition is determined by mass spectrometry

  15. First start-up of nuclear criticality safety experiment facility for uranyl nitrate solution

    International Nuclear Information System (INIS)

    Zhu Qingfu; Shi Yongqian; Shen Leisheng; Hu Dingsheng; Zhao Shouzhi; He Tao; Sun Zheng; Lin Shenghuo; Yao Shigui

    2005-01-01

    The uranyl nitrate solution experiment facility for the research on nuclear criticality safety is described. The nuclear fuel loading steps in the first start-up for water-reflected core are presented. During the experiments, the critical volume of uranyl nitrate solution was determined as 20479.62 mL with count rate inverse extrapolation method, reactivity interpolation method, and steady power method. By calculation, critical mass of 235 U was derived as 1579.184 g from experimental data. The worth of control rods was also calibrated in the first start-up of the facility. (authors)

  16. Interaction of aluminium(3) with uranyl ions in the course of joint hydrolysis

    International Nuclear Information System (INIS)

    Yusov, A.B.; Budantseva, N.A.; Fedoseev, A.M.; Astafurova, L.N.

    2001-01-01

    By means of spectrophotometry, luminescence and IR-spectroscopy one studied interaction of uranyl ions with Al 3+ ions in solutions at pH≥2 and in precipitates at pH≥5. It is shown that within 3-4 pH range the uranyl hydrolyzed forms interact with these of aluminium. Mixed hydroxoaquacomplexes are likely to be formed in solution with U:Al = 1:1 molar ratio. Large-size mixed polymers may be formed with pH increase. Varying of precipitation pH from 5 up to 14 does not minimize the importance of the oligomer mixed compounds for precipitation formation [ru

  17. Ultrastructure changes produced by the action of uranyl acetate on the human erythrocyte in vitro

    International Nuclear Information System (INIS)

    Wyatt, J.H.

    1975-06-01

    Human erythrocytes exposed in vitro to low concentrations of uranyl ions are immediately changed in shape to stomatocytes. Electron microscope examination demonstrates that cellular damage is confined to the plasma membrane. Endocytosis of the cell membrane produces groups of inside out membrane-lined vesicles within the cell; lipid from the membrane enters the cell, giving rise to intracellular myelin figures, and breaks are seen in the cell membrane. It is proposed that the lipid fraction of the cell membrane is the primary target for damage by uranyl ions. (author)

  18. Complete removal of uranyl nitrate from tissue matrix using supercritical fluid extraction

    International Nuclear Information System (INIS)

    Kumar, R.; Sivaraman, N.; Senthil Vadivu, E.; Srinivasan, T.G.; Vasudeva Rao, P.R.

    2003-01-01

    The removal of uranyl nitrate from tissue matrix has been studied with supercritical carbon dioxide modified with methanol alone as well as complexing reagents dissolved in methanol. A systematic study of various complexing agents led to the development of an extraction procedure for the quantitative recovery of uranium from tissue matrix with supercritical carbon dioxide modified with methanol containing small quantities of acetylacetone. The drying time and temperature employed in loading of uranyl nitrate onto tissue paper were found to influence the extraction efficiency significantly

  19. Characterization of osteopontin-uranyl interaction: role of multiple phosphorylations

    International Nuclear Information System (INIS)

    Qi, Lei

    2014-01-01

    While some metals are essential for Life, other ones are only toxicants for living organisms, tolerated below well-definite concentrations. This is the case for uranium, a natural element which has no known biological function. It is a low α emitter and its chemical toxicity rather than its radiological toxicity is a subject of concern. Once in the body, this metal reaches the blood and accumulates in the bones under the action of unknown mechanisms. Uranium mainly exists in form of uranyl ion (UO 2 2+ ) in aqueous media and particularly reacts with carboxylates, phenolates and phosphates of the proteins. Previous studies have highlighted that UO 2 2+ modulates the SPP1 expression, a gene which codes for osteopontin (OPN). This highly phosphorylated glycoprotein plays an important role in bone homeostasis. This role and its biochemical properties led us to hypothesize that OPN might be a potential target of UO 2 2+ and involved in its accumulation in bones. A simple and original purification process was optimized to produce very highly purified OPN starting from human and bovine milk. Various biophysical approaches were set up and confirmed that both bovine and human OPN display very high affinity for UO 2 2+ . Moreover, the formation of stable UO 2 -protein complexes originating from structural changes was evidenced. The major role of phosphorylations, both on the OPN's affinity for UO 2 2+ and the stability of the UO 2 -protein complexes, was confirmed. These results demonstrate that OPN presents all the characteristics to be a major UO 2 2+ binding-protein in vitro, and they open new insights in the understanding of the UO 2 2+ mineralization process mechanisms. (author) [fr

  20. Mechanism of acute renal failure after uranyl nitrate

    International Nuclear Information System (INIS)

    Blantz, R.C.; Konnen, K.

    1975-01-01

    Administration of 25 mg/kg uranyl nitrate (UN) to rats leads to a brief period of polyuria followed by progressive oliguria with death at 5 days. Factors that determine glomerular filtration rate (GFR) were examined in control Munich--Wistar rats (n = 16) and 2 h after either 15 mg/kg (n = 8) or 25 kg/kg (n = 7) of UN (i.v.) utilizing direct measurements of hydrostatic and oncotic pressures and plasma flow. Total kidney GFR was reduced to 47 percent of control in the low dose group and to 21 percent in the high dose group. The simultaneous nephron filtration rate (sngfr) was 28.6 +- 0.8 nl/min/g kidney wt in control, 29.1 +- 1.0 in the low dose group, and 18.1 +- 1.2 (P less than 0.001) in the higher dose group. Nephron plasma flow was equal to control at both doses of UN. Also directly measured hydrostatic pressure gradient across the glomerular capillary was not changed. The effective filtration pressure achieved equilibrium in control animals but became significantly positive at the efferent end of the capillary at both doses of UN and increased. Total glomerular permeability (L/sub p/A) was progressively reduced from control (0.089 +- 0.005 nl/s/g kidney wt/mm Hg) at low dose UN (0.047 +- 0.013) and high dose (0.024 +- 0.003 nl/s/g kidney wt/mm Hg). Therefore UN decreases GFR by two mechanisms: (a) tubular damage leading to back-diffusion of solutes and (b) a primary reduction in sngfr due to reduced L/sub p/A

  1. Study of the extraction mechanisms by TBP saturated by uranyl nitrate; Etude des mecanismes d'extraction du TBP sature par le nitrate d'uranyle

    Energy Technology Data Exchange (ETDEWEB)

    Meze, F

    2004-02-15

    This work deals with a particular phenomenon likely to occur in the nuclear waste reprocessing process PUREX. It was shown earlier by Russian works that the extractant molecule, tributyl phosphate (TBP), saturated by uranyl nitrate keeps its extraction capacities for nitric acid and tetravalent actinides. This study is composed of three parts. Firstly, some liquid-liquid extraction experiments were conducted to verify the ability of TBP saturated by uranyl nitrate to conserve its extraction capacities for nitric acid. Then, during these experiments, the UV and infrared spectra of both phases were recorded to obtain the organic phase speciation. At last, the informations gathered during the experimental part were used to build a general species distribution model of the H{sub 2}O/HNO{sub 3}/UO{sub 2}(NO{sub 3}){sub 2}/TBP system. (author)

  2. Syntheses and crystal structures of two novel alkaline uranyl chromates A2(UO2)(CrO4)2 (A=Rb, Cs) with bidentate coordination mode of uranyl ions by chromate anions

    International Nuclear Information System (INIS)

    Siidra, Oleg I.; Nazarchuk, Evgeny V.; Krivovichev, Sergey V.

    2012-01-01

    Single crystals of Cs 2 (UO 2 )(CrO 4 ) 2 and Rb 2 (UO 2 )(CrO 4 ) 2 were prepared by solid state reactions. The structures are based upon the [(UO 2 )(CrO 4 ) 2 ] 2− chains. Within the chains, UrO 5 pentagonal bipyramids (Ur=uranyl) form Ur 2 O 8 dimers, which are linked via CrO 4 tetrahedra into one-dimensional chains. The CrO 4 tetrahedra coordinate uranyl ions in both mono- and bidentate fashion, which is unusual for uranyl chromates. The bidentate coordination has a strong influence upon geometrical parameters of both U and Cr coordination polyhedra. The conformation of the chains in 1 and 2 is different due to the different size of the Cs + and Rb + cations. - Graphical abstract: Uranyl chromate chain with monodentate and bidentate coordination mode of uranyl cations by CrO 4 tetrahedra in Cs 2 (UO 2 )(CrO 4 ) 2 . Highlights: ► Single crystals of novel uranyl chromates were prepared by solid state reactions. ► The CrO 4 tetrahedra coordinate uranyl ions in both mono- and bidentate fashion. ►The bidentate coordination has a strong influence upon geometrical parameters.

  3. The system uranyl nitrate-dietyl ether-water. Extraction by water in spray and packed columns from uranyl nitrate-either solutions

    International Nuclear Information System (INIS)

    Perez Luina, A.; Gutierrez Jodra, L.

    1960-01-01

    This paper is a continuation of the one published in Chemical Engineering Progress. Symposium Series, 50, n. 12, 127 (1954). New runs for spray columns, are given and other concentrations in uranyl nitrate for the packed columns. New correlations for the overall H.T.U. are also given. The individual H.T.U. have been grapycally calculated and show that the film resistances have similar values, being independent of the concentration of the ether phase. (Author) 24 refs

  4. An optional focusing SELENE extension to conventional neutron guides: A case study for the ESS instrument BIFROST

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, U.B., E-mail: uhansen@nbi.ku.dk [Niels Bohr Institute, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen (Denmark); Bertelsen, M. [Niels Bohr Institute, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen (Denmark); Stahn, J. [Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Lefmann, K. [Niels Bohr Institute, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen (Denmark)

    2017-04-21

    The high brilliance at the European Spallation Source (ESS) will allow for performing experiments with much smaller samples than at present neutron facilities and in much more complex sample environments. However the higher flux also results in higher background from unwanted neutrons not originating from scattering of the sample. We here present a new design idea for beam delivery, where a 165 m ballistic guide system with good transport properties is followed by a 4–8 m SELENE guide system similar to Montel optics used for X-ray optics. We have investigated the system by detailed Monte-Carlo simulations using McStas. We show that under certain conditions, this set-up works surprisingly well, with a brilliance transfer of 20–60% for neutrons of wavelength 4 Å and above. We demonstrate that the guide system is able to focus the beam almost perfectly onto samples sizes in the range of 0.1–2 mm. We furthermore show that our SELENE system is insensitive to gravity and to realistic values of guide waviness. We argue that this guide system can be useful as an optional guide insert when small samples are used in the vicinity of bulky sample environment, e.g. for high-field or high-pressure experiments.

  5. Investigation of stacked elemental layers for Cu(In,Ga)Se{sub 2} thin film preparation by rapid thermal selenization

    Energy Technology Data Exchange (ETDEWEB)

    Stroth, Christiane; Ohland, Joerg; Mikolajczak, Ulf; Madena, Thomas; Keller, Jan; Parisi, Juergen; Hammer, Maria; Riedel, Ingo [Energy and Semiconductor Research Laboratory, Department of Physics, University of Oldenburg, 26111 Oldenburg (Germany)

    2013-07-01

    Rapid thermal selenization of pure metallic (Cu-In-Ga) or selenium-containing (Cu-In-Ga-Se) precursors is a favorable method to fabricate Cu(In,Ga)Se{sub 2} absorber films for application in thin film solar cells. Because of its upscaling potential and the short process time it is a promising approach for the fabrication of CIGSe photovoltaic modules on industrial scale. As a preliminary work for prospective plasma-enhanced selenization of stacked elemental layers (SEL) the elements copper, indium and gallium were sequentially deposited on molybdenum coated soda-lime glass by thermal evaporation. The stacking order was varied and the precursors were annealed with different heating rates. Morphology, elemental depth distribution and phases of the layers were investigated before and after annealing using scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. Furthermore the influence of different heating rates on phase transitions during annealing was studied by in-situ X-ray diffraction.

  6. Standard test method for isotopic analysis of hydrolyzed uranium hexafluoride and uranyl nitrate solutions by thermal ionization mass spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2005-01-01

    1.1 This method applies to the determination of isotopic composition in hydrolyzed nuclear grade uranium hexafluoride. It covers isotopic abundance of 235U between 0.1 and 5.0 % mass fraction, abundance of 234U between 0.0055 and 0.05 % mass fraction, and abundance of 236U between 0.0003 and 0.5 % mass fraction. This test method may be applicable to other isotopic abundance providing that corresponding standards are available. 1.2 This test method can apply to uranyl nitrate solutions. This can be achieved either by transforming the uranyl nitrate solution to a uranyl fluoride solution prior to the deposition on the filaments or directly by depositing the uranyl nitrate solution on the filaments. In the latter case, a calibration with uranyl nitrate standards must be performed. 1.3 This test method can also apply to other nuclear grade matrices (for example, uranium oxides) by providing a chemical transformation to uranyl fluoride or uranyl nitrate solution. 1.4 This standard does not purport to address al...

  7. Band gap engineering of tandem structured CIGS compound absorption layer fabricated by sputtering and selenization

    Energy Technology Data Exchange (ETDEWEB)

    Kang, San; Sharma, Rahul; Sim, Jae-Kwan [Semiconductor Materials Processing Laboratory, School of Advanced Materials Engineering, College of Engineering, Research Center for Advanced Materials Development (RCAMD), Chonbuk National University, Deokjin-dong 664-14, Jeonju 561-756 (Korea, Republic of); Lee, Cheul-Ro, E-mail: crlee7@jbnu.ac.kr [Semiconductor Materials Processing Laboratory, School of Advanced Materials Engineering, College of Engineering, Research Center for Advanced Materials Development (RCAMD), Chonbuk National University, Deokjin-dong 664-14, Jeonju 561-756 (Korea, Republic of)

    2013-06-25

    Highlights: ► Systematic band gap engineering to fabricate tandem Cu(In,Ga)Se{sub 2} absorption layers. ► XRD shows prominent (1 1 2) reflection shift for attributed CIS, CIGS, and CGS phases. ► Optical transmittance and reflectance spectrum are improved towards infrared region. ► The Cu/In + Ga and Ga/In + Ga effect is matched with highest efficient solar cell. ► Tandem CIS/CIGS/CGS layer, the band gap is increased from 1.15 to 2.06 eV. -- Abstract: Band gap engineering was executed to fabricate a multi-junction stacked i.e. tandem Cu(In,Ga)Se{sub 2} (CIGS) absorption layer. The CIGS absorption layers consist of multi-junction stacked CIS/CIGS/CGS thin films from bottom to top with increasing band gap. Tandem CIGS layers were fabricated by using three precursor of CuIn, In/CuGa/In, and CuGa onto the Mo coated soda-lime glass (SLG) by the sequential sputtering of CuIn, CuGa, and In targets. The CIG precursors were converted into CIGS absorption thin film by selenization process. From the X-ray diffraction (XRD) pattern of CIS/CIGS/CGS tandem layer, with the prominent peak shift for (1 1 2) reflections was attributed to the individual CIS, CIGS, and CGS phases at 26.76°, 27.15°, and 27.65° diffraction angles, respectively. The morphologies and atomic (at%) composition uniformity onto the surface and along the depth were extensively analyzed with field effect scanning electron microscope (FESEM) attached energy dispersive spectroscopy (EDS) and secondary ion mass spectroscopy (SIMS). The optical properties such as transmittance, reflectance and absorbance were found to improve in the infrared region for all the tandem CIGS layers. Near the fundamental absorption edge, the absorption coefficient was approached to 10{sup 5} cm{sup −1} for CIS/CIGS/CGS tandem layer. The straight-line behavior indicates that the films have a direct band gap. The band gap was found to increase from 1.15 to 1.74 eV with the Ga-grading along the depth of individual CIS, CIGS

  8. Band gap engineering of tandem structured CIGS compound absorption layer fabricated by sputtering and selenization

    International Nuclear Information System (INIS)

    Kang, San; Sharma, Rahul; Sim, Jae-Kwan; Lee, Cheul-Ro

    2013-01-01

    Highlights: ► Systematic band gap engineering to fabricate tandem Cu(In,Ga)Se 2 absorption layers. ► XRD shows prominent (1 1 2) reflection shift for attributed CIS, CIGS, and CGS phases. ► Optical transmittance and reflectance spectrum are improved towards infrared region. ► The Cu/In + Ga and Ga/In + Ga effect is matched with highest efficient solar cell. ► Tandem CIS/CIGS/CGS layer, the band gap is increased from 1.15 to 2.06 eV. -- Abstract: Band gap engineering was executed to fabricate a multi-junction stacked i.e. tandem Cu(In,Ga)Se 2 (CIGS) absorption layer. The CIGS absorption layers consist of multi-junction stacked CIS/CIGS/CGS thin films from bottom to top with increasing band gap. Tandem CIGS layers were fabricated by using three precursor of CuIn, In/CuGa/In, and CuGa onto the Mo coated soda-lime glass (SLG) by the sequential sputtering of CuIn, CuGa, and In targets. The CIG precursors were converted into CIGS absorption thin film by selenization process. From the X-ray diffraction (XRD) pattern of CIS/CIGS/CGS tandem layer, with the prominent peak shift for (1 1 2) reflections was attributed to the individual CIS, CIGS, and CGS phases at 26.76°, 27.15°, and 27.65° diffraction angles, respectively. The morphologies and atomic (at%) composition uniformity onto the surface and along the depth were extensively analyzed with field effect scanning electron microscope (FESEM) attached energy dispersive spectroscopy (EDS) and secondary ion mass spectroscopy (SIMS). The optical properties such as transmittance, reflectance and absorbance were found to improve in the infrared region for all the tandem CIGS layers. Near the fundamental absorption edge, the absorption coefficient was approached to 10 5 cm −1 for CIS/CIGS/CGS tandem layer. The straight-line behavior indicates that the films have a direct band gap. The band gap was found to increase from 1.15 to 1.74 eV with the Ga-grading along the depth of individual CIS, CIGS, and CGS thin films

  9. Precipitation characteristics of uranyl ions at different pHs depending on the presence of carbonate ions and hydrogen peroxide.

    Science.gov (United States)

    Kim, Kwang-Wook; Kim, Yeon-Hwa; Lee, Se-yoon; Lee, Jae-Won; Joe, Kih-Soo; Lee, Eil-Hee; Kim, Jong-Seung; Song, Kyuseok; Song, Kee-Chan

    2009-04-01

    This work studied the dissolution of uranium dioxide and precipitation characteristics of uranyl ions in alkaline and acidic solutions depending on the presence of carbonate ions and H2O2 in the solutions at different pHs controlled by adding HNO3 or NaOH in the solution. The chemical structures of the precipitates generated in different conditions were evaluated and compared by using XRD, SEM, TG-DT, and IR analyses together. The sizes and forms of the precipitates in the solutions were evaluated, as well. The uranyl ions were precipitated in the various forms, depending on the solution pH and the presences of hydrogen peroxide and carbonate ions in the solution. In a 0.5 M Na2CO3 solution with H2O2, where the uranyl ions formed mixed uranyl peroxy-carbonato complexes, the uranyl ions were precipitated as a uranium peroxide of UO4(H20)4 at pH 3-4, and precipitated as a clarkeite of Na2U2Ox(OH)y(H2O)z above pH 13. In the same carbonate solution without H2O2, where the uranyl ions formed uranyl tris-carbonato complex, the uranyl ions were observed to be precipitated as a different form of clarkeite above pH 13. The precipitate of uranyl ions in a nitrate solution without carbonate ions and H2O2 at a high pH were studied together to compare the precipitate forms in the carbonate solutions.

  10. Application of the NICADonnan model for proton, copper and uranyl binding to humic acid

    NARCIS (Netherlands)

    Saito, T.; Nagasaki, S.; Tanaka, S.; Koopal, L.K.

    2004-01-01

    Humic acids are natural organic materials that play an important role in the migration of heavy metal and actinide ions in aquatic and soil systems. In the present study, the binding of protons, copper ions and uranyl ions to the purified Aldrich humic acid (PAHA) is investigated and the results are

  11. Vibrational spectra of monouranates and uranium hydroxides as reaction products of alkali with uranyl nitrate

    International Nuclear Information System (INIS)

    Komyak, A.I.; Umrejko, D.S.; Posledovich, M.R.

    2013-01-01

    Vibrational (IR absorption and Raman scattering) spectra for the reaction products of uranyl nitrate hexahydrate with NaOH and KOH have been studied. As a result of exchange reactions, the uranyl-ion coordinated nitrate groups are completely replaced by hydroxyl ions and various uranium and uranyl oxides or hydrates are formed. An analysis of the vibrations has been performed in terms of the frequencies of a free or coordinated nitrate group; comparison with the vibrations of the well-known uranium oxides and of the uranyl group UO 2 2+ has been carried out. Vibrational spectra of a free nitrate group are characterized by four vibrational frequencies 1050, 724, 850, and 1380 cm -1 , among which the frequencies at 724 and 1380 cm -1 are doubly degenerate and attributed to E’ symmetry of the point group D 3h . When this group is uranium coordinated, its symmetry level is lowered to C 2v , all vibrations of this group being active both in Raman and IR spectra. The doubly degenerate vibrations are exhibited as two bands and a frequency of the out-of-plane vibration is lowered to 815 cm -1 . (authors)

  12. Identification of Uranyl Surface Complexes an Ferrihydrite: Advanced EXAFS Data Analysis and CD-MUSIC Modeling

    NARCIS (Netherlands)

    Rossberg, A.; Ulrich, K.U.; Weiss, S.; Tsushima, S.; Hiemstra, T.; Scheinost, A.C.

    2009-01-01

    Previous spectroscopic research suggested that uranium(VI) adsorption to iron oxides is dominated by ternary uranyl-carbonato surface complexes across an unexpectedly wide pH range. Formation of such complexes would have a significant impact on the sorption behavior and mobility of uranium in

  13. Modeling of critical experiments employing Raschig rings in uranyl nitrate solution

    International Nuclear Information System (INIS)

    Tanner, J.E.

    1989-01-01

    Four critical experiments employing borated glass rings in concentrated uranyl nitrate solution yielded k eff higher by 0. 04 when modeled with a flux-weighted, homogenized cross section set than when modeled with discrete rings. k eff varied by 0.014 for a 10% boron uncertainty and by up to 0.04 for a 10% packing fraction uncertainty

  14. Study of the mechanism and kinetics of the reduction of uranyl ions in phosphoric acid solutions

    International Nuclear Information System (INIS)

    El Kacemi, K.; Tyburce, B.; Belcadi, S.

    1982-01-01

    The electrochemical reduction of uranyl ions in 0.1 to 9 M phosphoric acid has been investigated by polarography, cyclic voltammetry, chronopotentiometry and potentiostatic coulometry. In concentrated phosphoric acid solutions (H 3 PO 4 3 PO 4 concentrations. So, when the concentration of U(VI) increases and/or that of H 3 PO 4 reduces, the system becomes reversible. (author)

  15. Recuperation of uranyl ions from effluents by means of microbiological collectors

    International Nuclear Information System (INIS)

    Cecal, A.; Palamaru, I.; Humelnicu, D.; Goanta, M.; Rudic, V.; Salaru, V.V.; Gulea, A.

    1997-01-01

    This paper deals with the study of bioaccumulation of uranyl ions (UO 2 2+ ) from industrial effluents, using microbiological collectors: Nostoc linkia sp., Tolipotrix sp., Spirulina sp., Porphyridium cruentum and also the glucide extract of P. cruentum. The values of retaining degree of UO 2 2+ on the biomass, for several experimental conditions, were established between 14.22 and 91.99%

  16. Surface analysis of uranyl fluoride layers with a glow discharge lamp

    International Nuclear Information System (INIS)

    Nel, J.T.; Stander, C.M.; Boehmer, R.G.

    1991-01-01

    Surface analysis with a Grimm-type glow discharge lamp was used to analyse uranyl fluoride layers that had formed on a nickel substrate after exposure to UF 6 . Narrow-band optical filters were used to isolate the intensities of three fluorine emission lines. An in-depth profile of layer composition was obtained. (author)

  17. Method of separation of uranium from contaminating ions in an aqueous feed liquid containing uranyl ions

    International Nuclear Information System (INIS)

    Sundar, P.S.; Elikan, L.; Lyon, W.L.

    1975-01-01

    A coupled cationic/anionic method for the separation of uranium from contaminated aqueous solutions which contain uranyl ions is proposed. The fluid is extracted using an organic solvent containing a reagent which, together with the uranyl ions, forms a soluble aggregate in that solvent. As an example, 0.1 - 1 Mol/l Di-2-ethyl-hexyl-phosphorous acid in kerosene is mentioned. The organic solvent is then treated with a sealing liquid (volume ratio 20 - 35). For separation, an aqueous carbonate solution or a sulfuric acid solution can be used; the most favorable pH-values and concentrations for both cases are mentioned. The U +4 -ion at the sulfuric acid separation is subsequently oxidized to the uranyl ion with air. In each case, an extraction with an amine follows; after that, the amine is separated using an ammonium-carbonate solution and the uranium aggregate is precipitated, for example as ammonium uranyl tricarbonate, and then further processed to uranium oxide. The solvents and fluids used are led back in closed circuit; a flow diagram is given. (UWI) [de

  18. Complexes of uranyl with N-oxides of heterocyclic amines. Electron-vibrational absorption spectra

    International Nuclear Information System (INIS)

    Jezowska-Trzebiatowska, B.; Wieczorek, M.

    1977-01-01

    A number of coordination compounds formed by uranyl chloride and nitrate with N-oxides of heterocyclic amines have been prepared and characterized by spectral measurements in the absorption region 20000-50000 cm -1 . The electrons and vibronic transitions have been determined and discussed. (author)

  19. Kinetic investigation of uranyl-uranophile complexation. 1. Macrocyclic kinetic effect and macrocyclic protection effect

    International Nuclear Information System (INIS)

    Tabushi, I.; Yoshizawa, A.

    1986-01-01

    Equilibria and rates of ligand-exchange reactions between uranyl tricarbonate and dithiocarbamates and between uranyl tris-(dithiocarbamates) and carbonate were studied under a variety of conditions. The dithiocarbamates used were acyclic diethyl-dithiocarbamate and macrocyclic tris(dithiocarbamate). The acyclic ligand showed a triphasic (successive three-step) equilibrium with three different equilibrium constants while the macrocyclic ligand showed a clear monophasic (one-step) equilibrium with a much larger stability constant for the dithiocarbamate-uranyl complex. The macrocyclic ligand showed the S/sub N/2-type ligand-exchange rate in the forward as well as reverse process, while the first step of the acyclic ligand-exchange reaction proceeded via the S/sub N/1-type mechanism. This kinetic macrocyclic effect on molecularity is interpreted as the result of a unique topological requirement of uranyl complexation. The macrocyclic ligand also exhibited a clear protection effect, leading to the large stability constant. 19 references, 10 figures, 2 tables

  20. Cyclic phosphopeptides to rationalize the role of phosphoamino acids in uranyl binding to biological targets

    Energy Technology Data Exchange (ETDEWEB)

    Starck, Matthieu; Laporte, Fanny A.; Oros, Stephane; Sisommay, Nathalie; Gathu, Vicky; Lebrun, Colette; Delangle, Pascale [INAC/SyMMES, UMR5819, Universite Grenoble Alpes, CEA, CNRS, Grenoble (France); Solari, Pier Lorenzo [Synchrotron SOLEIL, L' orme des Merisiers, Saint-Aubin, Gif-sur-Yvette (France); Creff, Gaelle; Den Auwer, Christophe [Institut de Chimie de Nice, UMR7272, Universite Cote d' Azur, Nice (France); Roques, Jerome [Institut de Physique Nucleaire d' Orsay, CNRS-IN2P3, Univ. Paris-Sud, Universite Paris-Saclay (France)

    2017-04-19

    The specific molecular interactions responsible for uranium toxicity are not yet understood. The uranyl binding sites in high-affinity target proteins have not been identified yet and the involvement of phosphoamino acids is still an important question. Short cyclic peptide sequences, with three glutamic acids and one phosphoamino acid, are used as simple models to mimic metal binding sites in phosphoproteins and to help understand the mechanisms involved in uranium toxicity. A combination of peptide design and synthesis, analytical chemistry, extended X-ray absorption fine structure (EXAFS) spectroscopy, and DFT calculations demonstrates the involvement of the phosphate group in the uranyl coordination sphere together with the three carboxylates of the glutamate moieties. The affinity constants measured with a reliable analytical competitive approach at physiological pH are significantly enhanced owing to the presence of the phosphorous moiety. These findings corroborate the importance of phosphoamino acids in uranyl binding in proteins and the relevance of considering phosphoproteins as potential uranyl targets in vivo. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  1. Nuclear fuel technology - Determination of uranium in uranyl nitrate solutions of nuclear grade quality - Gravimetric method

    International Nuclear Information System (INIS)

    2003-01-01

    This International Standard specifies a precise and accurate gravimetric method for determining the mass fraction of uranium in uranyl nitrate solutions of nuclear grade quality containing more than 100 g/kg of uranium. Non-volatile impurities influence the accuracy of the method

  2. Potential New Ligand Systems for Binding Uranyl Ions in Seawater Environments

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2014-12-13

    Work began this quarter on a new project involving a combined computational and biosynthetic approach to selective recognition of uranyl ion in aqueous solution. This project exploits the results of computational studies to discover new ligand classes. Synthetic studies will follow to generate target systems for uranyl binding and determination of binding constants. The process will be iterative, with results from computation informing synthesis, and vice versa. The theme of the ligand classes to be examined initially will be biologically based. New phosphonate-containing α-amino acid N-carboxyanhydride (NCA) monomers were used recently to prepare well-defined phosphonate-containing poly-peptides and block copolypeptides. Our first approach is to utilize these phosphate- and phosphonate-containing NCAs for the coordination of uranyl. The work includes the laboratory-scale preparation of a series of NCAs and the full thermodynamic and spectroscopic characterization of the resulting uranyl complexes. We are also evaluating the sequestering activity in different physiological and environmental conditions of these copolymers as well as their biodegradability.

  3. Synthesis, structural investigation and kinetic studies of uranyl(VI) unsymmetrical Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Asadi, M.; Zeinali, A.; Ranjkeshshorkaei, M.; Fejfarová, Karla; Eigner, Václav; Dušek, Michal; Dehnokhalaji, A.

    2014-01-01

    Roč. 126, č. 6 (2014), s. 1673-1683 ISSN 0974-3626 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl schiff base complexes * kinetic study * kinetics of thermal decomposition * X-ray crystallography * cyclic voltammetry Subject RIV: CA - Inorganic Chemistry Impact factor: 1.191, year: 2014

  4. Kinetics of thermal decomposition and kinetics of substitution reaction of nano uranyl Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Zeinali, A.; Dušek, Michal; Eigner, Václav

    2014-01-01

    Roč. 46, č. 12 (2014), s. 718-729 ISSN 0538-8066 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : uranyl * Schiff base * kinetics * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.517, year: 2014

  5. Uranyl Photocleavage of Phosphopeptides Yields Truncated C-Terminally Amidated Peptide Products

    DEFF Research Database (Denmark)

    Elnegaard, Rasmus L B; Møllegaard, Niels Erik; Zhang, Qiang

    2017-01-01

    photocleavage reaction of a tetraphosphorylated β-casein model peptide. We show that the primary photocleavage products of the uranyl-catalysed reaction are C-terminally amidated. This could be of great interest to the pharmaceutical industry, as efficient peptide amidation reactions are one of the top...

  6. Criticality parameters for uranyl nitrate or plutonium nitrate systems in tributyl phosphate/kerosine and water

    International Nuclear Information System (INIS)

    Weber, W.

    1985-01-01

    This report presents the calculated values of smallest critical masses and volumina and neutron physical parameters for uranyl nitrate (3, 4, 5% U-235) or plutonium nitrate (5% Pu-240), each in a 30 per cent solution of tributyl phosphate (TBP)/kerosine. For the corresponding nitrate-water solutions, newly calculated results are presented together with a revised solution density model. A comparison of the data shows to what extent the criticality of nitrate-TBP/kerosine systems can be assessed on the basis of nitrate-water parameters, revealing that such data can be applied to uranyl nitrate/water systems, taking into account that the smallest critical mass of uranyl nitrate-TBP/kerosine systems, up to a 5 p.c. U-235 enrichment, is by 4.5 p.c. at the most smaller than that of UNH-water solutions. Plutonium nitrate (5% Pu-240) in the TBP/kerosine solution will have a smallest critical mass of up to 7 p.c. smaller, as compared with the water data. The suitability of the computing methods and cross-sections used is verified by recalculating experiments carried out to determine the lowest critical enrichment of uranyl nitrate. The calculated results are well in agreement with experimental data. The lowest critical enrichment is calculated to be 2.10 p.c. in the isotope U-235. (orig.) [de

  7. Re-evaluating neptunium in uranyl phases derived from corroded spent fuel

    International Nuclear Information System (INIS)

    Fortner, J. A.; Finch, R. J.; Kropf, A. J.; Cunnane, J. C.; Chemical Engineering

    2004-01-01

    Interest in mechanisms that may control radioelement release from corroded commercial spent nuclear fuel (CSNF) has been heightened by the selection of the Yucca Mountain site in Nevada as the repository for high-level nuclear waste in the United States. Neptunium is an important radionuclide in repository models owing to its relatively long half-life and its high aqueous mobility as neptunyl [Np(V)O+2]. The possibility of neptunium sequestration into uranyl alteration phases produced by corroding CSNF would suggest-a process for lowering neptunium concentration and subsequent migration from a geologic repository. However, there remains little experimental evidence that uranyl compounds will, in fact, serve as long-term host phases for the retention of neptunium under conditions expected in a deep geologic repository. To directly explore this possibility, we examined specimens of uranyl alteration phases derived from humid-air-corroded CSNF by X-ray absorption spectroscopy to better determine neptunium uptake in these phases. Although neptunium fluorescence was readily observed from as-received CSNF, it was not observed from the uranyl alteration rind. We establish upper limits for neptunium incorporation into CSNF alteration phases that are significantly below previously reported concentrations obtained by using electron energy loss spectroscopy (EELS). We attribute the discrepancy to a plural-scattering event that creates a spurious EELS peak at the neptunium-MV energy

  8. Inhibition Mechanism of Uranyl Reduction Induced by Calcium-Carbonato Complexes

    Science.gov (United States)

    Jones, M. E.; Bargar, J.; Fendorf, S. E.

    2015-12-01

    Uranium mobility in the subsurface is controlled by the redox state and chemical speciation, generally as minimally soluble U(IV) or soluble U(VI) species. In the presence of even low carbonate concentrations the uranyl-carbonato complex quickly becomes the dominant aqueous species; they are, in fact, the primary aqueous species in most groundwaters. Calcium in groundwater leads to ternary calcium-uranyl-carbonato complexes that limit the rate and extent of U(VI) reduction. This decrease in reduction rate has been attributed to surface processes, thermodynamic limitations, and kinetic factors. Here we present a new mechanism for the inhibition of ferrous iron reduction of uranyl-carbonato species in the presence of calcium. A series of experiments under variable Ca conditions were preformed to determine the role of Ca in the inhibition of U reduction by ferrous iron. Calcium ions in the Ca2UO2(CO3)3 complex sterically prevent the interaction of Fe(II) with U(VI), in turn preventing the Fe(II)-U(VI) distance required for electron transfer. The mechanism described here helps to predict U redox transformations in suboxic environments and clarifies the role of Ca in the fate and mobility of U. Electrochemical measurements further show the decrease of the U(VI) to U(V) redox potential of the uranyl-carbonato complex with decreasing pH suggesting the first electron transfer is critical determining the rate and extent of uranium reduction.

  9. Observation of Radiolytic Field Alteration of the Uranyl Cation in Bicarbonate Solution

    Energy Technology Data Exchange (ETDEWEB)

    Snow, Lanee A.; McNamara, Bruce K.; Sinkov, Sergey I.; Cho, Herman M.; Friese, Judah I.

    2006-12-01

    In previous work we demonstrated that radiolysis of uranyl tris carbonate in near neutral pH to alkaline carbonate solutions, could be followed by 13C NMR. Radiolysis of the complex produced novel uranyl peroxo carbonate solution state species, whose structures depended on the pH and radiolytic dose rate. In this work, we investigate speciation of the uranyl carbonate trimer which is predominant in bicarbonate solution near pH 5.9. We observe radiolytically derived speciation to different mixed peroxy carbonate species than seen in the higher pH solutions. Auto radiolysis of uranium (VI) carbonate solutions between pH 5.9 and 7.2 is shown to alter the uranium speciation over relatively short periods of time and was followed by 13C NMR and visible spectrophotometry, using dissolved 233(UO2)3(CO3)6 6- both as the radiolysis source (D= 14.9 Gy/hr) and as a trap for the newly formed hydrogen peroxide. Direct addition of hydrogen peroxide to solutions of the uranyl-carbonate trimer is shown to reproduce the 13 C NMR signatures of the complexe(s) formed by radiolysis, but additionally a variety of new complexes are revealed. Ratios of H2O2/trimer < 1.5 produced a uranyl peroxo carbonate adduct, that is shown to be common to the radiolytically produced species. Ratios of H2O2/ trimer >1 resulted in formation of stable higher order peroxo carbonate complexes. The 13C NMR signatures and visible spectra of these complexes are described here. Rigorous characterization of the species is an ongoing effort.

  10. Corrosion evaluation of uranyl nitrate solution evaporator and denitrator in Tokai reprocessing plant

    International Nuclear Information System (INIS)

    Yamanaka, Atsushi; Hashimoto, Kowa; Uchida, Toyomi; Shirato, Yoji; Isozaki, Toshihiko; Nakamura, Yoshinobu

    2011-01-01

    The Tokai reprocessing plant (TRP) adopted the PUREX method in 1977 and has reprocessed spent nuclear fuel of 1140 tHM (tons of heavy metals) since then. The reprocessing equipment suffers from various corrosion phenomena because of high nitric acidity, solution ion concentrations, such as uranium, plutonium, and fission products, and temperature. Therefore, considering corrosion performance in such a severe environment, stainless steels, titanium steel, and so forth were employed as corrosion resistant materials. The severity of the corrosive environment depends on the nitric acid concentration and the temperature of the solution, and uranium in the solution reportedly does not significantly affect the corrosion of stainless steels and controls the corrosion rates of titanium steel. The TRP equipment that handles uranyl nitrate solution operates at a low nitric acid concentration and has not experienced corrosion problems until now. However, there is a report that corrosion rates of some stainless steels increase in proportion to rising uranium concentrations. The equipment that handles the uranyl nitrate solution in the TRP includes the evaporators, which concentrate uranyl nitrate to a maximum concentration of about 1000 gU/L (grams of uranium per liter), and the denitrator, where uranyl nitrate is converted to UO 3 powder at about 320degC. These equipments are therefore required to grasp the degree of the progress of corrosion to handle high-temperature and high-concentration uranyl nitrate. The evaluation of this equipment on the basis of thickness measurement confirmed only minor corrosion and indicated that the equipment would be fully adequate for future operation. (author)

  11. Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

    Science.gov (United States)

    Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.; Fendorf, Scott; Kumar, Naresh; Lowry, Gregory V.; Brown, Gordon E.

    2017-10-01

    As part of a larger study of the reactivity and mobility of uranyl (U(VI)O22+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0-835 ppm) or Suwanee River Fulvic Acid (SRFA) (0-955 ppm). No evidence was found for reduction of uranyl by either form of NOM after 24 h of exposure. The following three size fractions were considered in this study: (1) ≥0.2 μm (Fh-NOM aggregates), (2) 0.02-0.2 μm (dispersed Fh nanoparticles and NOM macro-molecules), and (3) <0.02 μm (dissolved). The extent to which U(VI) is sorbed in aggregates or dispersed as colloids was assessed by comparing U, Fe, and NOM concentrations in these three size fractions. Partitioning of uranyl between Fh and NOM was determined in size fraction (1) using X-ray absorption spectroscopy (XAS). Uranyl sorption on Fh-NOM aggregates was affected by the presence of NOM in different ways depending on pH and type of NOM (ESHA vs. SRFA). The presence of ESHA in the uranyl-Fh-NOM ternary system at pH 4.6 enhanced uranyl uptake more than the presence of SRFA. In contrast, neither form of NOM affected uranyl sorption at pH 7.0 over most of the NOM concentration range examined (0-500 ppm); at the highest NOM concentrations (500-955 ppm) uranyl uptake in the aggregates was slightly inhibited at pH 7.0, which is interpreted as being due to the dispersion of Fh aggregates. XAS at the U LIII-edge was used to characterize molecular-level changes in uranyl complexation as a result of sorption to the Fh-NOM aggregates. In the absence of NOM, uranyl formed dominantly inner-sphere, mononuclear, bidentate sorption complexes on Fh. However, when NOM concentration was increased at pH 4.6, the

  12. The gas-phase bis-uranyl nitrate complex ((UO2)2(NO3)5)-: infrared spectrum and structure

    International Nuclear Information System (INIS)

    Groenewold, G.S.; van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; McIlwain, Michael E.

    2011-01-01

    The infrared spectrum of the bis-uranyl nitrate complex ((UO 2 ) 2 (NO 3 ) 5 ) - was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate v 3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex ((UO 2 ) 2 (NO 3 ) 5 ) - compared to the mono-complex (UO 2 (NO 3 ) 3 ) - , as indicated by a higher O-U-O asymmetric stretching (v 3 ) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the v 3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The lowest energy structure predicted by density functional theory (B3LYP functional) calculations was one in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

  13. The gas-phase bis-uranyl nitrate complex ((UO2)2(NO3)5)-: infrared spectrum and structure

    International Nuclear Information System (INIS)

    Groenewold, Gary S.; van Stipdonk, Michael J.; Oomens, Jos; de Jong, Wibe; McIlwain, Michael E.

    2011-01-01

    The infrared spectrum of the bis-uranyl nitrate complex ((UO 2 ) 2 (NO 3 ) 5 ) - was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate nu3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex ((UO 2 ) 2 (NO 3 ) 5 ) - compared to the mono-complex (UO 2 (NO 3 ) 3 ) - , as indicated by a higher O-U-O asymmetric stretching (nu3) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the ν 3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The structure was calculated using density functional theory (B3LYP functional), which produced a structure in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

  14. Selenized milk casein in the diet of BALB/c nude mice reduces growth of intramammary MCF-7 tumors

    International Nuclear Information System (INIS)

    Warrington, Jenny M; Kim, Julie JM; Stahel, Priska; Cieslar, Scott RL; Moorehead, Roger A; Coomber, Brenda L; Corredig, Milena; Cant, John P

    2013-01-01

    Dietary selenium has the potential to reduce growth of mammary tumors. Increasing the Se content of cows’ milk proteins is a potentially effective means to increase Se intake in humans. We investigate the effects of selenized milk protein on human mammary tumor progression in immunodeficient BALB/c nude mice. Four isonitrogenous diets with selenium levels of 0.16, 0.51, 0.85 and 1.15 ppm were formulated by mixing low- and high-selenium milk casein isolates with a rodent premix. MCF-7 cells were inoculated into the mammary fat pad of female BALB/c nude mice implanted with slow-release 17 β-estradiol pellets. Mice with palpable tumors were randomly assigned to one of the four diets for 10 weeks, during which time weekly tumor caliper measurements were conducted. Individual growth curves were fit with the Gompertz equation. Apoptotic cells and Bcl-2, Bax, and Cyclin D1 protein levels in tumors were determined. There was a linear decrease in mean tumor volume at 70 days with increasing Se intake (P < 0.05), where final tumor volume decreased 35% between 0.16 and 1.15 ppm Se. There was a linear decrease in mean predicted tumor volume at 56, 63 and 70 days, and the number of tumors with a final volume above 500 mm 3 , with increasing Se intake (P < 0.05). This tumor volume effect was associated with a decrease in the proportion of tumors with a maximum growth rate above 0.03 day -1 . The predicted maximum volume of tumors (V max ) and the number of tumors with a large V max , were not affected by Se-casein. Final tumor mass, Bcl-2, Bax, and Cyclin D1 protein levels in tumors were not significantly affected by Se-casein. There was a significantly higher number of apoptotic cells in high-Se tumors as compared to low-Se tumors. Taken together, these results suggest that turnover of cells in the tumor, but not its nutrient supply, were affected by dairy Se. We have shown that 1.1 ppm dietary Se from selenized casein can effectively reduce tumor progression in an MCF-7

  15. Formation of the second organic phase during uranyl nitrate extraction from aqueous solution by 30% tributylphosphate solution in paraffin

    International Nuclear Information System (INIS)

    Yhrkin, V.G.

    1996-01-01

    For extraction systems aqueous solution of uranyl nitrate-30% solution of tributylphosphate in individual paraffins from C 13 to C 17 the influence of the second organic phase of uranyl nitrate concentration in aqueous and organic phases, the length of hydrocarbon chain of paraffin hydrocarbon and temperature from 25 to 50 deg C on formation conditions has been defected. A special method of achieving the conditions of organic phase stratification from three-phase region, involving definition of equilibrium phases composition by density and refractive index, has been elaborated for more precise definition of organic phase homogeneity region. It has been revealed that without addition of nitric acid to uranyl nitrate solution the organic phase homogeneity limits can be achieved solely on paraffins C 15 , C 16 and C 17 and only under conditions similar to equeous phase saturation in terms of uranyl nitrate. 16 refs., 2 figs

  16. A microscopic study of the action of uranyl acetate on the erythrocyte at varying molarity and toxicity

    International Nuclear Information System (INIS)

    Wyatt, J.H.

    1977-03-01

    Phase contrast and dark field microphotographs were made to record variation of the shape and size changes seen when human erythrocytes are exposed in a number of ways to uranyl acetate in vitro. The degree of hemolysis produced by varying the toxicity of the uranyl acetate solutions was measured, and the results are discussed with particular reference to the possible influence of pH. (author)

  17. Kinetic studies of uranyl ion adsorption on acrylonitrile (AN)/polyethylene glycol (PEG) interpenetrating networks (IPN)

    International Nuclear Information System (INIS)

    Aycik, G.A.; Gurellier, R.

    2004-01-01

    Full text: The kinetics of the adsorption of uranyl ions on amidoximated acrylonitrile (AN)/ polyethylene glycol (PEG) interpenetrating network (IPNs) from aqueous solutions was studied as a function of time and temperature. The IPNs were prepared by irradiation initiated gamma polymerisation using Co-60 gamma source. Adsorption capacities were performed for definite uranyl ion concentrations of 1x10 -2 M and at four different temperatures as 290K, 298K, 308K and 318K by gamma spectrometer. Adsorption time was increased from zero to 48 hours. The results indicate that adsorption capacity increases linearly with increasing temperature. Temperature and agitation hardly influence equilibrium and kinetics and decreasing of temperature results in a slightly greater time to reach equilibrium. The adsorption of uranyl ions has been studied in a multi step mechanism processes thus comparing chemical sorption and diffusion sorption processes. The experimental data was analysed using various kinetic models to determine the best-fit equation for the adsorption mechanisms. However, it was shown that all models, in general according to the reaction time and uranyl ion concentration in the solution, could describe the adsorption of uranyl ion onto amidoximated IPN, the adsorption kinetics was best described by zeroth order and intraparticle diffusion model whereas that of in increasing time by pseudo first and pseudo second order response respectively. External-intraparticle diffusion and zeroth order process in the IPN structure is proposed as a mass transfer mechanism and the results indicate a diffusion-controlled process. The Mean Activation Energy Of Uranyl Ions Adsorption Was Found As 4,1 Kj/Mole By Using Arrhenius Equation. The Rate Constant, The Equilibrium Adsorption Capacity And The Initial Adsorption Rate Were Calculated For All Models At Each Temperature. Kinetic Parameters Of All Models And The Normalized Standard Deviations Between The Measured And Predicted

  18. Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

    International Nuclear Information System (INIS)

    Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella

    2016-01-01

    Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U V species into the stable mixed-valent star-shaped U VI /U V oxo cluster [U(UO 2 ) 5 (μ 3 -O) 5 (PhCOO) 5 (Py) 7 ]. This cluster is only the second example of a U VI /U V cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U V center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U 12 IV U 4 V O 24 cluster {[K(Py) 2 ] 2 [K(Py)] 2 [U 16 O 24 (PhCOO) 24 (Py) 2 ]}.

  19. Reactive transport of uranyl: fixation mode on silica and goethite; experiments in columns and closed reactors; simulations

    International Nuclear Information System (INIS)

    Gabriel, U.

    1998-01-01

    Uranium contaminated areas are found in mine waste disposal sites, former military areas, etc. The present study focuses on the identification or mechanisms which may lead contaminated soils to become a sudden potential threat to surface and ground waters. Mechanisms were studied on model material at two levels. On the molecular scale, the complexation of uranyl at trace metal concentrations was investigated with amorphous silica. Complexation is shown to occur via the formation of surface complexes, characterised by different time-resolved laser-induced luminescence spectra and life times and stoichiometry. On the macro-scale the transport behaviour of uranyl in a cristobalite-goethite-carbonate-uranyl system was investigated with laboratory column and batch experiments. Uranium mobility was found to be controlled by the interaction between physical transport and a reversible, rate-controlled, fixation reaction. Sorption was shown to be an ensemble of competing solution and surface complexation reactions, leading to an apparent non-linear (Langmuir-like) adsorption isotherm. Finally the impact of a sudden change in background geochemistry was studied. Conditions leading to a dramatic mobilization of uranium from mildly contaminated systems were experimentally identified. Maximal uranyl concentration are controlled by the total extractable uranyl in the system and limited by uranyl solubility. Evolution of the background geochemical conditions is thus an important part of contaminated sites risk assessment. (author)

  20. Production of U3O8 by uranyl formate precipitation and calcination in a full-scale pilot facility

    International Nuclear Information System (INIS)

    Kendrick, L.S.; Wilson, W.A.; Mosley, W.C.

    1984-08-01

    The uranyl formate process for the production of U 3 O 8 with a controlled particle size has been extensively studied on a laboratory scale. Based on this study, a pilot-scale facility (the Uranyl Formate Facility) was built to investigate the key steps of the process on a larger scale. These steps were the precipitation of a uranyl formate monohydrate salt and the calcination of this salt to U 3 O 8 . Tests of the facility and process were conducted at conditions recommended by the laboratory-scale studies for a full-scale production facility. These tests demonstrated that U 3 O 8 of the required particle size for the PM process can be produced on a plant scale by the calcination of uranyl formate crystals. The performance of the U 3 O 8 produced by the uranyl formate process in fuel tube fabrication was also investigated. Small-scale extrusion tests of U 3 O 8 -Al cores which used the U 3 O 8 produced in the Uranyl Formate Facility were conducted. These tests demonstrated that the U 3 O 8 quality was satisfactory for the PM process

  1. Determination of the stability of the uranyl ion sipped in τ-hydrogen phosphate of zirconium in sodic form

    International Nuclear Information System (INIS)

    Ordonez R, E.; Fernandez V, S.M.; Drot, R.; Simoni, E.

    2005-01-01

    The stability of the uranyl sipped in the zirconium τ-hydrogen phosphate in sodic form (τ-NaZrP), was carried out characterizing the complexes formed by Laser spectroscopy in the visible region and by X-ray photoelectron spectroscopy. The material was prepared by a new synthesis technique working in nitrogen atmosphere and to low temperatures. The sorption of the uranyl ion was made in acid media with concentrations of 10 -4 and 10 -5 of uranyl nitrate and with ion forces of 0.1 and 0.5 M of NaClO 4 . The spectra of induced fluorescence with laser (TRLFS) show that the uranyl is fixed in very acid media in three well differentiated species, to pH less acid, the specie of long half life disappears and are only those of short half life. The results of the binding energy obtained by XPS indicate that the binding energy of the uranyl confer it a stable character to the complex formed in the τ-NaZP, that makes to this material appropriate to retain to the uranyl in solution to high ion forces and in acid media. (Author)

  2. Isolation of a star-shaped uranium(V/VI) cluster from the anaerobic photochemical reduction of uranyl(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Chatelain, Lucile; White, Sarah; Scopelliti, Rosario; Mazzanti, Marinella [Ecole Polytechnique Federale de Lausanne (EPFL) (Switzerland). Inst. de Sciences et Ingenierie Chimiques

    2016-11-07

    Actinide oxo clusters are an important class of compounds due to their impact on actinide migration in the environment. The photolytic reduction of uranyl(VI) has potential application in catalysis and spent nuclear fuel reprocessing, but the intermediate species involved in this reduction have not yet been elucidated. Here we show that the photolysis of partially hydrated uranyl(VI) in anaerobic conditions leads to the reduction of uranyl(VI), and to the incorporation of the resulting U{sup V} species into the stable mixed-valent star-shaped U{sup VI}/U{sup V} oxo cluster [U(UO{sub 2}){sub 5}(μ{sub 3}-O){sub 5}(PhCOO){sub 5}(Py){sub 7}]. This cluster is only the second example of a U{sup VI}/U{sup V} cluster and the first one associating uranyl groups to a non-uranyl(V) center. The U{sup V} center in 1 is stable, while the reaction of uranyl(V) iodide with potassium benzoate leads to immediate disproportionation and formation of the U{sub 12}{sup IV}U{sub 4}{sup V}O{sub 24} cluster {[K(Py)_2]_2[K(Py)]_2[U_1_6O_2_4(PhCOO)_2_4(Py)_2]}.

  3. [Pb2F2](SeO4): a heavier analogue of grandreefite, the first layered fluoride selenate

    Science.gov (United States)

    Charkin, Dmitri O.; Plokhikh, Igor V.; Zadoya, Anastasiya I.; Kazakov, Sergey M.; Zaloga, Alexander N.; Kozin, Michael S.; Depmeier, Wulf; Siidra, Oleg I.

    2018-01-01

    Co-precipitation of PbF2 and PbSeO4 in weakly acidic media results in the formation of [Pb2F2](SeO4), the selenate analogue of the naturally occurring mineral grandreefite, [Pb2F2](SO4). The new compound is monoclinic, C2/ c, a = 14.0784(2) Å, b = 4.6267(1) Å, c = 8.8628(1) Å, β = 108.98(1)°, V = 545.93(1) Å3. Its structure has been refined from powder data to R B = 1.55%. From thermal studies, it is established that the compound is stable in air up to about 300 °C, after which it gradually converts into a single phase with composition [Pb2O](SeO4), space group C2/ m, and lattice parameters a = 14.0332(1) Å, b = 5.7532(1) Å, c = 7.2113(1) Å, β = 115.07(1)°, V = 527.37(1) Å3. It is the selenate analogue of lanarkite, [Pb2O](SO4), and phoenicochroite, [Pb2O](CrO4), and its crystal structure was refined to R B = 1.21%. The formation of a single decomposition product upon heating in air suggests that this happens by a thermal hydrolysis mechanism, i.e., Pb2F2SeO4 + H2O (vapor) → Pb2OSeO4 + 2HF↑. This relatively low-temperature process involves complete rearrangement of the crystal structure—from a 2D architecture featuring slabs [Pb2F2]2+ formed by fluorine-centered tetrahedra into a structure characterized by 1D motifs based on [OPb2]2+ chains of oxocentered tetrahedra. The comparative crystal chemistry of the obtained anion-centered structural architectures is discussed.

  4. Uranyl complexes as scaffolding or spacers for cucurbit[6]uril molecules in homo- and heterometallic species, including a uranyl-lanthanide complex

    Energy Technology Data Exchange (ETDEWEB)

    Thuery, Pierre [NIMBE, CEA, CNRS, Universite Paris-Saclay, CEA Saclay, Gif-sur-Yvette (France)

    2017-06-16

    The reaction of uranyl nitrate with cucurbit[6]uril (CB6) and carboxylic or sulfonic ligands under hydrothermal conditions and in the presence of additional metal cations (K{sup I} or Ce{sup III}) or cosolvents provided four complexes, which were crystallographically characterized. The compound [(UO{sub 2}){sub 2}K{sub 2}(CB6)(adc){sub 2}(NO{sub 3}){sub 2}(H{sub 2}O){sub 2}].5H{sub 2}O (1), where H{sub 2}adc is 1,3-adamantanedicarboxylic acid, crystallizes in the form of a central K{sub 2}(CB6){sup 2+} column surrounded by two one-dimensional (1D) polymeric UO{sub 2}(adc)(NO{sub 3}){sup -} chains attached to the column by nitrate bridges, with a perfect match of the repeat lengths in the two subunits. The longer 1,3-adamantanediacetic acid (H{sub 2}adac) gives the complex [(UO{sub 2}){sub 2}(adac){sub 2}(HCOOH){sub 2}].CB6.6H{sub 2}O (2), in which the 1D uranyl-containing polymer and columns of CB6 molecules form a layered arrangement held by weak CH..O hydrogen bonds. The complex formed with the dipotassium salt of methanedisulfonic acid (K{sub 2}mds), [(UO{sub 2}){sub 2}K{sub 2}(CB6)(mds){sub 2}(OH){sub 2}(H{sub 2}O){sub 8}].4H{sub 2}O (3), is a 1D polymer, in which K{sub 2}(CB6){sup 2+} units are connected to one another by doubly hydroxide-bridged uranyl dimers in which the disulfonates are terminal, chelating ligands; connection between the two subunits is solely through potassium oxo-bonding to uranyl. The complex [(UO{sub 2}){sub 2}Ce{sub 2}(CB6)(C{sub 2}O{sub 4}){sub 3}(NO{sub 3}){sub 4}(H{sub 2}O){sub 6}].2H{sub 2}O (4) is a 1D polymer containing bridging oxalate ligands formed in situ, in which CB6 is coordinated to the lanthanide cations only; one nitrate ligand and one water ligand, hydrogen-bonded to each other, are included in the CB6 cavity, with the possible occurrence of interactions between nitrate oxygen atoms and ureido carbon atoms. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Water structure and aqueous uranyl(VI) adsorption equilibria onto external surfaces of beidellite, montmorillonite, and pyrophyllite: results from molecular simulations.

    Science.gov (United States)

    Greathouse, Jeffery A; Cygan, Randall T

    2006-06-15

    Molecular dynamics simulations were performed to provide a systematic study of aqueous uranyl adsorption onto the external surface of 2:1 dioctahedral clays. Our understanding of this key process is critical in predicting the fate of radioactive contaminants in natural groundwaters. These simulations provide atomistic detail to help explain experimental trends in uranyl adsorption onto natural media containing smectite clays. Aqueous uranyl concentrations ranged from 0.027 to 0.162 M. Sodium ions and carbonate ions (0.027-0.243 M) were also present in the aqueous regions to more faithfully model a stream of uranyl-containing groundwater contacting a mineral system comprised of Na-smectite. No adsorption occurred near the pyrophyllite surface, and there was little difference in uranyl adsorption onto the beidellite and montmorillonite, despite the difference in location of clay layer charge between the two. At low uranyl concentration, the pentaaquouranyl complex dominates in solution and readily adsorbs to the clay basal plane. At higher uranyl (and carbonate) concentrations, the mono(carbonato) complex forms in solution, and uranyl adsorption decreases. Sodium adsorption onto beidellite occurred both as inner- and outer-sphere surface complexes, again with little effect on uranyl adsorption. Uranyl surface complexes consisted primarily of the pentaaquo cation (85%) and to a lesser extent the mono(carbonato) species (15%). Speciation diagrams of the aqueous region indicate that the mono(carbonato)uranyl complex is abundant at high ionic strength. Oligomeric uranyl complexes are observed at high ionic strength, particularly near the pyrophyllite and montmorillonite surfaces. Atomic density profiles of water oxygen and hydrogen atoms are nearly identical near the beidellite and montmorillonite surfaces. Water structure therefore appears to be governed by the presence of adsorbed ions and not by the location of layer charge associated with the substrate. The water

  6. Biosensing for the Environment and Defence: Aqueous Uranyl Detection Using Bacterial Surface Layer Proteins

    Directory of Open Access Journals (Sweden)

    David J.R. Conroy

    2010-05-01

    Full Text Available The fabrication of novel uranyl (UO22+ binding protein based sensors is reported. The new biosensor responds to picomolar levels of aqueous uranyl ions within minutes using Lysinibacillus sphaericus JG-A12 S-layer protein tethered to gold electrodes. In comparison to traditional self assembled monolayer based biosensors the porous bioconjugated layer gave greater stability, longer electrode life span and a denser protein layer. Biosensors responded specifically to UO22+ ions and showed minor interference from Ni2+, Cs+, Cd2+ and Co2+. Chemical modification of JG-A12 protein phosphate and carboxyl groups prevented UO22+ binding, showing that both moieties are involved in the recognition to UO22+.

  7. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom)

    2012-12-07

    Switching on uranium(V) reactivity: The silylated uranium(V) dioxo complex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] (A) is inert to oxidation, but after two-electron reduction to [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-} (1), it can be desilylated to form [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} (2) with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U{sup VI/V} couple in dioxygen reduction. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Interaction of uranyl ions with snake venom proteins from Lachesis muta muta

    International Nuclear Information System (INIS)

    MacCordick, H.J.; Taghva, F.

    1997-01-01

    The reaction product of uranyl nitrate with whole-protein Bushmaster snake venom in nitrate buffer at pH 3.5 has been studied. The maximum uptake of uranium was 291 μmol U x g -1 of venom. The infrared spectrum of the product showed an asymmetric O-U-O vibration at 921 cm -1 typical of complex formation with the uranyl ion. Stability measurements with the UO 2 2+ -protein complex in neutral medium indicated moderate hydrolytic stability, with 14% dissociation after 16 hours at 0 deg C. Neutron irradiation and desorption studies with a 235 U-labelled complex showed that generated fission products such as lanthanides and barium were readily lixiviated at pH 7, whereas Ru and Zr were highly retained by the protein substrate. (author)

  9. Thermometric titration of a free acid and of uranyl in spent fuel element solutions

    International Nuclear Information System (INIS)

    Zamek, M.; Strafelda, F.

    1975-01-01

    A method was elaborated of determining nitric acid in the presence of uranyl nitrate in both aqueous and non-aqueous solutions using a pyridine aqueous solution as a titration agent, and of determining excess uranyl after a hydrogen peroxide addition by a further titration using the same agent. Even a hundred-fold excess of magnesium did not disturb the titration. The method is used in operating solution analyses in the extraction fuel reprocessing in the presence of a small amount of plutonium and of fission products. The reproducibility and accuracy of the method varied in the order of tens to units per cent depending on the concentration of components to be determined. The procedure is applicable for test volumes ranging between 0.1 and 10 ml in concentrations of 1 to 10 -3 M. (author)

  10. Synthesis and investigation of uranyl molybdate UO2MoO4

    International Nuclear Information System (INIS)

    Nagai, Takayuki; Sato, Nobuaki; Kitawaki, Shin-ichi; Uehara, Akihiro; Fujii, Toshiyuki; Yamana, Hajimu; Myochin, Munetaka

    2013-01-01

    In order to examine easily synthetic conditions of uranyl molybdate, UO 2 MoO 4 , used for the reprocessing process study of spent nuclear oxide fuels in alkaline molybdate melts, the uranium molybdate compounds were produced from U 3 O 8 powder and anhydrous MoO 3 reagent. The results of having investigated them in solid state by using X-ray diffractometry and Raman spectrometry, it was confirmed that UO 2 MoO 4 could be synthesized by heating mixed powder of U 3 O 8 and MoO 3 with stoichiometric mole ratio at 770 °C for 4 h under air atmosphere. Moreover, adding this UO 2 MoO 4 into Li 2 MoO 4 -Na 2 MoO 4 eutectic melt, most of the dissolved uranium species in the melt were observed as hexa–valent uranyl ions by absorption spectrophotometry

  11. Obtention of Uo3 by means of denitration of uranyl nitrate in a fluidized-bed

    International Nuclear Information System (INIS)

    Santos, W.R. dos; Costa, P.A.

    1990-01-01

    A fluidized-bed pilot unit for the production of UO 3 installed at IPEN-CNEN/SP is described. Its capacity is of 20 kg U/h in a continuous process. The main components of this pilot unit are: a system for the concentration of nuclearly pure uranyl nitrate (≅ 100 g U/L), a system for the denitration of the concentrated uranyl nitrate, an absorption system for NO 2 produced during the denitration reaction and, finally, a system for the dissolution of UO 3 that does not meet the specifications. The operational troubles found during the initial runs are presented. The results of the physical and chemical analysis of the UO 3 produced are discussed and a comparison is made for the UO 3 obtained by both fluidized-bed and wet processes. (author) [pt

  12. Determination of uranyl nitrate diffusion coefficients in organic and aqueous media using the porous diaphragm method

    International Nuclear Information System (INIS)

    Chierice, G.O.

    1974-01-01

    The diffusion coefficient is one of the parameters necessary for the obtention of the extraction exponential coefficients, that are contained within the H.T.U. (height of transfer unity) calculation expression, when operating with continuous organic phase. The organic phase used was tri-n-butyl-phosphate (TBP) and varsol in the 35% and 65% proportions respectively. After each experiment, the uranium content present in each compartment was spectrophotometrically determined and the quantities contained in the aqueous phases were determined by means of volumetric titration. It was found out that the uranyl ion diffusion coefficient is two and one half times less in organic phase, this just being attributed to the greater interactions of the uranyl ions in organic than in aqueous medium

  13. PVC membrane based potentiometric sensor for uranyl ion using thenoyl trifluoro acetone as ionophore

    International Nuclear Information System (INIS)

    Nanda, D.; Chouhan, H.P.S.; Maiti, B.

    2004-01-01

    Uranyl ion selective electrode based on thenoyl trifluoro acetone (TTA) incorporated into a polyvinyl chloride (PVC) membrane has been developed where dibutyl phthalate and sodium tetraphenyl borate have been used as plasticizer and anion excluder respectively. The PVC membrane containing the active ionophore, TTA, and the other ingredients has been directly cast a graphite electrode. The electrode shows near Nernstian response to UO 2 2+ in the concentration range of 10 -1 to 10 -6 mol. L -1 an average slope of 30 mV/decade. Alkali and alkaline earth ions do not interfere with the determination of uranyl ion. Interference of transition metal ions and Th (IV) is eliminated using EDTA. (author)

  14. Interfacial tension in systems involving TBP in dodecane, nitric acid, uranyl nitrate and water

    International Nuclear Information System (INIS)

    Kolarik, Z.; Pipkin, N.

    1982-08-01

    The interfacial tension was measured at 25 0 C in the systems TBP - n-dodecane/nitric acid - water and TBP - n-dodecane/nitric acid - uranyl nitrate - water. Empirical equations describing the interfacial tension as a function of the concentration of TBP in the starting organic phase and of uranium-(VI) and nitric acid in the equilibrium aqueous phase were suggested. In the absence of uranium (VI), the interfacial tension can also be correlated with the concentration of water in the equilibrium organic phase. Free TBP, hydrated or nonhydrated, and hydrated TBP solvates of nitric acid are interfacially active. Anhydrous TBP solvates of nitric acid and the TBP solvate of uranyl nitrate, which neither is hydrated, do not exhibit any visible interfacial activity. (orig.) [de

  15. Crystallization characteristics of ammonium uranyl carbonate (AUC) in ammonium carbonate solutions

    International Nuclear Information System (INIS)

    Kim, T.J.; Jeong, K.C.; Park, J.H.; Chang, I.S.; Choi, C.S.

    1994-01-01

    Ammonium carbonate solutions with an excessive amount of NH 3 were produced in a commercial AUC (ammonium uranyl carbonate) conversion plant. In this study the AUC crystals, precipitated with uranyl nitrate and ammonium carbonate solutions prepared in the laboratory, were characterized to determine the feasibility of recycling ammonium carbonate solution. The AUC crystals were easily agglomerated with the increasing concentration of CO 3 2- and mole ratio of NH 4 + /CO 3 2- in ammonium carbonate solution. Effects of a mixing system for the solution in the AUC crystallizer and the feed location of the solution onthe agglomeration of AUC crystals were also studied along with the effects of agglomerated AUC powders on UO 2 powders. Finally, the feasibility of manufacturing UO 2 fuel with a sintered pellet density of 10.52 g/cm 3 , using the AUC powders generated in this experiment, was demonstrated. (orig.)

  16. Formation of CuInSe{sub 2} films from metal sulfide and selenide precursor nanocrystals by gas-phase selenization, an in-situ XRD study

    Energy Technology Data Exchange (ETDEWEB)

    Capon, B., E-mail: boris.capon@ugent.be [Department of Solid State Sciences, Ghent University, Krijgslaan 281-S1, B-9000 Ghent (Belgium); Dierick, R. [Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, B-9000 Ghent (Belgium); Hens, Z. [Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, B-9000 Ghent (Belgium); Center for Nano and Biophotonics, Ghent University, Ghent (Belgium); Detavernier, C. [Department of Solid State Sciences, Ghent University, Krijgslaan 281-S1, B-9000 Ghent (Belgium)

    2016-08-01

    In this work phase pure CuInSe{sub 2} thin flms were obtained by selenization of ternary CuInSe{sub 2} and CuInS{sub 2} nanocrystals and mixtures of binary nanocrystals such as CuS, In{sub 2}S{sub 3}, Cu{sub 2}Se and In{sub 2}Se{sub 3}. The temperature of the selenium source was kept at 400 °C during selenization. Monitoring the process using in-situ x-ray diffraction, the effect of selenization on the phase formation and grain growth in the precursor film was investigated. Whereas CuInSe{sub 2} and CuInS{sub 2} nanocrystals exhibit little grain growth, we found that mixtures of binary nanocrystals can show significant sintering depending on the reaction conditions. For the mixture of CuS and In{sub 2}S{sub 3} nanocrystals, the crystallinity and the morphology of the obtained fims strongly depends on the Cu/In ratio, with a Cu excess strongly promoting grain growth. With mixtures of Cu{sub 2}Se and In{sub 2}Se{sub 3} nanocrystals the selenium partial pressure plays a crucial role. Selenium evaporation from the mixed compounds results in CuInSe{sub 2} films composed of relatively small crystallites. Higher selenium partial pressures however resulted in improved sintering. Incomplete propagation of the selenization reaction through the layer was observed though, only leading to a well sintered CuInSe{sub 2} top layer above a fine grained bottom layer. - Highlights: • Different types of colloidal nanocrystals were used as precursors to obtain CuInSe{sub 2} films by gas-phase selenization. • In-situ XRD was used to study the effect of selenization on the phase formation and grain growth in the precursor films. • For a mixture of binary metal sulfides the crystallinity and the morphology strongly depend on the Cu/In ratio. • Higher selenium partial pressures result in improved sintering for a mixture of binary metal selenides.

  17. Novel two-dimensional uranyl-organic assemblages in the citrate and D(-)-citramalate families

    International Nuclear Information System (INIS)

    Thuery, P.

    2008-01-01

    Uranyl nitrate reacts with D(-)-citramalic acid (H(3)citml) under mild hydrothermal conditions to give the two-dimensional polymer [UO 2 (Hcitml)] 1, in which each ligand chelates one metal atom through its hydroxyl and alpha- carboxylate groups and binds to three others in monodentate fashion. The resulting neutral layers display isolated uranyl pentagonal bipyramidal polyhedra. Whereas citric acid (H(4)cit) has been shown previously to give various three- and mono-dimensional uranyl organic assemblages, complexation under hydrothermal conditions in the presence of either NaOH/NEt 4 Cl or pyridine yields the complexes [NEt 4 ] 2 [(UO 2 ) 3 (cit) 2 (H 2 O) 2 ]· 2H 2 O 2 and [Hpy] 2 )[(UO 2 ) 3 (cit)(Hcit)(OH)] 3, respectively, which both crystallize as two- dimensional frameworks. The layers are either planar and separated by the counter ions in 2 or corrugated and hydrogen bonded to one another in 3. In both 2 and 3, [UO 2 (cit)] 2 4- dimeric subunits with edge-sharing pentagonal bipyramidal uranium coordination polyhedra are present but, in both cases and in contrast with previous structures containing [UO 2 (Hcit)] 2 2- dimers, the carboxylate group not involved in the dimer formation is coordinated to another uranyl unit, which is part of either a centrosymmetric hexagonal bipyramidal bis-aquated group or a different, [(UO 2 ) 2 (Hcit)(OH)] dimer. These examples of two- dimensional assemblages further illustrate the variety of architectures which can be obtained with citric and related acids and the important structure-directing effects of the counter ions. (author)

  18. Removal of toxic uranium from synthetic nuclear power reactor effluents using uranyl ion imprinted polymer particles.

    Science.gov (United States)

    Preetha, Chandrika Ravindran; Gladis, Joseph Mary; Rao, Talasila Prasada; Venkateswaran, Gopala

    2006-05-01

    Major quantities of uranium find use as nuclear fuel in nuclear power reactors. In view of the extreme toxicity of uranium and consequent stringent limits fixed by WHO and various national governments, it is essential to remove uranium from nuclear power reactor effluents before discharge into environment. Ion imprinted polymer (IIP) materials have traditionally been used for the recovery of uranium from dilute aqueous solutions prior to detection or from seawater. We now describe the use of IIP materials for selective removal of uranium from a typical synthetic nuclear power reactor effluent. The IIP materials were prepared for uranyl ion (imprint ion) by forming binary salicylaldoxime (SALO) or 4-vinylpyridine (VP) or ternary SALO-VP complexes in 2-methoxyethanol (porogen) and copolymerizing in the presence of styrene (monomer), divinylbenzene (cross-linking monomer), and 2,2'-azobisisobutyronitrile (initiator). The resulting materials were then ground and sieved to obtain unleached polymer particles. Leached IIP particles were obtained by leaching the imprint ions with 6.0 M HCl. Control polymer particles were also prepared analogously without the imprint ion. The IIP particles obtained with ternary complex alone gave quantitative removal of uranyl ion in the pH range 3.5-5.0 with as low as 0.08 g. The retention capacity of uranyl IIP particles was found to be 98.50 mg/g of polymer. The present study successfully demonstrates the feasibility of removing uranyl ions selectively in the range 5 microg - 300 mg present in 500 mL of synthetic nuclear power reactor effluent containing a host of other inorganic species.

  19. Stability and kinetics of uranyl ion complexation by macrocycles in propylene carbonate

    International Nuclear Information System (INIS)

    Fux, P.

    1984-06-01

    A thermodynamic study of uranyl ion complexes formation with different macrocyclic ligands was realized in propylene carbonate as solvent using spectrophotometric and potentiometric techniques. Formation kinetics of two UO 2 complexes: a crown ether (18C6) and a coronand (22) was studied by spectrophotometry in propylene carbonate with addition of tetraethylammonium chlorate 0.1M at 25 0 C. Possible structures of complexes in solution are discussed [fr

  20. Fabrication of ceramic grade UO2 by direct conversion of uranyl nitrate hexahydrate

    International Nuclear Information System (INIS)

    Lainetti, P.E.O.; Riella, H.G.

    1992-01-01

    A method of direct conversion of uranyl nitrate hexahydrate (UNH) solution to ceramic grade uranium dioxide powders by thermal denitration in a furnace that combines atomization nozzle and a gas stirred bed is described. The main purpose of this work is to show that this alternative process is technically viable, specially if the recovery of the scrap generated in the nuclear fuel pellet production is required, without further generation of new liquid wastes. (author)

  1. Crystal structure of the (REE)–uranyl carbonate mineral shabaite-(Nd)

    Czech Academy of Sciences Publication Activity Database

    Plášil, Jakub; Škoda, R.

    2017-01-01

    Roč. 62, č. 2 (2017), s. 97-105 ISSN 1802-6222 R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : shabaite-(Nd) * uranyl carbonate * rare-earth elements * crystal structure * mineral evolution Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Geology Impact factor: 0.609, year: 2016

  2. Rapid determination of fluoride in uranyl nitrate solution obtained in conversion process of uranium tetrafluoride

    International Nuclear Information System (INIS)

    Levin, R.; Feldman, R.; Sahar, E.

    1976-01-01

    In uranium production the conversion of impure uranium tetrafluoride by sodium hydroxide was chosen as a current process. A rapid method for determination of fluoride in uranyl-nitrate solution was developed. The method includes precipitation of uranium as diuranate, separation by centrifugation, and subsequent determination of fluoride in supernate by titration with thorium nitrate. Fluoride can be measured over the range 0.15-2.5 gr/gr U, with accuracy of +-5%, within 15 minutes. (author)

  3. Thermodynamic properties of actinide complexes. IV. Thorium(IV)- and uranyl(VI)-malonate systems

    Energy Technology Data Exchange (ETDEWEB)

    Di Bernardo, P; Di Napoli, V; Cassol, A; Magon, L [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi

    1977-01-01

    The stability constants and the enthalpies of formation of thorium(IV)- and uranyl(VI)-malonate complexes have been determined by potentiometric and calorimetric titrations in 1.00 M solutions of Na(ClO/sub 4/) at 25/sup 0/C. All complexes formed are found to be stabilized by a large entropy gain. The values for the stability constants agree with an ionic bonding model. The malonate behaves as a bidentate ligand forming only chelate complexes.

  4. Uranyl ion complexation by the tripodal ligand nitrilo-tri-acetate

    Energy Technology Data Exchange (ETDEWEB)

    Thuery, P. [CEA Saclay, DSM/DRECAM/SCM, F-91191 Gif Sur Yvette, (France)

    2007-07-01

    Reaction of uranyl nitrate with N-(2-acetamido)iminodiacetic acid (ADA) under hydrothermal conditions resulted in the hydrolysis of the amide group and the isolation of the complex [(UO{sub 2})(HNTA)(H{sub 2}O){sub 2}], in which each nitrilo-tri-acetate ligand, protonated at the N site, bridges three metal atoms to give rise to infinite ladder-like ribbons built from 2:2 metallacycles. (author)

  5. Selectivity in Ligand Binding to Uranyl Compounds: A Synthetic, Structural, Thermodynamic and Computational Study

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Univ. of California, Berkeley, CA (United States)

    2017-12-06

    The uranyl cation (UO22+) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. We believe that the goal of developing a practical system for uranium separation from seawater will not be attained without new insights into our existing fundamental knowledge of actinide chemistry. We posit that detailed studies of the kinetic and thermodynamic factors that influence interactions between f-elements and ligands with a range of donor atoms is essential to any major advance in this important area. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. We anticipate that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials.

  6. Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

    Science.gov (United States)

    Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

    2017-11-02

    Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A bibliographical review on the radiolysis of uranyl nitrate solutions in nitric acid medium

    International Nuclear Information System (INIS)

    Siri, Sandra; Mondino, Angel V.

    2004-01-01

    A bibliographical study on the effects of ionizing radiation on uranyl nitrate solutions in nitric acid medium was performed, and the state of knowledge on this subject is presented. The main experimental and theoretical results on water, nitric acid and uranium solutions radiolysis are reviewed and critically evaluated. This paper provides a collection of references as an aid to the development of practical applications, and to stimulate new research on fundamental processes in these systems. (author) [es

  8. Crystal structure of the (REE)-uranyl carbonate mineral kamotoite-(Y)

    Czech Academy of Sciences Publication Activity Database

    Plášil, Jakub; Petříček, Václav

    2017-01-01

    Roč. 81, č. 3 (2017), s. 653-660 ISSN 0026-461X R&D Projects: GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : kamotoite-(Y) * uranyl carbonate * rare-earth elements * crystal structure Subject RIV: DB - Geology ; Mineralogy OBOR OECD: Geology Impact factor: 1.285, year: 2016

  9. Synthesis, X-ray crystallography, spectroscopy, electrochemistry, thermal and kinetic study of uranyl Schiff base complexes

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Golzard, F.; Eigner, Václav; Dušek, Michal

    2013-01-01

    Roč. 66, č. 20 (2013), s. 3629-3646 ISSN 0095-8972 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : X-ray crystallography * uranyl Schiff base complex * kinetics of thermal decomposition * cyclic voltammetry * kinetics and mechanism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.224, year: 2013

  10. Renal hemodynamics in uranyl acetate-induced acute renal failure of rabbits

    International Nuclear Information System (INIS)

    Sudo, M.; Honda, N.; Hishida, A.; Nagase, M.

    1977-01-01

    The role of renal hemodynamic alterations in the curtailment of renal function was studied in rabbits with uranyl acetate-induced acute renal failure. The day following the i.v. injection of uranyl acetate (2 mg/kg of body wt), renal blood flow (RBF) and clearance of creatinine (Ccr) decreased to approximately 60 and 20% of controls, respectively. Intracortical fractional flow distribution, estimated by radioactive microsphere method, did not change. The extraction ratio of para-aminohippurate (EPAH) decreased and the renal extraction of sodium (CNa/Ccr) increased, with minimal structural change in the kidney. Urine output increased two to three times that of the control. After three days oliguria appeared despite complete recovery of RBF. The zonal flow redistributed toward the deep cortex. CCr and EPAH reached their minimums, concomitantly with tubular necrosis and intratubular casts. After seven days animals could be divided into the oliguric and diuretic groups. CCr and EPAH were higher in the diuretic group, while there was no significant difference in RBF and the flow distribution between groups. Regeneration of damaged tubular cells was found in the diuretic group but not in the oliguric group. The findings suggest the minor roles of RBF and the intracortical flow distribution, and a fundamental role of back leakage of filtrate across damaged tubular epithelium in the maintenance of reduced CCR and urine output during the oliguric stage in rabbits with uranyl acetate-induced renal failure

  11. A relativistic density functional study of uranyl hydrolysis and complexation by carboxylic acids in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Ray, Rupashree Shyama

    2009-02-10

    In this work, the complexation of uranium in its most stable oxidation state VI in aqueous solution was studied computationally, within the framework of density functional (DF) theory. The thesis is divided into the following parts: Chapter 2 briefly summarizes the relevant general aspects of actinide chemistry and then focuses on actinide environmental chemistry. Experimental results on hydrolysis, actinide complexation by carboxylic acids, and humic substances are presented to establish a background for the subsequent discussion. Chapter 3 describes the computational method used in this work and the relevant features of the parallel quantum chemistry code PARAGAUSS employed. First, the most relevant basics of the applied density functional approach are presented focusing on relativistic effects. Then, the treatment of solvent effects, essential for an adequate modeling of actinide species in aqueous solution, will be introduced. At the end of this chapter, computational parameters and procedures will be summarized. Chapter 4 presents the computational results including a comparison to available experimental data. In the beginning, the mononuclear hydrolysis product of UO{sub 2}{sup 2+}, [UO{sub 2}OH]{sup +}, will be discussed. The second part deals with actinide complexation by carboxylate ligands. First of all the coordination number for uranylacetate will be discussed with respect to implications for the complexation of actinides by humic substances followed by the uranyl complexation of aromatic carboxylic acids in comparison to earlier results for aliphatic ones. In the end, the ternary uranyl-hydroxo-acetate are discussed, as models of uranyl humate complexation at ambient condition.

  12. Calorimetric measurement of the enthalpy of extraction of uranyl nitrate by tri-n-amyl phosphate

    International Nuclear Information System (INIS)

    Srinivasan, T.G.; Vasudeva Rao, P.R.; Venugopal, V.; Sood, D.D.

    2002-01-01

    Enthalpy of extraction of uranyl nitrate by tri n-amyl phosphate (TAP) and its solutions in n-dodecane has been directly measured by solution calorimetry for the first time. Measurements have been made at 303±1 K, in both forward as well as the reverse extraction modes. The enthalpies of the accompanying reactions such as the dilution of the uranyl nitrate in the aqueous phase, the hydration of TAP, the mixing of TAP and n-dodecane, the mixing of the metal-solvate (UO 2 (NO 3 ) 2 ·2TAP) and n-dodecane and mixing of the metal-solvate and TAP have also been independently measured and used to derive both the equilibrium state enthalpies and the standard state enthalpies for the extraction. Two distinct standard states have been used for the organic phase, viz., 1) all solutes infinitely diluted in diluent (ΔH*) and 2) all solutes infinitely diluted in the water saturated extractant (ΔH 0 ). The results have been compared with the enthalpies of extraction measured by employing the temperature dependence of the distribution ratio as well as calorimetry reported in the literature for extraction of uranyl nitrate by TAP and TBP. (author)

  13. Enhancement of uranyl fluorescence using trimesic acid: Ligand sensitization and co-fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Maji, S. [Chemistry Group, Materials Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Viswanathan, K.S., E-mail: vish@igcar.gov.in [Chemistry Group, Materials Chemistry Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)

    2011-09-15

    Trimesic acid (TMA) was shown to sensitize and enhance uranyl fluorescence in aqueous medium, with the enhancement being a maximum at pH 5.0. Fluorescence spectra and lifetime data together suggest that TMA complexes with uranyl (UO{sub 2}{sup 2+}). The fluorescence of UO{sub 2}{sup 2+} in its acid complex is further enhanced by more than two orders of magnitude following the addition of Y{sup 3+}; a process referred to as co-fluorescence, leading to the possibility of detecting uranium at sub ng/mL level. The present study demonstrates, for the first time, fluorescence enhancement of the uranyl species due to co-fluorescence. - Highlights: > Trimesic acid was shown to sensitize and enhance the fluorescence of uranium in aqueous medium. > This ligand also exhibited co-fluorescence of uranium with Y{sup 3+}. > To the best of our knowledge this is the first report of co-fluorescence in uranium. > The enhancement of uranium fluorescence, resulted in detection limits in the ng/mL regime.

  14. A relativistic density functional study of uranyl hydrolysis and complexation by carboxylic acids in aqueous solution

    International Nuclear Information System (INIS)

    Ray, Rupashree Shyama

    2009-01-01

    In this work, the complexation of uranium in its most stable oxidation state VI in aqueous solution was studied computationally, within the framework of density functional (DF) theory. The thesis is divided into the following parts: Chapter 2 briefly summarizes the relevant general aspects of actinide chemistry and then focuses on actinide environmental chemistry. Experimental results on hydrolysis, actinide complexation by carboxylic acids, and humic substances are presented to establish a background for the subsequent discussion. Chapter 3 describes the computational method used in this work and the relevant features of the parallel quantum chemistry code PARAGAUSS employed. First, the most relevant basics of the applied density functional approach are presented focusing on relativistic effects. Then, the treatment of solvent effects, essential for an adequate modeling of actinide species in aqueous solution, will be introduced. At the end of this chapter, computational parameters and procedures will be summarized. Chapter 4 presents the computational results including a comparison to available experimental data. In the beginning, the mononuclear hydrolysis product of UO_2"2"+, [UO_2OH]"+, will be discussed. The second part deals with actinide complexation by carboxylate ligands. First of all the coordination number for uranylacetate will be discussed with respect to implications for the complexation of actinides by humic substances followed by the uranyl complexation of aromatic carboxylic acids in comparison to earlier results for aliphatic ones. In the end, the ternary uranyl-hydroxo-acetate are discussed, as models of uranyl humate complexation at ambient condition.

  15. Mechanistic study of the interaction of uranyl ions with zirconium oxide and zirconium silicate

    International Nuclear Information System (INIS)

    Lomenech, C.

    2002-04-01

    This work deals with structural and thermodynamic studies of the sorption of uranyl species on zircon and zirconia. After determination of the specific areas, of the pH of the isoelectric points, and of the sorption site numbers, thermodynamic data were obtained using alpha spectrometry, for different uranyl concentrations, different background electrolytes (NaClO 4 or KNO 3 ) and different ionic strengths. The structural identification of the surface complexes and sorption sites was carried out using several spectroscopies: XPS spectroscopy allowed a determination of the nature of the sorption sites (≡Zr-O- on zirconia and ≡Si-O- on zircon). Whereas fluorescence decay measurements gave the number of surface species, the combined use of XPS spectroscopy and laser spectro-fluorimetry enabled us to correlate differences in bonding energies and emission wavelengths with differences in the nature of the background electrolyte or in the pH of sorption; DRIFT spectroscopy was a powerful tool for the determination of the presence of sorbed uranyl nitrate species. EXAFS results clearly showed a splitting of the equatorial oxygen atoms in two shells, corresponding to a polydentate, inner-sphere complex. EXAFS results also indicated strong similarities between dry samples and in situ experiments, which confirms the validity of all the spectroscopic measurements. Macroscopic thermodynamic data were then modeled using a surface complexation model (2 pK and constant capacitance models), the results of the structural study being used as constraints for the simulation code FITEQL. (author)

  16. Determination of parameters dissolution of yellow-cake. Production of uranyl nitrate - Gas precipitation of AUC

    International Nuclear Information System (INIS)

    Mellah, A.

    1987-07-01

    The different stages of the purification cycle of yellow-cakes have been studied thoroughly in order to obtain an ammonium uranyl carbonate (AUC) as an intermediate product of uranium dioxide (UO 2 ). The optimal parameters of yellow-cake dissolution, filtration, extraction by solvent, scrubbing and stripping were determined. An original program of thermodynamic calculation was developed for the determination of the free energies of yellow-cake dissolution reactions. Different numerical methods were used to determine the kinetic constant, the reaction order and correlation equations of uranyl nitrate density as a function of U and H + concentrations, before and after the extraction cycle. For the first time, Algerian filteraids were used for the filtration of uranyl nitrate solutions with satisfactory results. A laboratory designed installation enabled the precipitation of AUC by injection of ammonia and carbon dioxide gases. Interesting results have been obtained and further investigations should be carried out in order to optimize all the paremeters of the gas precipitation of AUC

  17. The thermal denigration in fluid-bed to make uranyl product

    International Nuclear Information System (INIS)

    Ma Zhenrong; Cui Yulin; Zhu Changbing; Fan Chuanyong; Liu Yanfeng

    2010-01-01

    Nuclear fuel reprocessing plant used the thermal denigration to high concentration of uranyl nitrate solution in fluid-bed to make uranyl product. First the uranyl nitrate solution were concentrated in evaporator, into 300 gU/L, 600 gU/L, 750 gU/L and 1000 gU/L.When the fluid-bed was in good fluidity state at 320 degree C, the solution was sprayed all over the surface of the fine crystal seeds through the dual-channel air-blast nozzles to make new crystal seed and to make them grow up. The denigration reaction occurred when the internal temperature of the fluid-bed was kept at about 300 degree C by the outside and inside heat apparatus. The product were transported crossing the valve and spiral transfer to pack. The tail gas was purified and discharged. Through the fluid-bed's running, the variation discipline of temperature and the pressure, the effect curve of the quality of product accumulated to pressure drop were determined. At the same time, the gentrification temperature, the distributed heat and the transfer mode were tested. (authors)

  18. Complexes of vanadyl and uranyl ions with the chelating groups of humic matter

    International Nuclear Information System (INIS)

    Goncalves, M.L.S.; Mota, A.M.

    1987-01-01

    The uranyl and vanadyl complexes formed with salicylic, phthalic and 3,4-dihydroxybenzoic acids have been studied by potentiometry in order to determine the stability constants of the Msub(m) Lsub(n) species formed in solution, and the constants for hydrolysis and polymeric complexes, at 25.0 0 , in 0.10, 0.40 and 0.70M sodium perchlorate. MINIQUAD was used in process the data to find the best models for the species in solution, and calculate the formation constants. The uranyl-salicylic acid sytem was also studied by spectrophotometry and the program SQUAD used to process the data obtained. The best models for these systems show that co-ordination of the uranyl ion by carboxylate groups is easier than for the vanadyl ion, whereas the vanadyl ion seems to form more stable complexes with phenolate groups. Both oxo-cations seem to tend to hydrolyse rather than form complexes when the L:M ratios are greater than unity. Although the change in the constants with ionic strength is small, the activity coefficients of the salicylate and phthalate species have been calculated at ionic strengths 0.40 and 0.70M, along with the interaction parameters with Na + , from the stability constants found for the species ML and H 2 L, according to the Bronsted-Guggenheim expression. (author)

  19. Water-Reflected 233U Uranyl Nitrate Solutions in Simple Geometry

    International Nuclear Information System (INIS)

    Elam, K.R.

    2001-01-01

    A number of critical experiments involving 233 U were performed in the Oak Ridge National Laboratory Building 9213 Critical Experiments Facility during the years 1952 and 1953. These experiments, reported in Reference 1, were directed toward determining bounding values for the minimum critical mass, minimum critical volume, and maximum safe pipe size of water-moderated solutions of 233 U. Additional information on the critical experiments was found in the experimental logbooks. Two experiments utilizing uranyl nitrate (UO 2 (NO 3 ) 2 ) solutions in simple geometry are evaluated in this report. Experiment 37 is in a 10.4-inch diameter sphere, and Experiment 39 is in a 10-inch diameter cylinder. The 233 U concentration ranges from 49 to 62 g 233 U/l. Both experiments were reflected by at least 6 inches of water in all directions. Paraffin-reflected uranyl nitrate experiments, also reported in Reference 1, are evaluated elsewhere. Experiments with smaller paraffin reflected 5-, 6-, and 7.5-inch diameter cylinders are evaluated in U233-SOL-THERM-004. Experiments with paraffin reflected 8-, 8.5-, 9-, 10-, and 12-inch diameter cylinders are evaluated in U233-SOL-THERM-002. Later experiments with highly-enriched 235 U uranyl fluoride solution in the same 10.4-inch diameter sphere are reported in HEU-SOL-THERM-010. Both experiments were judged acceptable for use as criticality-safety benchmark experiments

  20. Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

    International Nuclear Information System (INIS)

    Medvedkov, Ya. A.; Serezhkina, L. B.; Grigor’ev, M. S.; Serezhkin, V. N.

    2016-01-01

    Two new malonate-containing uranyl complexes with carbamide of the formulas [UO 2 (C 3 H 2 O 4 )(Urea) 2 ] (I) and [UO 2 (C 3 H 2 O 4 )(Urea) 3 ] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO 2 (C 2 O 4 )(Urea) 3 ] (III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO 2 (C 3 H 2 O 4 )(Urea) 2 ] ∞ belonging to the crystal-chemical group AT 11 M 2 1 (A = UO 2 2+ , T 11 = C 3 H 2 O 4 2- , M 1 = Urea) of uranyl complexes. Crystals II and III are composed of the molecular complexes [UO 2 (L)(Urea) 3 ], where L = C 3 H 2 O 4 2- or C 2 O 4 2- , belonging to the crystal-chemical group AB 01 M 3 1 (A = UO 2 2+ , B 01 = C 3 H 2 O 4 2- or C 2 O 4 2- , M 1 = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi–Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.

  1. Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF α mediators

    International Nuclear Information System (INIS)

    Orona, N.S.; Tasat, D.R.

    2012-01-01

    Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO 3 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO 3 . We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O 2 − ). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O 2 − may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O 2 − may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through all the range of doses tested.

  2. Preparation of Cu{sub 2}ZnSnSe{sub 4} solar cells by low-temperature co-evaporation and following selenization

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Chao, E-mail: chao.gao@kit.edu; Hetterich, Michael [Institute of Applied Physics, Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe (Germany); Schnabel, Thomas; Abzieher, Tobias; Ahlswede, Erik [Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg (ZSW), 70565 Stuttgart (Germany); Powalla, Michael [Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg (ZSW), 70565 Stuttgart (Germany); Light Technology Institute (LTI), Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe (Germany)

    2016-01-04

    Cu{sub 2}ZnSnSe{sub 4} (CZTSe) thin films are prepared by a two-step method which involves co-evaporation of Cu, Zn, Sn, and Se on molybdenum-coated soda-lime glass at low substrate temperature and a following selenization. Solar cells with efficiencies of up to 6.5% can be achieved. The influence of the selenium deposition rates during co-evaporation and the nitrogen pressure during selenization on the properties of the CZTSe films are investigated. It is found that these two parameters can significantly affect the morphology and crystallinity of the CZTSe films. The possible reasons for the experimental results are discussed.

  3. Series of mixed uranyl-lanthanide (Ce, Nd) organic coordination polymers with aromatic polycarboxylates linkers.

    Science.gov (United States)

    Mihalcea, Ionut; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

    2012-09-17

    Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.

  4. Hydrothermal synthesis of uranyl squarates and squarate-oxalates: hydrolysis trends and in situ oxalate formation.

    Science.gov (United States)

    Rowland, Clare E; Cahill, Christopher L

    2010-07-19

    We report the synthesis of two uranyl squarates and two mixed-ligand uranyl squarate-oxalates from aqueous solutions under hydrothermal conditions. These products exhibit a range of uranyl building units from squarates with monomers in (UO(2))(2)(C(4)O(4))(5).6NH(4).4H(2)O (1; a = 16.731(17) A, b = 7.280(8) A, c = 15.872(16) A, beta = 113.294(16) degrees , monoclinic, P2(1)/c) and chains in (UO(2))(2)(OH)(2)(H(2)O)(2)(C(4)O(4)) (2; a = 12.909(5) A, b = 8.400(3) A, c = 10.322(4) A, beta = 100.056(7) degrees , monoclinic, C2/c) to two squarate-oxalate polymorphs with dimers in (UO(2))(2)(OH)(C(4)O(4))(C(2)O(4)).NH(4).H(2)O (3; a = 9.0601(7) A, b = 15.7299(12) A, c = 10.5108(8) A, beta = 106.394(1) degrees , monoclinic, P2(1)/n; and 4; a = 8.4469(6) A, b = 7.7589(5) A, c = 10.5257(7) A, beta = 105.696(1) degrees , monoclinic, P2(1)/m). The dominance at low pH of monomeric species and the increasing occurrence of oligomeric species with increasing pH suggests that uranyl hydrolysis, mUO(2)(2+) + nH(2)O right harpoon over left harpoon [(UO(2))(m)(OH)(n)](2m-n) + nH(+), has a significant role in the identity of the inorganic building unit. Additional factors that influence product assembly include in situ hydrolysis of squaric acid to oxalic acid, dynamic metal to ligand concentration, and additional binding modes resulting from the introduction of oxalate anions. These points and the effects of uranyl hydrolysis with changing pH are discussed in the context of the compounds presented herein.

  5. Structural evolution of a uranyl peroxide nano-cage fullerene: U60, at elevated pressures

    Science.gov (United States)

    Turner, K. M.; Lin, Y.; Zhang, F.; McGrail, B.; Burns, P. C.; Mao, W. L.; Ewing, R. C.

    2015-12-01

    U60 is a uranyl peroxide nano-cage that adopts a highly symmetric fullerene topology; it is topologically identical to C60. Several studies on the aqueous-phase of U60 clusters, [UO2(O2)(OH)]6060-, have shown its persistence in complex solutions and over lengthy time scales. Peroxide enhances corrosion of nuclear fuel in a reactor accident-uranyl peroxides often form near contaminated sites. U60 (Fm-3) crystallizes with approximate formula: Li68K12(OH)20[UO2(O2)(OH)]60(H2O)310. Here, we have used the diamond anvil cell (DAC) to examine U60 to understand the stability of this cluster at high pressures. We used a symmetric DAC with 300 μm culet diamonds and two different pressure-transmitting media: a mixture of methanol+ethanol and silicone oil. Using a combination of in situ Raman spectroscopy and synchrotron XRD, and electrospray ionization mass spectroscopy (ESI-MS) ex situ, we have determined the pressure-induced evolution of U60. Crystalline U60 undergoes an irreversible phase transition to a tetragonal structure at 4.1 GPa, and irreversibly amorphizes at 13 GPa. The amorphous phase likely consists of clusters of U60. Above 15 GPa, the U60 cluster is irreversibly destroyed. ESI-MS shows that this phase consists of species that likely have between 10-20 uranium atoms. Raman spectroscopy complements the diffraction measurements. U60 shows two dominant vibrational modes: a symmetric stretch of the uranyl U-O triple bond (810 cm-1), and a symmetric stretch of the U-O2-U peroxide bond (820 cm-1). As pressure is increased, these modes shift to higher wavenumbers, and overlap at 4 GPa. At 15 GPa, their intensity decreases below detection. These experiments reveal several novel behaviors including a new phase of U60. Notably, the amorphization of U60 occurs before the collapse of its cluster topology. This is different from the behavior of solvated C60 at high pressure, which maintains a hcp structure up to 30 GPa, while the clusters disorder. These results suggest

  6. Crystal chemistry of uranyl carboxylate coordination networks obtained in the presence of organic amine molecules

    Energy Technology Data Exchange (ETDEWEB)

    Mihalcea, Ionut; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS) - UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

    2014-03-15

    Three uranyl isophthalates (1,3-bdc) and two uranyl pyromellitates (btec) of coordination-polymer type were hydrothermally synthesized (200 C for 24 h) in the presence of different amine-based molecules [1,3-diaminopropane (dap) or dimethylamine (dma) originating from the in situ decomposition of N,N-dimethylformamide]. (UO{sub 2}){sub 2}(OH){sub 2}(H{sub 2}O)(1,3-bdc).H{sub 2}O (1) is composed of inorganic tetranuclear cores, which are linked to each other through the isophthalato ligand to generate infinite neutral ribbons, which are intercalated by free H{sub 2}O molecules. The compounds (UO{sub 2}){sub 1.5}(H{sub 2}O)(1,3-bdc){sub 2}.0.5H{sub 2}dap.1.5H{sub 2}O (2) and UO{sub 2}(1,3-bdc){sub 1.5}.0.5H{sub 2}dap.2H{sub 2}O (3) consist of discrete uranyl-centered hexagonal bipyramids connected to each other by a ditopic linker to form a single-layer network for 2 or a double-layer network for 3. The protonated diamine molecules are located between the uranyl-organic sheets and balance the negative charge of the layered sub-networks. The phase (UO{sub 2}){sub 2}O(btec).2Hdma.H{sub 2}O (4) presents a 2D structure built up from tetranuclear units, which consist of two central sevenfold coordinated uranium centers and two peripheral eightfold coordinated uranium centers. The connection of the resulting tetramers through the pyromellitate molecules generates an anionic layerlike structure, in which the protonated dimethylammonium species are inserted. The compound UO{sub 2}(btec).2Hdma (5) is also a lamellar coordination polymer, which contains isolated eightfold coordinated uranium cations linked through pyromellitate molecules and intercalated by protonated dimethylammonium species. In both phases 4 and 5, the btec linker has non-bonded carboxyl oxygen atoms, which preferentially interact with the protonated amine molecules through a hydrogen-bond network. The different illustrations show the structural diversity of uranyl-organic coordination polymers with organic

  7. Selenium deficiency occurs in some patients with moderate-to-severe cirrhosis and can be corrected by administration of selenate but not selenomethionine: a randomized controlled trial123

    Science.gov (United States)

    Burk, Raymond F; Hill, Kristina E; Motley, Amy K; Byrne, Daniel W; Norsworthy, Brooke K

    2015-01-01

    Background: Selenomethionine, which is the principal dietary form of selenium, is metabolized by the liver to selenide, which is the form of the element required for the synthesis of selenoproteins. The liver synthesizes selenium-rich selenoprotein P (SEPP1) and secretes it into the plasma to supply extrahepatic tissues with selenium. Objectives: We conducted a randomized controlled trial to determine whether cirrhosis is associated with functional selenium deficiency (the lack of selenium for the process of selenoprotein synthesis even though selenium intake is not limited) and, if it is, whether the deficiency is associated with impairment of selenomethionine metabolism. Design: Patients with Child-Pugh (C-P) classes A, B, and C (mild, moderate, and severe, respectively) cirrhosis were supplemented with a placebo or supranutritional amounts of selenium as selenate (200 or 400 μg/d) or as selenomethionine (200 μg/d) for 4 wk. Plasma SEPP1 concentration and glutathione peroxidase (GPX) activity, the latter due largely to the selenoprotein GPX3 secreted by the kidneys, were measured before and after supplementation. Results: GPX activity was increased more by both doses of selenate than by the placebo in C-P class B patients. The activity was not increased more by selenomethionine supplementation than by the placebo in C-P class B patients. Plasma selenium was increased more by 400 μg Se as selenate than by the placebo in C-P class C patients. Within the groups who responded to selenate, there was a considerable variation in responses. Conclusion: These results indicate that severe cirrhosis causes mild functional selenium deficiency in some patients that is associated with impaired metabolism of selenomethionine. This trial was registered at clinicaltrials.gov as NCT00271245. PMID:26468123

  8. Community ecology of the metazoan parasites of Atlantic Moonfish, Selene setapinnis (Osteichthyes: Carangidae from the coastal zone of the state of Rio de Janeiro, Brazil

    Directory of Open Access Journals (Sweden)

    A. S. Cordeiro

    Full Text Available Eighty-nine specimens of Selene setapinnis (Mitchill, 1815 collected from the coastal zone of the State of Rio de Janeiro (21-23ºS, 41-45ºW and 23º05'S, 44º30'W, Brazil, from August 2001 to May 2002, were necropsied to study their metazoan parasites. Eighty-one (91% specimens of S. setapinnis were parasitized by one or more metazoan species. Twenty-one species of parasites were collected: 8 digeneans, 3 monogeneans, 2 cestodes, 5 nematodes, and 3 copepods. The endoparasites (digeneans, cestodes, and nematodes were 74.1% of total number of parasite specimens collected. The monogenean Pseudomazocraes selene (Hargis, 1957 was the most dominant species with the highest prevalence in the parasite community of S. setapinnis. The metazoan parasites of this host species showed the typical aggregated pattern of distribution. Only one parasite species (Acanthocolpoides pauloi Travassos, Freitas & Buhrnheim, 1955 showed positive correlation between the host total length and parasite abundance in S. setapinnis. Caligus robustus Bassett-Smith, 1898, P. selene, and Terranova sp. demonstrated positive correlation between the host total length and prevalence. Larvae of Terranova sp. showed influence of the host sex on its prevalence. A pair of ectoparasite species, P. selene-C. robustus, exhibited positive covariation between their abundances. Two pairs of endoparasite species, L. microstomum-P. merus and A. pauloi-P. merus showed significant covariation among their abundances; and the pair Terranova sp.-Raphidascaris sp. had positive co-ocorrence and covariation in the infracommunities of S. setapinnis. Like the parasite communities of the other carangid fishes from Rio de Janeiro, the parasite community of S. setapinnis is apparently only a slightly ordered species complex, characterized by dominance of endoparasite species.

  9. Electrochemical studies on the reduction of uranyl ions in nitric acid-hydrazine media at platinum electrode

    International Nuclear Information System (INIS)

    Mishra, Satyabrata; Sini, K.; Mallika, C.; Kamachi Mudali, U.; Jagadeeswara Rao, Ch.

    2015-01-01

    Production of uranous nitrate with good conversion efficiency is one of the major steps in the aqueous reprocessing of spent fuels of nuclear reactors, as U(IV) is used for the separation of Pu from U by the selective reduction of Pu(IV) into practically non-extractable Pu(III) in aqueous streams. Electro-reduction of uranyl ions has the advantage of not introducing corrosive chemicals into the process stream. High current efficiency with maximum conversion of U(VI) to U(IV) can be achieved in continuous as well as batch mode electro-reduction, if the process is voltage-controlled rather than current controlled. As potentiostatic studies reveal the mechanism of reduction of uranyl ions in potential controlled electrolysis, the reduction behavior of uranyl ions (UO 2 2+ ) in nitric acid and nitric acid-hydrazine media were investigated by Cyclic Voltammetric (CV) and Chronopotentiometric (CP) techniques using platinum working electrode at 298 K. Heterogeneous electron transfer rate constant (ks) for uranyl reduction was estimated at a very low concentration of nitric acid (0.05 M) using Klinger and Kochi equation. Values of the diffusion coefficients were determined as a function of acidity with and without hydrazine. Reduction of uranyl ions was found to be under kinetic as well as diffusion control when the concentration of nitric acid was 0.05 M and in the absence of hydrazine. However, as the acidity of the supporting electrolyte increased, the reduction was purely under kinetic control. (author)

  10. Uranyl sensor based on a N,N?-bis(salicylidene)-2-hydroxy-phenylmethanediamine and multiwall carbon nanotube electrode

    International Nuclear Information System (INIS)

    Sayed Mehdi Ghoreishi; Mohsen Behpour; Samaneh Mazaheri; Hossein Naeimi

    2012-01-01

    The electrochemical determination of uranyl was investigated by using carbon paste electrode modified with a Schiff base namely N,N'-bis(salicylidene)-2-hydroxy-phenylmethanediamine (SHPMD/CPE) and also in the presence of carbon nanotube (SHPMD/CNT/CPE). The both modified electrodes displayed an irreversible peak at E pa = 0.798 V versus Ag/AgCl. The electrocatalytic reduction of uranyl has been studied on SHPMD/CNT/CPE, using cyclic and differential pulse voltammetry, chronocoulometry and linear sweep techniques. Electrochemical parameters including the diffusion coefficient (D), the electron transfer coefficient (α), the ionic exchange current (i) and the redox reaction rate constant (K) were determined for the reduction of uranyl on the surface of the modified electrodes. Linear range concentration is 0.002-0.6 μmol L -1 and the detection limit of uranyl is 0.206 nmol L -1 . The proposed method was used to detect uranyl in natural waters and good recovery was achieved. (author)

  11. Texture control and growth mechanism of WSe{sub 2} film prepared by rapid selenization of W film

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hongchao [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Chongyi Zhangyuan Tungsten Industry Corporation Limited, Ganzhou 341300 (China); Gao, Di; Li, Kun; Pang, Mengde; Xie, Senlin [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Liu, Rutie, E-mail: llrrtt@csu.edu.cn [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China); Zou, Jianpeng [State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083 (China)

    2017-02-01

    Highlights: • We present a highly efficient method for preparing WSe{sub 2} film by rapid selenization. • The W film phase composition has little effect on WSe{sub 2} film orientation. • W film density is a critical factor that influences the WSe{sub 2} orientation. • A growth model was proposed for two kinds of WSe{sub 2} film textures. - Abstract: The tungsten diselenide (WSe{sub 2}) films with different orientation present unique properties suitable for specific applications, such as WSe{sub 2} with a C-axis⊥substrate for optoelectronics and WSe{sub 2} with a C-axis // substrate for electrocatalysts. Orientation control of WSe{sub 2} is essential for realizing the practical applications. In this letter, a WSe{sub 2} film has been prepared via rapid selenization of a magnetron-sputtered tungsten (W) film. The influence of the magnetron-sputtered W film on WSe{sub 2} film growth was studied systematically. Scanning electron microscopy, X-ray diffractometry and high-resolution transmission electron microscopy were used to evaluate the morphology, microstructure and phase composition of the W and WSe{sub 2} films. The substrate temperature has a significant effect on the W film phase composition, but little effect on the WSe{sub 2} film orientation. The WSe{sub 2} orientation can be controlled by changing the W film microstructure. A dense W film that is deposited at low pressure is conducive to the formation of WSe{sub 2} with a C-axis⊥substrate, whereas a porous W film deposited at high pressure favors the formation of WSe{sub 2} with a C-axis // substrate. A growth model for the WSe{sub 2} film with different texture has been proposed based on the experimental results. The direction of selenium (Se) vapor diffusion differs at the top and side surfaces. This is a key factor for the preparation of anisotropic WSe{sub 2} films. Highly oriented WSe{sub 2} films with a C-axis⊥substrate grow from the dense W film deposited at low pressure because Se vapor

  12. Thermal decomposition of uranyl nitrate hexahydrate. Study of intermediate reaction products; Decomposition thermique du nitrate d'uranyle hexahydrate etude des intermediaires de cette decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Chottard, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1970-07-01

    The thermal decomposition of uranyl nitrate hexahydrate has been carried but at constant pressure and constant rate of reaction. The following intermediary products have been shown to exist and isolated: UO{sub 2}(NO{sub 3}){sub 2}.3H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}. 2H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}. H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2} and UO{sub 3}. These products, together with the hexahydrate UO{sub 2} (NO{sub 3}){sub 2}.6H{sub 2}O, have been studied by: - X-ray diffraction, using the Debye-Scherrer method.- infra-red spectrography: determination of the type of bonding for the water and the nitrate groups. - nuclear magnetic resonance: study of the mobility of water molecules. The main results concern: - the water molecule bonds in the series of hydrates with 6.3 and 2 H{sub 2}O. - isolation and characterization of uranyl nitrate monohydrate, together with the determination of its molecular structure. - the mobility of the water molecules in the series of the hydrates with 6.3 and 2 H{sub 2}O. An analysis is made of the complementary results given by infra-red spectroscopy and nuclear magnetic resonance; they are interpreted for the whole of the hydrate series. [French] La decomposition thermique du nitrate d'uranyle hexahydrate a ete effectuee en operant a pression et vitesse de decomposition constantes. Les produits intermediaires suivants ont ete mis en evidence et isoles: UO{sub 2}(NO{sub 3}){sub 2}, 3H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2}, 2H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2},H{sub 2}O; UO{sub 2}(NO{sub 3}){sub 2} et UO{sub 3}. Ces composes, ainsi que l'hexahydrate UO{sub 2}(NO{sub 3} ){sub 2}, 6H{sub 2}O ont ete etudies par: - diffraction des rayons X, selon la methode Debye-Scherrer.- spectrographie infra-rouge: determination des modes de liaison de l'eau et des groupements nitrate. - resonance magnetique nucleaire: etude de la mobilite des molecules d'eau. Les principaux resultats portent sur: - les liaisons des molecules d'eau dans la

  13. The Effect of E-Selen Antioxidant on the Fatty Acids Content of the Homogenate of Unirradiated and Irradiated Pupae of Ceratitis Capitata

    International Nuclear Information System (INIS)

    Zaghloul, Y.S.; Abbassy, S.A.; Elakhdar, E.A.H.; Elakhdar, E.A.H.

    2011-01-01

    As antioxidant E-selen was added to the larval artificial diets of the Mediterranean fruit fly, Ceratitis capitata. The produced full grown pupae were exposed to gamma rays at dose rate of 90 Gy. The fatty acid contents of the normal and irradiated insects were analyzed to test to what extent, the uptake of the antioxidant will ameliorate the physiological damage induced to the medfly pupae, as a result of their exposure to irradiation. The results obtained by using Gas-liquid chromatography of fatty acid methyl esters, showed the palmitic and oleic acids to be the most predominant fatty acids in all pupal homogenates in both normal and irradiated pupae, either by the uptake of doses of the E-selen or without. The uptake of E-Selen with a dose of 0.3 mg led to a complete absence of the lauric and myristic acids in the homogenates of the unirradiated pupae of the medfly. This absence of lauric and myristic acids was accompanied by a decrease in the concentrations of the palmitic and linoleic acids reaching 25.17% and 32.98%, respectively as compared to pupae without the uptake of antioxidant. The concentrations of both the stearic and oleic acids showed an obvious increment reaching 199.22% and 58.94%, respectively, relative to those reared on the defined media and no added E.Selen. Exposure of the pupae to a dose of 90 Gy, resulted in an increment in the concentrations of the saturated lauric and myristic acid reaching 96.77% and 34.07%, respectively, relative to the untreated ones. While, at the same dose level, there were decrements in the concentrations of the palmitic, stearic, oleic and linoleic acids with percentages reaching 6.4, 9.22, 3.65 and 1.15%, respectively as compared to unirradiated controls. Irradiation of the pupae with sterilizing dose (90 Gy) after up taking the E-Selen in their larval diets, led to the increase of the concentrations of lauric, oleic and linoleic acids by ratios of 16.82, 8.84 and 29.26%, respectively as compared to their

  14. Derivation of an empirical formula for determining water content of mixed uranyl nitrate-thorium nitrate solutions

    International Nuclear Information System (INIS)

    Min, Duck Kee; Choi, Byung Il; Ro, Seung Gy; Eom, Tae Yoon; Kim, Zong Goo

    1986-01-01

    Densities of a large number of mixed uranyl nitrate-thorium nitrate solutions were measured with pycnometer. By the least squares analysis of the experimental result, an empirical formula for determining water content of mixed uranyl nitrate-thorium nitrate solutions as functions of uranium concentration, thorium concentration and nitric acid normality is derived; W=1.0-0.3580 C u -0.4538 C Th -0.0307H + where W, C u , C Th , and H + stand for water content(g/cc), uranium concentration (g/cc), thorium concentration(g/cc), and nitric acid normality, respectively. Water contents of the mixed uranyl nitrate-thorium nitrate solutions are calculated by using the empirical formular, and compared with the values calculated by Bouly's equation in which an additional data, solution density, is required. The two results show good agreements within 2.7%. (Author)

  15. Application of membrane LaF3 electrode in the determination of stability constants of Uranyl Fluoride complex in solution

    International Nuclear Information System (INIS)

    Muzakky; Iswani GS; Mintolo

    1996-01-01

    A membrane electrode LaF 3 has been applied in the determination of uranyl fluoride complex stability constant in solution. The determination is based on the detection of free F ion in solution as a result of hydrolysis reaction (process) of uranyl ions into the uranyl hydroxide form at low pH. The experiment results showed that there was no effect of ammonium carbonate 2 M titran, flow rate on the electrode response. The F release is optimum at pH 1. The free F ion in solution is calculated from the standard curve at pH 1, after the fluoride concentration at the same pH has been corrected. Using the plot of average number of ligand binding (n) versus minus log of free ligand (-log F) the value of β1 = 4.4, β2 = 7.48, β3=9.73, and β4 = 11.67

  16. Study of Pitch Attitude Estimation Using a High-Definition TV (HDTV) Camera on the Japanese Lunar Explorer SELENE (KAGUYA)

    Science.gov (United States)

    Sobue, Shinichi; Yamazaki, Junichi; Matsumoto, Shuichi; Konishi, Hisahiro; Maejima, Hironori; Sasaki, Susumu; Kato, Manabu; Mitsuhashi, Seiji; Tachino, Junichi

    The lunar explorer SELENE (also called KAGUYA) carried thirteen scientific mission instruments to reveal the origin and evolution of Moon and to investigate the possible future utilization of Moon. In addition to the scientific instruments, a high-definition TV (HDTV) camera provided by the Japan Broadcasting Corporation (NHK) was carried on KAGUYA to promote public outreach. We usually use housekeeping telemetry data to derive the satellite attitude along with orbital determination and propagated information. However, it takes time to derive this information, since orbital determination and propagation calculation require the use of the orbital model. When a malfunction of the KAGUYA reaction wheel occurred, we could not have correct attitude information. This means that we don’t have a correct orbital determination in timely fashion. However, when we checked HDTV movies, we found that horizon information on the lunar surface derived from HDTV moving images as a horizon sensor was very useful for the detection of the attitude of KAGUYA. We then compared this information with the attitude information derived from orbital telemetry to validate the accuracy of the HDTV derived estimation. As a result of this comparison, there are good pitch attitude estimation using HDTV derived estimation and we could estimate the pitch angle change during the KAGUYA mission operation simplify and quickly. In this study, we show the usefulness of this HDTV camera as a horizon sensor.

  17. Local Lunar Gravity Field Analysis over the South Pole-aitken Basin from SELENE Farside Tracking Data

    Science.gov (United States)

    Goossens, Sander Johannes; Ishihara, Yoshiaki; Matsumoto, Koji; Sasaki, Sho

    2012-01-01

    We present a method with which we determined the local lunar gravity field model over the South Pole-Aitken (SPA) basin on the farside of the Moon by estimating adjustments to a global lunar gravity field model using SELENE tracking data. Our adjustments are expressed in localized functions concentrated over the SPA region in a spherical cap with a radius of 45deg centered at (191.1 deg E, 53.2 deg S), and the resolution is equivalent to a 150th degree and order spherical harmonics expansion. The new solution over SPA was used in several applications of geophysical analysis. It shows an increased correlation with high-resolution lunar topography in the frequency band l = 40-70, and admittance values are slightly different and more leveled when compared to other, global gravity field models using the same data. The adjustments expressed in free-air anomalies and differences in Bouguer anomalies between the local solution and the a priori global solution correlate with topographic surface features. The Moho structure beneath the SPA basin is slightly modified in our solution, most notably at the southern rim of the Apollo basin and around the Zeeman crater

  18. Deposition of CuIn(Se,S)2 thin films by sulfurization of selenized Cu/In alloys

    International Nuclear Information System (INIS)

    Sheppard, C.J.; Alberts, V.; Bekker, W.J.

    2004-01-01

    The relatively small band gap values (close to 1eV) of CuInSe 2 thin films limits the conversion efficiencies of completed CuInSe 2 /CdS/ZnO solar cell devices. In the case of traditional two-stage growth techniques, limited success has been achieved to increase the band gap by substituting indium with gallium. In this study, sputtered copper-indium alloys were exposed to a H 2 Se/Ar atmosphere under defined conditions in order to produce partially reacted CuInSe 2 structures. These films were subsequently exposed to a H 2 S/Ar atmosphere to produce monophasic CuIn(Se, S) 2 quaternary alloys. The homogeneous incorporation of S into CuInSe 2 led to a systematic shift in the lattice parameters and band gap of the ab- sorber films. From these studies optimum selenization/sulfurization conditions were determined for the deposition of homogeneous CuIn(Se,S) 2 thin films with an optimum band gap values between 1.15 and 1.2 eV. (copyright 2004 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  19. Sneaking of the Solar Wind Ions Into the Lunar Anti-subsolar Region Revealed by SELENE (Kaguya)

    Science.gov (United States)

    Nishino, M. N.; Fujimoto, M.; Saito, Y.; Shoichiro, Y.; Asamura, K.; Tanaka, T.; Tsunakawa, H.; Shibuya, H.; Matsushima, M.; Shimizu, H.; Takahashi, F.; Maezawa, K.; Terasawa, T.

    2008-12-01

    The moon spends more than 80 percent of its life staying in the solar wind (SW), where a quasi-vacuum region called the lunar wake is formed on the night side. The SW electrons with higher energy can come to the lunar night-side surface, while it has been thought that the SW ions are unlikely to approach the low altitude region on the night side because their thermal speed is much lower than the SW bulk speed. Here we show detection of SW ions sneaking into the anti-subsolar region at ~100 km altitude, using recent comprehensive measurement by a Japanese lunar orbiter SELENE (Kaguya). The sneaking of SW ions into the deepest lunar wake was accompanied by an enhancement of counter-streaming electrons along the SW magnetic field. A part of the ions detected in the anti-subsolar region came from the lunar surface, which means that the ions of solar wind origin reflected at the night-side surface. One possibility is that electron- rich wake environment strengthened the bipolar electric field at the wake boundary to let solar-wind ions approach the lunar night side, and the other scenario is that enhancement of ions in the wake let ambient electrons to come in. The sneaking mechanism of the solar wind ions in terms of plasma and electromagnetic environment around/inside the lunar wake will be discussed.

  20. Effect of uranyl nitrate and free acid concentration in feed solution of gelation on UO2 kernel quality

    International Nuclear Information System (INIS)

    Masduki, B.; Wardaya; Widarmoko, A.

    1996-01-01

    An investigation on the effect of uranium and free nitric acid concentration of uranyl nitrate as feed of gelation process on quality of UO 2 kernel was done.The investigation is to look for some concentration of uranyl nitrate solutions those are optimum as feed for preparation of gelled UO 3 . Uranyl nitrate solution of various concentration of uranium (450; 500; 550; 600; 650; 700 g/l) and free nitric acid of (0.9; 1.0; 1.1 N) was made into feed solutions by adding urea and HMTA with mole ratio of urea/uranium and HMTA/uranium 2.1 and 2.0. The feed solutions were changed into spherical gelled UO 3 by dropping was done to get the optimum concentrations of uranyl nitrate solutions. The gelled UO 3 was soaked and washed with 2.5% ammonia solution for 17 hours, dried at 70 o C, calcined at 350 o C for 3 hours then reduced at 850 o C for 3 hours. At every step of the steps process the colour and percentage of well product of gelled UO 3 were noticed. The density and O/U ratio of end product (UO 2 kernel) was determined, the percentage of well product of all steps process was also determined. The three factor were used to chose the optimum concentration of uranyl nitrate solution. From this investigation it was concluded that the optimum concentration of uranyl nitrate was 600 g/l uranium with free nitric acid 0,9 - 1,0 N, the percentage of well product was 97% density of 6.12 - 4.8 g/cc and O/U ratio of 2.15 - 2.06. (author)

  1. DFT study of uranyl peroxo complexes with H2O, F-, OH-, CO3(2-), and NO3(-).

    Science.gov (United States)

    Odoh, Samuel O; Schreckenbach, Georg

    2013-05-06

    The structural and electronic properties of monoperoxo and diperoxo uranyl complexes with aquo, fluoride, hydroxo, carbonate, and nitrate ligands have been studied using scalar relativistic density functional theory (DFT). Only the complexes in which the peroxo ligands are coordinated to the uranyl moiety in a bidentate mode were considered. The calculated binding energies confirm that the affinity of the peroxo ligand for the uranyl group far exceeds that of the F(-), OH(-), CO3(2-), NO3(-), and H2O ligands. The formation of the monoperoxo complexes from UO2(H2O)5(2+) and HO2(-) were found to be exothermic in solution. In contrast, the formation of the monouranyl-diperoxo, UO2(O2)2X2(4-) or UO2(O2)2X(4-/3-) (where X is any of F(-), OH(-), CO3(2-), or NO3(-)), complexes were all found to be endothermic in aqueous solution. This suggests that the monoperoxo species are the terminal monouranyl peroxo complexes in solution, in agreement with recent experimental work. Overall, we find that the properties of the uranyl-peroxo complexes conform to well-known trends: the coordination of the peroxo ligand weakens the U-O(yl) bonds, stabilizes the σ(d) orbitals and causes a mixing between the uranyl π- and peroxo σ- and π-orbitals. The weakening of the U-O(yl) bonds upon peroxide coordination results in uranyl stretching vibrational frequencies that are much lower than those obtained after the coordination of carbonato or hydroxo ligands.

  2. The research of technology and equipment for a microwave denitration process of the uranyl nitrate solution

    International Nuclear Information System (INIS)

    Bao Weimin; Wang Xuejun; Ma Xuquan; Shi Miaoyi; Zhang Zhicheng; Bao Zhu Tian.

    1991-01-01

    In order to improve the present process of converting the plutonium nitrate into oxide powder in the nuclear fuel cycle, a new conversion process for the direct denitration using microwave heating has been developed. Microwave denitration is based on intramolecular polarization of a material in electric field and has no need of a process of heat transfer during microwave heating, so that the whole material can be heated quickly and uniformly. The thermal decomposition reactions of Pu, U, Th and RE nitrate have been analyzed and compared. The uranyl nitrate solution was chosen as imitative plutonium nitrate solution. The performance parameters ε r tanδ of U, Th and RE nitrate and oxide in microwave field were measured. The data obtained show that all of them could absorb microwave energy well and cause heating decomposition reactions. The microwave denitration test unit was designed and made. Denitration tests for rare-earths nitrate and uranyl nitrate solutions were performed. It could be completed in one step that the uranyl nitrate solution was evaporated, dryed and denitrated in a vessel. The denitrated products are a porous lump and easy to scrape off from the denitration vessel. The main forms of the products UO 3 ·0.8H 2 O and U 3 O 8 which have excellent powder properties. The capacity of the denitration unit is 1.3 kg UO 3 /h. According to the experimental results the simplicity, feasibility and good repeatability of the process have been fully proved. The unit operates easily and is adaptable to conversion of nitrate in nuclear fuel cycle. (author)

  3. Computer simulation of uranyl uptake by the rough lipopolysaccharide membrane of Pseudomonas aeruginosa.

    Science.gov (United States)

    Lins, Roberto D; Vorpagel, Erich R; Guglielmi, Matteo; Straatsma, T P

    2008-01-01

    Heavy metal environmental contaminants cannot be destroyed but require containment, preferably in concentrated form, in a solid or immobile form for recycling or final disposal. Microorganisms are able to take up and deposit high levels of contaminant metals, including radioactive metals such as uranium and plutonium, into their cell wall. Consequently, these microbial systems are of great interest as the basis for potential environmental bioremediation technologies. The outer membranes of Gram-negative microbes are highly nonsymmetric and exhibit a significant electrostatic potential gradient across the membrane. This gradient has a significant effect on the uptake and transport of charged and dipolar compounds. However, the effectiveness of microbial systems for environmental remediation will depend strongly on specific properties that determine the uptake of targeted contaminants by a particular cell wall. To aid in the design of microbial remediation technologies, knowledge of the factors that determine the affinity of a particular bacterial outer membrane for the most common ionic species found in contaminated soils and groundwater is of great importance. Using our previously developed model for the lipopolysaccharide (LPS) membrane of Pseudomonas aeruginosa, this work presents the potentials of mean force as the estimate of the free energy profile for uptake of sodium, calcium, chloride, uranyl ions, and a water molecule by the bacterial LPS membrane. A compatible classical parameter set for uranyl has been developed and validated. Results show that the uptake of uranyl is energetically a favorable process relative to the other ions studied. At neutral pH, this nuclide is shown to be retained on the surface of the LPS membrane through chelation with the carboxyl and hydroxyl groups located in the outer core.

  4. Structural variability in uranyl-lanthanide hetero-metallic complexes with DOTA and oxalato ligands

    International Nuclear Information System (INIS)

    Thuery, P.

    2009-01-01

    Four novel 4f-5f hetero-metallic complexes could be obtained from the reaction of uranyl and lanthanide nitrates with DOTA (H 4 L) under hydrothermal conditions. In all cases, as in the previous examples reported, additional oxalato ligands are formed in situ. Variations in the stoichiometry of the final products and the presence of hydroxo ions in some cases appear to result in a large structural variability. In the two isomorphous complexes [(UO 2 ) 2 Ln 2 (L) 2 (C 2 O 4 )] with Ln = Sm(1) or Eu(2), the lanthanide ion is located in the N 4 O 4 site and is also bound to a carboxylate oxygen atom from a neighbouring unit, to give zigzag chains which are further linked to one another by [(UO 2 ) 2 (C 2 O 4 )] 2+ di-cations, resulting in the formation of a 3D framework. In [(UO 2 ) 4 Gd 2 (L) 2 (C 2 O 4 ) 3 (H 2 O) 6 ].2H 2 O (3), 2D bilayer subunits of the 'double floor' type with uranyl oxalate pillars are assembled into a 3D framework by other, disordered uranyl ions. [(UO 2 ) 2 Gd(L)(C 2 O 4 )(OH)].H 2 O (4) is a 2D assembly in which cationic {[(UO 2 ) 2 (C 2 O 4 )(OH)] + } n chains are linked to one another by the [Gd(L)] - groups. The most notable feature of this compound is the environment of the 4f ion, which is eight-coordinate and twisted square anti-prismatic (TSA'), instead of nine-coordinate mono-capped square anti-prismatic (SA), as generally observed in DOTA complexes of gadolinium(III) and similarly-sized ions. (author)

  5. Effect of temperature on the mechanisms of interaction between uranyl ion and zirconium oxo-phosphate

    International Nuclear Information System (INIS)

    Almazan Torres, Maria Guadalupe

    2007-01-01

    Uranium sorption onto Zr 2 O(PO 4 ) 2 has been studied between 298 K and 363 K, in 0.1 M NaClO 4 medium. Potentiometric titrations were realized to determine temperature dependency of the acid-base properties (pH pcn , acidity constants). Classical batch experiments were performed at different temperatures. The sorption experiments revealed that the uranium sorption onto Zr 2 O(PO 4 ) 2 is favoured with the temperature. Structural characterization of the surface complexes was performed by both Time-Resolved Laser-Induced Fluorescence (TRLIF) and EXAFS spectroscopy. The TRLIF measurements vs. temperature revealed two uranyl surface complexes. No influence of the temperature onto the nature surface complex was observed. The EXAFS analysis showed a splitting of the equatorial oxygen atoms in two shells, corresponding to uranyl bidentate, inner-sphere complexes. The obtained structural uranyl surface complex information was used to simulate (using a constant capacitance model) the sorption edges. The proposed complexes equilibrium model consists of the following surface complexes: (≡ZrOH) 2 UO 2 2+ and (≡PO) 2 UO 2 . Besides the stability constants for the surface complexes, the thermodynamic parameters ΔH 0 and ΔS 0 were determined using the van't Hoff equation. The enthalpy values associated to the U(VI) retention onto Zr 2 O(PO 4 ) 2 , determined by the temperature dependence of the stability constants, testify that the formation of the complex (≡PO) 2 UO 2 (55 kJ/mol) is endothermic, while no influence of the temperature was observed for the formation of the complex (≡ZrOH) 2 UO 2 2+ . The adsorption reaction of the last complex is then driven by entropy. In addition, calorimetric measurements of uranium sorption onto Zr 2 O(PO 4 ) 2 were carried out to directly quantify the enthalpy associated to the retention processes. (author)

  6. Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

    Energy Technology Data Exchange (ETDEWEB)

    Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L. [Department of Chemistry, The George Washington University, Washington, DC (United States)

    2016-01-15

    The syntheses and crystal structures of six new compounds containing the UO{sub 2}{sup 2+} cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2{sup '}:6{sup '},2''-terpyridine (terpy), 4{sup '}-chloro-2,2{sup '}:6{sup '},2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. Behind adhesion of uranyl onto montmorillonite surface: A molecular dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Yang, W.; Zaoui, A., E-mail: azaoui@polytech-lille.fr

    2013-10-15

    Highlights: • We investigated the adsorption of uranyl onto Montmorillonite surface. • We studied the surface energy between layered Montmorillonite sheets. • We studied the work of adhesion between radionuclide and charged Montmorillonite. -- Abstract: We have performed molecular dynamics simulations to investigate the adsorption of radionuclide elements species onto substituted Montmorillonite (001) surface in the presence of different counterions. The structure and the dynamics of uranyl ion as well as its aquo, chloride ion, and carbonate complexes are analyzed. In addition, we have studied the surface energy between layered Montmorillonite sheets and the work of adhesion between radionuclide and charged Montmorillonite. The clay model used here is a Wyoming-type Montmorillonite with 0.75e negative charge per unit cell resulting from substitutions in Octahedral and Tetrahedral sheets. The system model was constructed based on CLAYFF force field potential model. To evaluate the thermodynamic work of adhesion, each surface and clay layer regions are converted to a thin film model. One and two species of radionuclide elements (UO{sub 2}(H{sub 2}O){sub 5},UO{sub 2}CO{sub 3}(H{sub 2}O){sub 5}, and UO{sub 2}Cl{sub 2}(H{sub 2}O){sub 5}) were deposited near the clay surface in a pseudo-two-dimensional periodic cell. Analysis shows that the uranyl ion structure is preserved with two axial oxygen atoms detected at 1.8 Å. Radial distribution functions results indicate that average U-O{sub w} distances are 2.45–2.61 Å, and 2.29–2.40 Å for U-O{sub c} distance. Average U-Cl distances are 2.78–3.08 Å, which is relatively larger than that of Uranium atom-Oxygen atom because of electrostatic factors.

  8. Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

    Energy Technology Data Exchange (ETDEWEB)

    Medvedkov, Ya. A.; Serezhkina, L. B., E-mail: Lserezh@samsu.ru [Samara State University (Russian Federation); Grigor’ev, M. S. [Russian Academy of Sciences, Frumkin Institute of Physical Chemistry and Electrochemistry (Russian Federation); Serezhkin, V. N. [Samara State University (Russian Federation)

    2016-05-15

    Two new malonate-containing uranyl complexes with carbamide of the formulas [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}] (I) and [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 3}] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO{sub 2}(C{sub 2}O{sub 4})(Urea){sub 3}] (III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO{sub 2}(C{sub 3}H{sub 2}O{sub 4})(Urea){sub 2}]{sub ∞} belonging to the crystal-chemical group AT{sup 11}M{sub 2}{sup 1} (A = UO{sub 2}{sup 2+}, T{sup 11} = C{sub 3}H{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea) of uranyl complexes. Crystals II and III are composed of the molecular complexes [UO{sub 2}(L)(Urea){sub 3}], where L = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, belonging to the crystal-chemical group AB{sup 01}M{sub 3}{sup 1} (A = UO{sub 2}{sup 2+}, B{sup 01} = C{sub 3}H{sub 2}O{sub 4}{sup 2-} or C{sub 2}O{sub 4}{sup 2-}, M{sup 1} = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi–Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.

  9. Probing the influence of N-donor capping ligands on supramolecular assembly in molecular uranyl materials

    International Nuclear Information System (INIS)

    Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L.

    2016-01-01

    The syntheses and crystal structures of six new compounds containing the UO 2 2+ cation, 3,5-dichlorobenzoic acid, and a chelating N-donor [2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dimethylphen), 2,2 ' :6 ' ,2''-terpyridine (terpy), 4 ' -chloro-2,2 ' :6 ' ,2''-terpyridine (Cl-terpy), or 2,4,6-tris(2-pyridyl)-s-triazine (TPTZ)] are reported. Single-crystal X-ray diffraction analysis of these materials enabled the exploration of the structural relationship between the benzoic acids and the chelating N-donor as well as providing a platform to evaluate the effects of ligand choice on uranyl hydrolysis and subsequent oligomerization. At an unadjusted pH (ca. 3), a mix of uranyl monomers and dimers are observed, dimer formation resulting from both bridging carboxylate linkers and hydroxo bridges. Assembly by halogen- and hydrogen-bonding interactions as well as π-π interactions was observed depending on the experimental conditions utilized. Further, spectroscopic characterization (both vibrational and luminescence) of complexes 1, 4, and 5 to explore the effects of the electron-donating ability of the capping ligand on the corresponding uranyl luminescence and vibrational spectra suggests that there is a relationship between the observed bathochromic shifts and the electron-donating ability of the capping ligands. (Copyright copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Spectropolarimetric analysis. Communication 14. Determination of uranyl with d-tartaric acid

    Energy Technology Data Exchange (ETDEWEB)

    Bakalov, V D; Dunina, V V; Potapov, V M [Moskovskij Gosudarstvennyj Univ. (USSR)

    1982-02-01

    The possibility has been shown of improving the sensitivity and precision of determination of uranium (6) in the form of its tartrate complex by using spectropolarimetry instead of polarimetry and circular dichroism instead of optical rotatory dispersion. The method makes it possible to reduce reagent consumption, to expand a range of uranium(6) concentration, which could be determined, due to changes of the cell length and reading range. On the basis of the circular dichroism spectrum of the uranyl-tartrate complex, its symmetry has been estimated to be Dsub(4h) with the coordination number of four on the equatorial plane.

  11. Study on the transport behavior of uranyl nitrate in aqueous and non-aqueous systems

    International Nuclear Information System (INIS)

    Roesel, B.

    1985-01-01

    The analytical ultracentrifuge has proven itself through diffusion measurements to be well suited for studying radioactive compounds. In the framework of this paper the extent to which the UV and schlieren optics of an analytical ultracentrifuge can be used for extraction-kinetic tests was tested. With this method there is also the possibility of determining the distribution coefficients right at the phase boundary. The results show the good possibility of application of the absorption and schlieren optics to the study of the transport behavior of uranyl nitrate in practice oriented solutions. (orig.) [de

  12. Skin contamination resulting from an uranyl nitrate burn. An incident study

    International Nuclear Information System (INIS)

    Quesne, B.; Auriol, B.; Berard, P.; Chalabreysse, J.

    1993-01-01

    The authors describe the circumstances of a burn incident on hand by a mixture of diluted nitric acid and uranyl nitrate. The burn is located on the left hand fingers. After important washings uranium remains on the fingers. During about ten days, the worker is examined and the therapy is going on till the total radioactivity disappearance. Urine collection of twenty four hours is prescribed during the treatment. The whole activity is kept on the burnt skin. The quick desquamation is the elimination way of the skin retention. 6 refs., 3 figs., 4 tabs

  13. Development of a reduction process of ammonium uranyl carbonate to uranium dioxide in a fluidized bed

    International Nuclear Information System (INIS)

    Gomes, R.P.; Riella, H.G.

    1990-07-01

    Laboratory development of ammonium uranyl carbonate (AUC) reduction to uranium dioxide (UO 2 ) using fluidized bed furnace technique is described. The reaction is carried out at 500-550 0 C using hydrogen, liberated from cracking of ammonia, as a reducing agent. As the AUC used is obtained from uranium hexafluoride (UF 6 ) it contains considerable amount of fluoride (approx. 500μg/g) as contaminant. The presence of fluoride leads to high corrosion rates and hence the fluoride concentration is reduced by pyrohydrolisis of UO 2 . Physical and Chemical properties of the final product (UO 2 ) obtained were characterized. (author) [pt

  14. U3O8 powder from uranyl-loaded cation exchange resin

    International Nuclear Information System (INIS)

    Mosley, W.C.

    1985-01-01

    Large batches of U 3 O 8 , suitable for powder metallurgy fabrication of Al-U 3 O 8 cores for reactor fuel tubes, have been produced by deep-bed calcination of granular uranyl-loaded macroporous sulfonate cation exchange resin at 900 to 950 0 C in air. Deep-bed calcination is the backup process for the reference process of rotary calcination and sintering. These processes are to be used for recycling uranium, and to produce U 3 O 8 in the Fuel Production Facility to be built at the Savannah River Plant. 2 refs., 6 figs

  15. Interfacial Interaction of Titania Nanoparticles and Ligated Uranyl Species: A Relativistic DFT Investigation.

    Science.gov (United States)

    Zhao, Hong-Bo; Zheng, Ming; Schreckenbach, Georg; Pan, Qing-Jiang

    2017-03-06

    To understand interfacial behavior of actinides adsorbed onto mineral surfaces and unravel their structure-property relationship, the structures, electronic properties, and energetics of various ligated uranyl species adsorbed onto TiO 2 surface nanoparticle clusters (SNCs) were examined using relativistic density functional theory. Rutile (110) and anatase (101) titania surfaces, experimentally known to be stable, were fully optimized. For the former, models studied include clean and water-free Ti 27 O 64 H 20 (dry), partially hydrated (Ti 27 O 64 H 20 )(H 2 O) 8 (sol) and proton-saturated [(Ti 27 O 64 H 20 )(H 2 O) 8 (H) 2 ] 2+ (sat), while defect-free and defected anatase SNCs involving more than 38 TiO 2 units were considered. The aquouranyl sorption onto rutile SNCs is energetically preferred, with interaction energies of -8.54, -10.36, and -2.39 eV, respectively. Energy decomposition demonstrates that the sorption is dominated by orbital attractive interactions and modified by steric effects. Greater hydrogen-bonding involvement leads to increased orbital interactions (i.e., more negative energy) from dry to sol/sat complexes, while much larger steric interaction in the sat complex significantly reduces the sorption interaction (i.e., more positive energy). For dry SNC, adsorbates were varied from aquo to aquo-carbonato, to carbonato, to hydroxo uranyl species. Longer U-O surf /U-Ti distances and more positive sorption energies were calculated upon introducing carbonato and hydroxo ligands, indicative of weaker uranyl sorption onto the substrate. This is consistent with experimental observations that the uranyl sorption rate decreases upon raising solution pH value or adding carbon dioxide. Anatase SNCs adsorbing aquouranyl are even more exothermic, because more bonds are formed than in the case of rutile. Moreover, the anatase sorption can be tuned by surface defects as well as its Ti and O stoichiometry. All the aquouranyl-SNC complexes show similar

  16. Development of fluidized-bed furnace for thermal treatment of ammonium uranyl carbonate

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, U C; Anuradha, M; Meena, R [Nuclear Fuel Complex, Hyderabad (India)

    1994-06-01

    At present the ammonium uranyl carbonate (AUC) route is developed at a scale of 10 kg/day of UO{sub 2}. This UO{sub 2} is directly compactible and sinterable to densities of 10.55-10.65 gm/cc. The equipment developed include precipitation tank with filtration and methanol washing and fluidized bed furnaces for thermal treatment of AUC and U{sub 3}O{sub 8}. During the design and development of these furnaces many experiments were conducted to study fluidization of AUC powder. In this paper the findings of these studies are presented. (author). 3 refs., 4 figs., 3 tabs.

  17. Effect of n-octanol on -uranyl extraction by tri-n-octylammonium sulfate

    International Nuclear Information System (INIS)

    Ochkin, A.V.; Kudrov, A.N.

    1984-01-01

    The effect of n-octanol on the extraction of uranyl sulfate by solutions of tri-n-octylamine sulfate in benzene has been studied. With the increase of alcohol concentration the coefficient of uranium distribution passes through the maximum. At low alcohol concentrations a decrease in water content in the organic phase is observed. It is shown that the increase in ammonium salt activity in replacement of part of hydrate At high alcohol concentration the decrease in uranium distribution coefficients is observed, which is related to TOA sulfate solvation by alcohol

  18. Benchmark calculation for water reflected STACY cores containing low enriched uranyl nitrate solution

    International Nuclear Information System (INIS)

    Miyoshi, Yoshinori; Yamamoto, Toshihiro; Nakamura, Takemi

    2001-01-01

    In order to validate the availability of criticality calculation codes and related nuclear data library, a series of fundamental benchmark experiments on low enriched uranyl nitrate solution have been performed with a Static Experiment Criticality Facility, STACY in JAERI. The basic core composed of a single tank with water reflector was used for accumulating the systematic data with well-known experimental uncertainties. This paper presents the outline of the core configurations of STACY, the standard calculation model, and calculation results with a Monte Carlo code and JENDL 3.2 nuclear data library. (author)

  19. Thermal Analysis of the Decomposition of Ammonium Uranyl Carbonate (AUC) in Different Atmospheres

    DEFF Research Database (Denmark)

    Hälldahl, L.; Sørensen, Ole Toft

    1979-01-01

    The intermediate products formed during thermal decomposition of ammonium uranyl carbonate (AUC) in different atmospheres, (air, helium and hydrogen) have been determined by thermal analysis, (TG, and DTA) and X-ray analysis. The endproducts observed are U3O8 and UO2 in air/He and hydrogen, respe......, respectively. The following intermediate products were observed in all atmospheres: http://www.sciencedirect.com.globalproxy.cvt.dk/cache/MiamiImageURL/B6THV-44K80TV-FB-1/0?wchp=dGLzVlz-zSkWW X-ray diffraction analysis showed that these phases were amorphous....

  20. Recovery of uranium from uranyl nitrate raffinate. Contributed Paper PE-06

    International Nuclear Information System (INIS)

    Anilkumar Reddy, A.M.; Shiva Kumar, M.; Varadan, K.M.K.; Babaji, P.; Sairam, S. Sheela; Saibaba, N.

    2014-01-01

    At New Uranium Oxide Fuel Plant, NUOFP(O) of Nuclear Fuel Complex (NFC), the Uranyl Nitrate Raffinate (UNR) generated during solvent extraction process is washed with Treated Lean Solvent(TLS) to recover residual U. Earlier this UNR consisting of 0.5-1 gm/l and 2.5 FA was neutralised with vapour ammonia. The slurry was then filtered over pre coat drum filter and the resultant Uranyl Nitrate Raffinate cake (UNRC) was stored in polyethylene lined MS drums. The valuable U was thus being locked up in UNRC. Also, the storage of UNRC drums required lot of floor space which have to be repacked frequently to contain the radioactivity. Hence the need has come to avoid the generation of UNRC and the recovery of U from the already generated UNRC. The generation of UNRC was avoided by developing alternate process of UNR treatment with Treated Lean Solvent for the removal of residual U and the resulting Acidic Raffinate Slurry (ARS) is disposed. The Uranium recovery from UNRC is done by dissolving the cake in Uranyl Nitrate Raffinate solution to leach the hexavalent Uranium by utilizing the free acidity in UNR. The leaching time is about six hours and the uranium forms uranyl nitrate. The resulting leach solutions are relatively dilute but complex acidic nitrate solutions containing wide variety of ions. Metallic ions commonly present include uranium, iron, magnesium, aluminium, sodium, calcium etc. The uranium concentration is normally 1-1.5 g/L. This uranium is separated by solvent extraction. The active agent in solvent extraction is Tri Butyl Phosphate in kerosene that can selectively extract uranium into an organic complex which is insoluble in aqueous. The organic used for extraction is Treated Lean Solvent in the quality of freshly prepared solvent and the resulting Acidic Raffinate Slurry is disposed by sale. The leaching of Uranium from UNRC was done in plant scale and about 1200 kgs of UNRC was successfully processed in trial batch. The paper deals with details of

  1. Uranyl(VI)-acetylacetonate coordination compounds with various N-heterocyclic ligands

    International Nuclear Information System (INIS)

    Kawasaki, Takeshi; Nishimura, Tatsuru; Kitazawa, Takafumi

    2010-01-01

    Seven uranyl(VI) complexes, [UO 2 (acac) 2 (L)] [L=4-methylpyridine (1), 4-ethylpyridine (2), 2,4-dimethylpyridine (3), (-)-nicotine (4), and imidazole (5)], [{UO 2 (acac) 2 } 2 -(4,4'-bipyridine)] (6), and [(2,2'-bipyridine) 2 H][UO 2 (acac)(NO 3 ) 2 ] (7) have been synthesized and characterized crystallographically. The coordination geometry of U has a UNO 6 pentagonal-bipyramidal coordination in 1-6, and a UO 8 hexagonal-bipyramidal coordination in 7. (author)

  2. Investigations on uranyl nitrate solubility in nitric acid in different concentrations at temperatures of 50C

    International Nuclear Information System (INIS)

    Deigele, E.

    1983-01-01

    The solubility of uranyl nitrate was studied in nitric acid solutions of different concentrations at a temperature of 5 0 C. This temperature was chosen with a view to using water as coolant and to facilitate the handling of the strong acid solutions. Accurate curves were established by a multitude of accurate measurements in the high concentration range. Further solubility curves can be derived from this basic curve. Some of the precipitates in the interesting regions of the solubility curve were analyzed. (orig./EF) [de

  3. Beryllium(II), manganese(II) and uranyl(VI)-salicylamide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Maurya, P L; Agarwala, B V; Dey, A K [Allahabad Univ. (India)

    1977-01-01

    The preparation, composition, general properties and i.r. absorption spectra of the solid chelates formed by salicylamide with beryllium(II), manganese(II) and uranyl(VI) are described. The complexes have been synthesized by refluxing a mixture of ethanolic solutions of the reactants (metal:ligand :: 1:2) for several hours in the presence of alkali. Attempts to isolate the complexes by the interaction of ethanolic solutions of the metal salts and the ligand in the absence of alkali did not succeed.

  4. Experience with a uranyl nitrate/uranium dioxide conversion pilot plant

    International Nuclear Information System (INIS)

    Arcuri, L.; Pietrelli, L.

    1984-01-01

    A plant for the precipitation of sinterable nuclear grade UO 2 powders is described in this report. The plant has been designed, built and set up by SNIA TECHINT. ENEA has been involved in the job as nuclear consultant. Main process steps are: dissolution of UO 2 powder or sintered UO 2 pellets, adjustment of uranyl nitrate solutions, precipitation of uranium peroxide by means of hydrogen peroxide, centrifugation of the precipitate, drying, calcination and reduction to uranium dioxide. The report is divided in two main section: the process description and the ''hot test'' report. Some laboratory data on precipitation of ammonium diuranate by means of NH 4 OH, are also reported

  5. Quenching of excited uranyl ion during its photochemical reduction by triphenylphosphine: Part III

    International Nuclear Information System (INIS)

    Sidhu, M.S.; Chahal, P.; Singh, R.J.

    1993-01-01

    Relative rates of bimolecular quenching of excited uranyl ion by some mono and di-substituted benzene derivatives have been measured during its photochemical reduction with triphenylphosphine. For the related compounds in a series it has been found that substituent groups enriching the aromatic π-electron cloud due to resonance stabilization, show an enhanced photophysical quenching action. The substituents decreasing the π-electron cloud and delocalization of positive charger over the benzene ring decrease the quenching action. (author). 16 refs., 2 figs., 1 tab

  6. Development of ammonium uranyl carbonate reduction to uranium dioxide using fluidized bed

    International Nuclear Information System (INIS)

    Gomes, R.P.; Riella, H.G.

    1988-01-01

    Laboratory development of Ammonium Uranyl Carbonate (AUC) reduction to uranium dioxide (UO 2 ) using fluidized bed furnace technique is described. The reaction is carried out at 500-550 0 C using hydrogen, liberated from cracking of ammonia, as a reducing agent. As the AUC used is obtained from uranium hexafluoride (UF 6 ) it contains considerable amounts of fluoride ( - 500μgF - /gTCAU) as contaminant. The presence of fluoride leads to high corrosion rates and hence the fluoride concentrations is reduced by pyrohydrolisis of UO 2 . Physical and Chemical proterties of the final product (UO 2 ) obtained were characterized. (author) [pt

  7. Photochemical methodologies for organic waste treatment: advanced oxidation process using uranyl ion with H2O2

    International Nuclear Information System (INIS)

    Naik, D.B.; Sarkar, S.K.; Mukherjee, T.

    2009-01-01

    Excited uranyl ion is able to degrade dyes such as thionine and methylene blue on irradiation with 254 nm/300 nm light. By adding H 2 O 2 along with uranyl ion, photodegradation takes place with visible light and also with enhanced rate. The hydroxyl radicals generated in the reoxidation of U(IV)/UO 2 + to UO 2 2+ are responsible for this enhanced degradation. The above advanced oxidation process (AOP) was applied to study the oxidation of 2-propanol to acetone. (author)

  8. Uranyl complexes of ν-polyketonates. Crystal and molecular structure of a mononuclear uranyl 1,3,5-triketonate and a novel trinuclear uranyl 1,3,5-triketonate with a trigonal-planar bridging oxide

    International Nuclear Information System (INIS)

    Lintvedt, R.L.; Heeg, M.J.; Ahmad, N.; Glick, M.D.

    1982-01-01

    Two uranyl complexes of 1,3,5-triketonate ligands have been crystallized and examined by X-ray diffraction techniques. The first is the mononuclear bis[1,5-diphenyl-1,3,5-pentanetrionato(1-)](methanol)dioxouranium(VI)-methanol,[UO 2 -(C 35 H 30 O 7 )(CH 3 OH)],UO 2 (H(DBA)) 2 (CH 3 OH).CH 3 OH, in which the uranium atom is bound to four enolic oxygens, two uranyl oxygens, and one methanolic oxygen. The triketonate ligands are in a cis configuration presumably due to the steric constraints of the methanol coordination. Crystal data are as follows: P2 1 /c, a = 9.932 (4), b = 30.29 (4), c = 11.671 (4) angstrom; ν = 103.03 0 , V = 3421 (2) angstrom 3 ; Z = 4, R 1 = 0.048, R 2 = 0.050. The second is a trinuclear UO 2 2 + anion containing a trigonal, tribridging oxide ion that results during attempts to prepare binuclear UO 2 2 + complexes of 1,3,5-triketonates. The compound bis(triethylammonium) tris(2,2',8,8'-tetramethyl-3,5,7-nonanetrionato)-μ 3 -oxo-tris(dioxo-uranate)(2-), [(C 2 H 5 ) 3 NH] 2 [U 3 O 6 (C 39 H 60 O 9 )O], [(C 2 H 5 ) 3 NH] 2 [(UO 2 ) 3 (DPA) 3 O], contains a nearly equilateral triangle of UO 2 2 + ions with a central O 2 - ion trigonally bonded to the three U atoms. One triketonate occupies each edge of the trangle with the central enolic oxygen bridging two U atoms and the terminal oxygens bound to one U atom. Each U is seven-coordinate in nearly pentagonal-bipyramidal geometry. Crystal data are as follows: C2/c, a = 27.90 (2), b = 15.65 (2), c = 31.81 (3) angstrom; ν = 107.8 (1) 0 , V = 13220 (20), angstrom 3 ; Z = 8, R 1 = 0.062, R 2 = 0.078

  9. Contribution to the study of the evaporation of aqueous uranyl nitrate solutions; Contribution a l'etude de l'evaporation des solutions aqueuses de nitrate d'uranyle

    Energy Technology Data Exchange (ETDEWEB)

    Billy, J [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1967-05-15

    This work was carried out with a view to define the conditions under which is affected the concentration of aqueous uranyl nitrate solutions one of the steps in uranium extraction metallurgy. The first port is devoted to the experimental determination of the physical characteristics of aqueous uranyl nitrate solutions, from dilute to concentrated solutions. The second part of this work is devoted to the isothermal evaporation of solution a west ted-wall column; this chemical engineering study has been more particularly devoted to the definition of the influence of the dynamics of the liquid phase on the exchange of matter between the two phases in contact. (author) [French] La concentration par evaporation des solutions aqueuses de nitrate d'uranyle constitue une etape de la metallurgie de l'uranium dont ce travail a voulu preciser la connaissance. Dans ce but, une premiere partie a ete consacree a la determination experimentale de caracteristiques physiques des solutions aqueuses de nitrate d'uranyle, des solutions diluees aux solutions saturees. Dans une deuxieme partie, ce travail a porte sur l'evaporation isotherme des solutions dans une colonne a paroi mouillee; cette etude de genie chimique a ete plus particulierement orientee de facon a preciser l'influence de la dynamique de la phase liquide sur l'echange de matiere entre les deux phases en contact. (auteur)

  10. Controlled deprotection and reorganization of uranyl oxo groups in a binuclear macrocyclic environment

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Guy M.; Arnold, Polly L.; Love, Jason B. [Edinburgh Univ. (United Kingdom). EaStCHEM School of Chemistry

    2012-12-07

    The silylated uranium(V) dioxo complex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] is inert to oxidation, but after two-electron reduction to [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-}, it can be desilylated to form [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} with reinstated uranyl character. Removal of the silyl group uncovers new redox and oxo rearrangement chemistry for uranium, thus reforming the uranyl motif and involving the U{sup VI/V} couple in dioxygen reduction. [German] Der silylierte Dioxouran(V)-Komplex [(Me{sub 3}SiOUO){sub 2}(L){sub 2}] (A) ist inert gegen Oxidation, kann aber nach Zweielektronenreduktion zu [(Me{sub 3}SiOUO){sub 2}(L)]{sup 2-} (1) zu [OU(μ-O){sub 2}UO(L){sub 2}]{sup 2-} (2) mit wiederhergestelltem Uranylcharakter desilyliert werden. Beim Entfernen der Silylgruppe zeigt sich eine neue Redox- und Oxoumlagerungschemie des Urans unter Rueckbildung des Uranylmotivs sowie der Beteiligung des U{sup VI/V}-Paars an einer Disauerstoffreduktion.

  11. Thermodynamic parameters of the complexation of uranyl(VI) by diethylenetriamine in dimethyl sulfoxide

    International Nuclear Information System (INIS)

    Cassol, A.; Bernardo, P. di; Portanova, R.; Tolazzi, M.; Tomat, G.; Zanonato, P.L.

    1993-01-01

    The changes in free energy, enthalpy, and entropy for the complex formation reactions between uranyl(VI) ion and diethylenetriamine (dien) in dimethyl sulfoxide have been determined by potentiometric and calorimetric measurements at 25 C in a medium of ionic strength 0.1 mol dm -3 . The amine forms a very stable 1:1 complex which results stabilized only by the highly favourable enthalpy change. Entropy change is negative and opposes the reaction. The comparison of the thermodynamic data concerning complexation of uranyl(VI) by charged and uncharged ligands reveals that in this case (uncharged ligand) the enthalpy contribution is mainly related to the formation of the metal-ligand bonds while the entropy term might be associated with the decrease in the translational and conformational entropy occurring in the complexation of the ligand. FTIR and calorimetric measurements have been carried out to study the effect of traces of water on the equilibria in solution. It has been found that water can interfere in the complexation reaction giving rise to the formation of a dinuclear hydroxo complex in which probably two μ 2 -OH bridges link two monomer moieties. (orig.)

  12. New insight into the ternary complexes of uranyl carbonate in seawater.

    Science.gov (United States)

    Beccia, M R; Matara-Aho, M; Reeves, B; Roques, J; Solari, P L; Monfort, M; Moulin, C; Den Auwer, C

    2017-11-01

    Uranium is naturally present in seawater at trace levels and may in some cases be present at higher concentrations, due to anthropogenic nuclear activities. Understanding uranium speciation in seawater is thus essential for predicting and controlling its behavior in this specific environmental compartment and consequently, its possible impact on living organisms. The carbonato calcic complex Ca 2 UO 2 (CO 3 ) 3 was previously identified as the main uranium species in natural seawater, together with CaUO 2 (CO 3 ) 3 2- . In this work, we further investigate the role of the alkaline earth cation in the structure of the ternary uranyl-carbonate complexes. For this purpose, artificial seawater, free of Mg 2+ and Ca 2+ , using Sr 2+ as a spectroscopic probe was prepared. Combining TRLIF and EXAFS spectroscopy, together with DFT and theoretical thermodynamic calculations, evidence for the presence of Sr alkaline earth counter ion in the complex structure can be asserted. Furthermore, data suggest that when Ca 2+ is replaced by Sr 2+ , SrUO 2 (CO 3 ) 3 2- is the main complex in solution and it occurs with the presence of at least one monodentate carbonate in the uranyl coordination sphere. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Oxo-exchange of gas-phase uranyl, neptunyl, and plutonyl with water and methanol.

    Science.gov (United States)

    Lucena, Ana F; Odoh, Samuel O; Zhao, Jing; Marçalo, Joaquim; Schreckenbach, Georg; Gibson, John K

    2014-02-17

    A challenge in actinide chemistry is activation of the strong bonds in the actinyl ions, AnO2(+) and AnO2(2+), where An = U, Np, or Pu. Actinyl activation in oxo-exchange with water in solution is well established, but the exchange mechanisms are unknown. Gas-phase actinyl oxo-exchange is a means to probe these processes in detail for simple systems, which are amenable to computational modeling. Gas-phase exchange reactions of UO2(+), NpO2(+), PuO2(+), and UO2(2+) with water and methanol were studied by experiment and density functional theory (DFT); reported for the first time are experimental results for UO2(2+) and for methanol exchange, as well as exchange rate constants. Key findings are faster exchange of UO2(2+) versus UO2(+) and faster exchange with methanol versus water; faster exchange of UO2(+) versus PuO2(+) was quantified. Computed potential energy profiles (PEPs) are in accord with the observed kinetics, validating the utility of DFT to model these exchange processes. The seemingly enigmatic result of faster exchange for uranyl, which has the strongest oxo-bonds, may reflect reduced covalency in uranyl as compared with plutonyl.

  14. New thermo-sensitive chelating surfactants for selective solvent-free extraction of uranyl nitrate

    International Nuclear Information System (INIS)

    Prevost, S.; Larpent, C.; Testard, F.; Coulombeau, H.; Baczko, K.; Berthon, L.; Desvaux, H.; Madic, C.; Zemb, T.

    2004-01-01

    Functional surfactants were synthesised by grafting a chelating group (amino-acid residue) to the tip of a poly-ethoxylated nonionic surfactant chain (C i E j : C i H 2i +1(OCH 2 CH 2 ) j OH)) or in a branched position. C i E j nonionic surfactants are known to be thermo-reversible and to exhibit a clouding phenomenon associated to phase separation of micelles. The functional surfactants retain both surface-active properties, characteristic thermo-reversible behaviour and have efficient complexing properties toward uranyl. In the presence of uranyl nitrate, small micelles are formed at ambient temperature and the de-mixing leads to a separation of the target ion trapped by the functional surfactant (cloud point extraction). Those surfactants are more efficient than mixture of classical C i E j and complexing agent solubilized in the micelles. This reveals a synergistic effect of the covalent bond between the chelating group and the nonionic surfactant C i E j . This paper presents a systematic study of the extraction and aggregation properties and the influence of the nature of the ions. (authors)

  15. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660{plus_minus}0.092 at 25 C, and extraction enthalpy is -5. 46{plus_minus}0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 {times} 10{sup 6}{plus_minus}3.56 {times} 10{sup 4} at 25 C; reaction enthalpy was -9.610{plus_minus}0.594 kcal/mol. Nitration complexation constant is 8.412{plus_minus}0.579, with an enthalpy of -10.72{plus_minus}1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured.

  16. PMR spectra and proton magnetic relaxation in uranyl nitrate-hexamethylenetetramine-urea-water gel forming system

    International Nuclear Information System (INIS)

    Vashman, A.A.; Pronin, I.S.; Brylkina, T.V.; Makarov, V.M.

    1979-01-01

    PMR spectra and proton relaxation in the nitrate-hexamethylenetetramine (HMTA)-urea-water gelling system are studied. According to PMR spectra products of HMTA chemical decomposition, which are supposed to be formed in the gelling process, have not been detected. Effect of hydrogen exchange upon PMR spectra of urea and water in the presence of HMTA and uranyl nitrate is studied. Periods of spin-lattice and spin-spin relaxations of water and HMTA protons in gels on the base of uranyl nitrate are found. Data on relaxation permitted to make qualitative conclusions upon the gel structure and HMTA molecule distribution over ''phases''. Nonproducibility of the results of period measurements in gels is the result of nonproducibility of the gel structure in the course of transformation of liquid solution into gel. Temperature dependences of proton relaxation in the gels are impossible yet to interpret on the basis of temperature behaviour of one correlation period, controlling dipole-dipole nuclear magnetic relaxation, and obeying Arrhenius dependence on the temperature

  17. Uranyl ion transport across tri-n-butyl phosphate/n-dodecane liquid membranes

    International Nuclear Information System (INIS)

    Shukla, J.P.; Misra, S.K.

    1991-01-01

    Carrier-facilitated transport of uranium (VI) against its concentration gradient from aqueous nitrate acidic solutions across organic bulk liquid membranes (BLM) and supported liquid membranes (SLM) containing TBP as the mobile carrier and n-dodecane as the membrane solvent was investigated. Extremely dilute uranyl nitrate solutions in about 2.5 M nitric acid generally constituted as the source phase. Uranyl transport appreciably increased with both stirring of the receiving phase and the carrier concentration in the organic membrane, while enhanced acidity of the strip side adversely affected the partioning of the cation into this phase. Among the several reagents tested, diluted ammonium carbonate (∼1M) solutions served efficiently as the stripant. Besides Accurel polypropylene (PP) film as the solid support for SLM, some silicon flat-sheet membranes with different inorganic fillers like silica, calcium silicate, calcium carbonate, chromium oxide, zinc oxide etc. and teflon membranes transported about 70% of uranium in nearly 7-8 hr employing 1 M ammonium carbonate as the strippant. Specifically, 30% TBP supported on Accurel flat-sheet supports transfered better than 70% of uranium from moderate acid feeds (2.5M) under similar conditions. Membranes supporting Aliquat-336, TLA, TOPO etc. yielded somewhat poor uranium recoveries. The feed : strip volume ratio showed an inverse relationship to the fraction of cation transported. (author). 9 refs., 2 tab s

  18. Weathering of natural uranyl oxide hydrates: Schoepite polytypes and dehydration effects

    International Nuclear Information System (INIS)

    Finch, R.J.; Miller, M.L.; Ewing, R.C.

    1992-01-01

    Partial dehydration of schoepite, UO 3 x2H 2 O, is reported to produce three discrete schoepite polytypes with characteristic unit cell parameters, but this has not been confirmed. The loss of structural water from the schoepite interlayer results in progressive modification to the structure; expansion parallel to schoepite cleavage planes, and extensive fracturing. Dehydration of schoepite commences at grain boundaries and progresses inward until the entire grain is converted to dehydrated schoepite, UO 3 x0.8H 2 O. The volume decrease associated with dehydration results in expanded grain boundaries. These gaps can provide pathways for the access of groundwater, and uranyl silicates and uranyl carbonates have precipitated within these gaps, replacing both schoepite and dehydrated schoepite. Schoepite, however, is not observed to re-precipitate where in contact with dehydrated schoepite. Thus, while the formation of schoepite early during the corrosion of uraninite may be favored, schoepite is not a long-term solubility limiting phase for oxidized uranium in natural ground waters containing dissolved silica or carbonate. (orig.)

  19. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    International Nuclear Information System (INIS)

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660±0.092 at 25 C, and extraction enthalpy is -5. 46±0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 x 10 6 ±3.56 x 10 4 at 25 C; reaction enthalpy was -9.610±0.594 kcal/mol. Nitration complexation constant is 8.412±0.579, with an enthalpy of -10.72±1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured

  20. Efficient tetracycline adsorption and photocatalytic degradation of rhodamine B by uranyl coordination polymer

    Science.gov (United States)

    Ren, Ya-Nan; Xu, Wei; Zhou, Lin-Xia; Zheng, Yue-Qing

    2017-07-01

    Two mixed uranyl-cadmium malonate coordination polymers [(UO2)2Cd(H-bipy)2(mal)4(H2O)2]·4H2O 1 and [(UO2)Cd(bipy)(mal)2]·H2O 2 (H2mal = malonic acid, bipy =4,4‧-bipyridine) have been synthesized in room temperature. Compound 1 represents a one-dimensional (1D) chain assembly of Cd(II) ions, uranyl centers and malonate ligands. Compound 2 exhibits a two-dimensional (2D) 2D +2D → 3D polycatenated framework based on inclined interlocked 2D 44 sql grids. The two compounds have been characterized by elemental analysis, IR and UV-vis spectroscopy, thermal analysis, powder X-ray diffraction and photoluminescence spectroscopy. And the ferroelectric property of 2 also has been studied. Moreover, compound 2 exhibits good photocatalytic activity for dye degradation under UV light and is excellent adsorbent for removing tetracycline antibiotics in the aqueous solution.

  1. TG/DTA and X ray Diffraction Studies on Ammonium Uranyl Nitrate

    International Nuclear Information System (INIS)

    Kim, Byung Ho; Lee, Young Bum; Jeong, Ji Young; Choi, Jong Hyun; Kim, Tae Joon; Nam, Ho Yun; Kim, Jong Man

    2011-01-01

    Ammonium uranyl nitrate (AUN) is an important intermediate product during conversion of a uranyl nitrate[UO 2 (NO 3 ) 2 ] solution to UO 2 powder for the fabrication of nuclear fuels, the so-called modified direct denitration (MDD) process. The MDD process involves the thermal decomposition of AUN double salts, which are prepared from a mixture consisting of a UO 2 (NO 3 ) 2 solution and NH 4 NO 3 . The physical and chemical properties of an oxide powder depend upon its thermal treatment. Three double salts are known for the UO 2 (NO 3 ) 2 - NH 4 NO 3 -H 2 O system, but there have been only a few studies done on thermal decomposition of these salts. Therefore, the objective of this study is to investigate the reaction pathways during a thermal decomposition and reduction of AUN to achieve a better knowledge of the influence of an AUN preparation process and thermal decomposition procedures on uranium oxides under a nitrogen, air, or hydrogen atmosphere

  2. Charge asymmetry of the purple membrane measured by uranyl quenching of dansyl fluorescence. [Halobacterium halobium

    Energy Technology Data Exchange (ETDEWEB)

    Renthal, R.; Cha, C.H.

    1984-05-01

    Purple membrane was covalently labeled with 5-(dimethylamino) naphthalene-1-sulfonyl hydrazine (dansyl hydrazine) by carbodiimide coupling to the cytoplasmic surface (carboxyl-terminal tail: 0.7 mol/mol bacteriorhodopsin) or by periodate oxidation and dimethylaminoborane reduction at the extracellular surface (glycolipids: 1 mol/mol). In 2 mM acetate buffer, pH 5.6, micromolar concentrations of UO/sub 2//sup 2 +/ were found to quench the dansyl groups on the cytoplasmic surface (maximum = 26%), while little quenching was observed at the extracellular surface (maximum = 4%). Uranyl ion quenched dansyl hydrazine in free solution at much higher concentrations. Uranyl also bound tightly to unmodified purple membrane, (apparent dissociation constant = 0.8 ..mu..M) as measured by a centrifugation assay. The maximum stoichiometry was 10 mol/mol of bacteriorhodopsin, which is close to the amount of phospholipid phosphorus in purple membrane. The results were analyzed on the assumptions that UO/sub 2//sup 2 +/ binds in a 1:1 complex with phospholipid phosphate and that the dansyl distributon and quenching mechanisms are the same at both surfaces. This indicates a 9:1 ratio of phosphate between the cytoplasmic and extracellular surfaces. Thus, the surface change density of the cytoplasmic side of the membrane is more negative than - 0.010 charges/A/sup 2/.

  3. Determination of uranium in uranium metal, uranium oxides, and uranyl nitrate solutions by potentiometric titration

    International Nuclear Information System (INIS)

    Tucker, H.L.; McElhaney, R.J.

    1983-01-01

    A simple, fast method for the determination of uranium in uranium metal, uranium oxides, and uranyl nitrate solutions has been adapted from the Davies-Gray volumetric method to meet the needs of Y-12. One-gram duplicate aliquots of uranium metal or uranium oxide are dissolved in 1:1 HNO 3 and concentrated H 2 SO 4 to sulfur trioxide fumes, and then diluted to 100-mL volume. Duplicate aliquots are then weighed for analysis. For uranyl nitrate samples, duplicate aliquots containing between 50 and 150 mg of U are weighed and analyzed directly. The weighed aliquot is transferred to a Berzelius beaker; 1.5 M sulfamic acid is added, followed in order by concentrated phosphoric acid, 1 M ferrous sulfate, and (after a 30-second interval) the oxidizing reagent. After a timed 3-minute waiting period, 100 mL of the 0.1% vanadyl sulfate-sulfuric acid mixture is added. The sample is then titrated past its endpoint with standard potassium dichromate, and the endpoint is determined by second derivative techniques on a mV/weight basis

  4. Establishing the traceability of a uranyl nitrate solution to a standard reference material

    International Nuclear Information System (INIS)

    Jackson, C.H.; Clark, J.P.

    1978-01-01

    A uranyl nitrate solution for use as a Working Calibration and Test Material (WCTM) was characterized, using a statistically designed procedure to document traceability to National Bureau of Standards Reference Material (SPM-960). A Reference Calibration and Test Material (PCTM) was prepared from SRM-960 uranium metal to approximate the acid and uranium concentration of the WCTM. This solution was used in the characterization procedure. Details of preparing, handling, and packaging these solutions are covered. Two outside laboratories, each having measurement expertise using a different analytical method, were selected to measure both solutions according to the procedure for characterizing the WCTM. Two different methods were also used for the in-house characterization work. All analytical results were tested for statistical agreement before the WCTM concentration and limit of error values were calculated. A concentration value was determined with a relative limit of error (RLE) of approximately 0.03% which was better than the target RLE of 0.08%. The use of this working material eliminates the expense of using SRMs to fulfill traceability requirements for uranium measurements on this type material. Several years' supply of uranyl nitrate solution with NBS traceability was produced. The cost of this material was less than 10% of an equal quantity of SRM-960 uranium metal

  5. Coupled Effect of Ferrous Ion and Oxygen on the Electron Selectivity of Zerovalent Iron for Selenate Sequestration.

    Science.gov (United States)

    Qin, Hejie; Li, Jinxiang; Yang, Hongyi; Pan, Bingcai; Zhang, Weiming; Guan, Xiaohong

    2017-05-02

    Although the electron selectivity (ES) of zerovalent iron (ZVI) for target contaminant and its utilization ratio (UR) decide the removal capacity of ZVI, little effort has been made to improve them. Taking selenate [Se(VI)] as a target contaminant, this study investigated the coupled influence of aeration gas and Fe(II) on the ES and UR of ZVI. Oxygen was necessary for effective removal of Se(VI) by ZVI without Fe(II) addition. Due to the application of 1.0 mM Fe(II), the ES of ZVI was increased from 3.2-3.6% to 6.2-6.8% and the UR of ZVI was improved by 5.0-19.4% under aerobic conditions, which resulted in a 100-180% increase in the Se(VI) removal capacity by ZVI. Se(VI) reduction by Fe 0 was a heterogeneous redox reaction, and the enrichment of Se(VI) on ZVI surface was the first step of electron transfer from Fe 0 core to Se(VI). Oxygen promoted the generation of iron (hydr)oxides, which facilitated the enrichment of Se(VI) on the ZVI particle surface. Therefore, the high oxygen fraction (25-50%) in the purging gas resulted in only a slight decrease in the ES of ZVI. Fe(II) addition resulted in a pH drop and promoted the generation of lepidocrocite and magnetite, which benefited Se(VI) adsorption and the following electron transfer from underlying Fe 0 to surface-located Se(VI).

  6. Selenium Accumulation Characteristics and Biofortification Potentiality in Turnip (Brassica rapa var. rapa Supplied with Selenite or Selenate

    Directory of Open Access Journals (Sweden)

    Xiong Li

    2018-01-01

    Full Text Available Selenium (Se is an essential trace element for humans. About 70% of the regions in China, including most of the Tibetan Plateau, are faced with Se deficiency problems. Turnip is mainly distributed around the Tibetan Plateau and is one of the few local crops. In the present study, we compared the absorption and translocation differences of Se (IV selenite and Se (VI selenate in turnip. The results showed that Se treatment, either by soil addition (0.2–2 mg Se kg−1 dry soil or by foliar spraying (50–200 mg L−1 Se, could significantly increase the Se concentrations in turnips, and 0.5 mg Se (IV or Se (VI kg−1 dry matter in soils could improve the biomasses of turnips. Moreover, turnip absorbed significantly more Se (VI than Se (IV at the same concentration and also transferred much more Se (VI from roots to leaves. Based on the Se concentrations, as well as the bioconcentration factors and translocation coefficients, we considered that turnip might be a potential Se indicator plant. Subsequently, we estimated the daily Se intake for adults based on the Se concentrations in turnip roots. The results indicated that Se (IV should be more suitable as an artificial Se fertilizer for turnips, although the levels found in most samples in this study could cause selenosis to humans. In addition, we also estimated the optimum and maximum Se concentrations for treating turnips based on the linear relations between Se concentrations in turnip roots and Se treatment concentrations. The results provided preliminary and useful information about Se biofortification in turnips.

  7. THE EFFECTS OF SODIUM SELENITE AND SELENIZED YEAST SUPPLEMENTATION INTO DIET FOR LAYING HENS ON SELECTED QUALITATIVE PARAMETERS OF TABLE EGGS

    Directory of Open Access Journals (Sweden)

    HENRIETA ARPÁŠOVÁ

    2009-10-01

    Full Text Available In this experiment the effects of supplementation of the diet for laying hens with sodium selenite (SS or selenized yeast (SY on whole egg and egg shell quality of layers were studied. The chickens of Shaver Starcross 288 strain were randomly divided at the day of hatching into 4 groups (n=12; in each. The birds were fed from Day 1 of life to 9 months of age with diets differing in amounts and/or forms of selenium. Control group received basal diet (BD containing selenium naturally occurring in feeds (0.1 mg Se/kg of dry matter (DM. First and second experimental group of chickens were fed with a same BD enriched with equivalent dose of Se 0.4 mg/kg DM in form of sodium selenite or selenized yeast, respectively. The feed for third experimental group of birds consisted of BD supplemented with selenized yeast to the final amount of selenium 1.0 mg/kg DM. The egg weight was significantly higher in the groups with SY supplementation only. On the contrary the egg shell ratio was significantly lower in the groups with SY supplementation in both amounts. The width of egg was significantly increased in the groups with selenium supplementation in both forms. The value of egg shell strength was significantly decreased in group with SY in the highest amount 0.9 mg/kg DM The average egg shell thickness was the highest in the experimental group with Se-yeast in amount 0.9 mg/kg DM, however different was not significant compared with control group. The results showed that the most of selected parameters of egg quality appeared to be significantly influenced by selenium supplementation into laying hen’s basal diet.

  8. Effect of selenization time on the structural and morphological properties of Cu(In,Ga)Se2 thin films absorber layers using two step growth process

    Science.gov (United States)

    Korir, Peter C.; Dejene, Francis B.

    2018-04-01

    In this work two step growth process was used to prepare Cu(In, Ga)Se2 thin film for solar cell applications. The first step involves deposition of Cu-In-Ga precursor films followed by the selenization process under vacuum using elemental selenium vapor to form Cu(In,Ga)Se2 film. The growth process was done at a fixed temperature of 515 °C for 45, 60 and 90 min to control film thickness and gallium incorporation into the absorber layer film. The X-ray diffraction (XRD) pattern confirms single-phase Cu(In,Ga)Se2 film for all the three samples and no secondary phases were observed. A shift in the diffraction peaks to higher 2θ (2 theta) values is observed for the thin films compared to that of pure CuInSe2. The surface morphology of the resulting film grown for 60 min was characterized by the presence of uniform large grain size particles, which are typical for device quality material. Photoluminescence spectra show the shifting of emission peaks to higher energies for longer duration of selenization attributed to the incorporation of more gallium into the CuInSe2 crystal structure. Electron probe microanalysis (EPMA) revealed a uniform distribution of the elements through the surface of the film. The elemental ratio of Cu/(In + Ga) and Se/Cu + In + Ga strongly depends on the selenization time. The Cu/In + Ga ratio for the 60 min film is 0.88 which is in the range of the values (0.75-0.98) for best solar cell device performances.

  9. Effects of nitrate, fulvate, phosphate, phthalate, salicylate and catechol on the sorption of uranyl onto SiO2. A comparative study

    International Nuclear Information System (INIS)

    Zhang Hongxia; Wen Chuanxi; Tao Zuyi; Wu Wangsuo

    2011-01-01

    We have performed a large number of batch sorption experiments of uranyl onto SiO 2 and examined the effects of nitrate or ionic strength, phosphate, fulvic acid(FA), phthalic acid (PH), salicylic acid (SA), and catechol (CA) on the uranyl sorption onto SiO 2 . Three sorption edges and three sorption isotherms at ionic strengths 0.05, 0.1, and 0.5 mol/L KNO 3 were used to investigate the effect of ionic strength or nitrate on the sorption and the Langmuir, Freundlich, and Dubinin-Radushkevich models are used to simulate the sorption isotherms, respectively. Five sorption edges in the presence of phosphate, FA, PH, SA, and CA were compared with that in the absence of complexing ligand. The results suggest that the effect of complexation of uranyl with nitrate on the uranyl sorption can be negligible and the sorption can be described Freundlich and D-R model very well. The positive effect of phosphate on the uranyl sorption was found, though the extent of effect was decreased with increasing pH. The positive effect and the negative effect of FA on the uranyl sorption were found at low pH and high pH ranges, respectively. The sorption edge of uranyl sorption remained unaffected in the presence of PH in the pH 2-10. In the presence of SA, the no effect and the negative effect on the uranyl sorption were, respectively, found at low pH and high pH ranges. The negative effect of CA on the uranyl sorption was found in the pH 2-10. (author)

  10. Sodium dodecyl sulfate coated alumina modified with a new Schiff's base as a uranyl ion selective adsorbent

    Energy Technology Data Exchange (ETDEWEB)

    Tashkhourian, J., E-mail: tashkhourian@susc.ac.ir [Department of Chemistry, College of Science, Shiraz University, 71454 Shiraz (Iran, Islamic Republic of); Moradi Abdoluosofi, L.; Pakniat, M. [Department of Chemistry, Faculty of Science, Persian Gulf University, Bushehr 75169 (Iran, Islamic Republic of); Montazerozohori, M. [Department of Chemistry, Faculty of Science, Yasouj University, Yasouj (Iran, Islamic Republic of)

    2011-03-15

    A simple and selective method was used for the preconcentration and determination of uranium(VI) by solid-phase extraction (SPE). In this method, a column of alumina modified with sodium dodecyl sulfate (SDS) and a new Schiff's base ligand was prepared for the preconcentration of trace uranyl(VI) from water samples. The uranium(VI) was completely eluted with HCl 2 M and determined by a spectrophotometeric method with Arsenazo(III). The preconcentration steps were studied with regard to experimental parameters such as amount of extractant, type, volume and concentration of eluent, pH, flow rate of sample source and tolerance limit of diverse ions on the recovery of uranyl ion. A preconcentration factor more than 200 was achieved and the average recovery of uranyl(VI) was 99.5%. The relative standard deviation was 1.1% for 10 replicate determinations of uranyl(VI) ion in a solution with a concentration of 5 {mu}g mL{sup -1}. This method was successfully used for the determination of spiked uranium in natural water samples.

  11. Treatment of uranyl nitrate and flouride solutions; Tratamiento de soluciones que contienen nitrato de uranilo y fluoruros

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigo Otero, A; Rodrigo Vilaseca, F; Morales Calvo, G

    1977-07-01

    A theoretical study on the fluoride complexes contained in uranyl and aluminium solutions has been carried out. Likewise concentration limits and Duhring diagrams for those solutions have been experimentally established. As a result, the optimum operation conditions for concentration by evaporation in the treatment plant, have been deduced. (Author) 12 refs.

  12. An unprecedented two-fold nested super-polyrotaxane: sulfate-directed hierarchical polythreading assembly of uranyl polyrotaxane moieties

    Energy Technology Data Exchange (ETDEWEB)

    Mei, Lei; Wu, Qun-yan; Yuan, Li-yong; Wang, Lin; An, Shu-wen; Xie, Zhen-ni; Hu, Kong-qiu; Shi, Wei-qun [Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing (China); Chai, Zhi-fang [Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing (China); School of Radiological and Interdisciplinary Sciences and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, Suzhou (China); Burns, Peter C. [Department of Chemistry and Biochemistry, University of Notre Dame, IN (United States)

    2016-08-01

    The hierarchical assembly of well-organized submoieties could lead to more complicated superstructures with intriguing properties. We describe herein an unprecedented polyrotaxane polythreading framework containing a two-fold nested super-polyrotaxane substructure, which was synthesized through a uranyl-directed hierarchical polythreading assembly of one-dimensional polyrotaxane chains and two-dimensional polyrotaxane networks. This special assembly mode actually affords a new way of supramolecular chemistry instead of covalently linked bulky stoppers to construct stable interlocked rotaxane moieties. An investigation of the synthesis condition shows that sulfate can assume a vital role in mediating the formation of different uranyl species, especially the unique trinuclear uranyl moiety [(UO{sub 2}){sub 3}O(OH){sub 2}]{sup 2+}, involving a notable bent [O=U=O] bond with a bond angle of 172.0(9) . Detailed analysis of the coordination features, the thermal stability as well as a fluorescence, and electrochemical characterization demonstrate that the uniqueness of this super-polyrotaxane structure is mainly closely related to the trinuclear uranyl moiety, which is confirmed by quantum chemical calculations. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Ratiometric colorimetric determination of coenzyme A using gold nanoparticles and a binuclear uranyl complex as optical probes

    International Nuclear Information System (INIS)

    Wu, Rurong; Liao, Lifu; Li, Shijun; Yang, Yanyan; Xiao, Xilin; Nie, Changming

    2016-01-01

    We describe a ratiometric colorimetric method for the determination of coenzyme A (CoA) by using gold nanoparticles (AuNPs) and bis-uranyl-bis-sulfosalophen (BUBSS) as optical probes. BUBSS is a binuclear uranyl complex and formed through the chelating reaction of two uranyl ions with bis-sulfosalophen. CoA is captured by the AuNPs via the thiol group and this leads to the formation of CoA-AuNPs. In a second step, BUBSS binds two CoA-AuNPs through a coordination reaction between the uranyl ions in BUBSS and the phosphate groups in CoA-AuNPs. This causes the CoA-AuNPs to aggregate and results in a color change from wine red to blue. A ratiometric colorimetric assay was established for CoA based on the ratiometric measurement of absorbance changes at 650 and 525 nm. Their ratio is linearly related to the concentration of CoA in the 0 to 1.2 μmol⋅L -1 range, with a 6 nmol⋅ L- 1 detection limit under optimal conditions. The method was successfully applied to the determination of CoA in spiked liver samples with recoveries between 99.4 and 102.6 %. (author)

  14. Determination of the dissociation constants of some organic complexing agents and stability constants of their uranyl complexes by spectrophotometry

    International Nuclear Information System (INIS)

    1989-01-01

    The dissociation constants of the weak acids derived from quinizarin (1,4-dihydroxy anthraquinone); QMF (2-(2-fury l methyl)), QMPH (2-(2-phenyl methyl)) and QMN (2-(2-naphthyl methyl)) quinizarin were determined. The stability constants of uranyl complexes with the above mentioned ligands were investigated by: 1. The molar-ratio method. 2. Computer program

  15. Use of the ion exchange method for determination of stability constants of uranyl ions with three soil humic acids

    International Nuclear Information System (INIS)

    Tao Zuyi; Du Jinzhou

    1994-01-01

    The ion exchange equilibrium method proposed by Ardakani and Stevenson has not been widely used to determine the stability constants of metal-soil organic matter complexes. In this paper the Ardakani-Stevenson's method has been modified and the stability constants of uranyl ion complexes with three soil humic acids were determined by using the modified Ardakani-Stevenson's method. (orig.)

  16. Preparation of SnSe thin films by encapsulated selenization; Saput tipis SnSe disediakan dengan kaedah penselenidan tertudung-tebat

    Energy Technology Data Exchange (ETDEWEB)

    Sabar, D Hutagalung [Universitas Sumatera Utara, Medan (Indonesia). Dept. of Physics; Sakrani, Samsudi; Wahab, Yussof [Universiti Teknologi Malaysia, Skudai, Johor Bahru (Malaysia). Dept. of Physics

    1994-12-31

    Tin selenide thin films were prepared by encapsulated selenization. A stacked layer of evaporated Sn and Se films were annealed in a carbon block at temperatures 100 - 500 degree Celsius for 3 hours. X-ray analysis and SEM (Scanning electron) micrograph results showed that SnSe was initially formed at 150 degree Celsius with crystal size 30.0 nm and reached optimum formation at 200 daximum of 57.4 % yield of 5-decene. Other factors such as reaction temperatures, types of solvent and wt% of rhenium loadings influence the activity of the catalytic system.

  17. Voltammetry of uranyl chloride in the LiCl - KCl eutectic; Voltammetrie du chlorure d'uranyle dans l'eutectique LiCl - KC1

    Energy Technology Data Exchange (ETDEWEB)

    Fondanaiche, J C [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1965-07-01

    Spent UO{sub 2} - PuO{sub 2} fuels can be reprocessed in a molten salt media. Uranium dioxide can easily be dissolved as UO{sub 2}Cl{sub 2} in a molten salt bath using chlorine gas. A study of quantitative analysis of an uranyl chloride solution in the LiCl-KCl eutectic at 400 C has been performed here using voltammetry (a large area-graphite indicator electrode has been employed). The precision which is obtained is around 6 per cent for concentrations below 10{sup -2} M. Precision decreases slightly for more concentrated solutions. The study of polarization curves allowed to give a reduction mechanism for the UO{sub 2}{sup ++} ion. For dilute solutions, this reduction proceeds through the UO{sub 2}{sup +} ion. But interpretation of current-potential curves is made difficult by the dismutation reaction of the UO{sub 2} ion and by the fact that the surface of the indicator electrode is not renewed. (author) [French] Le traitement des combustibles a base d'oxydes (UO{sub 2} - PUO{sub 2}) peut etre effectue au moyen des sels fondus. Le bioxyde d'uranium passe aisement en solution sous forme de UO{sub 2}Cl{sub 2} dans un bain de sels fondus par action du chlore. Nous avons etudie ici l'analyse quantitative d'une solution de chlorure d'uranyle dans l'eutectique LiCl - KCl a 400 C par voltammetrie (electrode indicatrice de graphite d'assez grande surface). La precision est d'environ 6 pour cent pour les concentrations inferieures a 10{sup -2} M; elle est legerement moins bonne pour les solutions plus concentrees. L'examen des courbes de polarisation a permis de donner un mecanisme de reduction de l'ion UO{sub 2}: pour les solutions diluees, cette reduction se fait par l'intermediaire de l'ion UO{sub 2}{sup +}. Mais l'interpretation des courbes intensite-potentiel est rendue delicate par la reaction de dismutation de l'ion UO{sub 2}{sup +} et par le fait que la surface de l'electrode indicatrice n'est pas renouvelee. (auteur)

  18. Uranyl nitrate-exposed rat alveolar macrophages cell death: Influence of superoxide anion and TNF α mediators

    Energy Technology Data Exchange (ETDEWEB)

    Orona, N.S. [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); Tasat, D.R., E-mail: deborah.tasat@unsam.edu.ar [School of Science and Technology, National University of General Martín, Avda Gral Paz 5445 (1650) San Martín, Buenos Aires (Argentina); School of Dentistry, University of Buenos Aires, M. T. de Alvear 2142 (1122), Buenos Aires (Argentina)

    2012-06-15

    Uranium compounds are widely used in the nuclear fuel cycle, military and many other diverse industrial processes. Health risks associated with uranium exposure include nephrotoxicity, cancer, respiratory, and immune disorders. Macrophages present in body tissues are the main cell type involved in the internalization of uranium particles. To better understand the pathological effects associated with depleted uranium (DU) inhalation, we examined the metabolic activity, phagocytosis, genotoxicity and inflammation on DU-exposed rat alveolar macrophages (12.5–200 μM). Stability and dissolution of DU could differ depending on the dissolvent and in turn alter its biological action. We dissolved DU in sodium bicarbonate (NaHCO{sub 3} 100 mM) and in what we consider a more physiological vehicle resembling human internal media: sodium chloride (NaCl 0.9%). We demonstrate that uranyl nitrate in NaCl solubilizes, enters the cell, and elicits its cytotoxic effect similarly to when it is diluted in NaHCO{sub 3}. We show that irrespective of the dissolvent employed, uranyl nitrate impairs cell metabolism, and at low doses induces both phagocytosis and generation of superoxide anion (O{sub 2}{sup −}). At high doses it provokes the secretion of TNFα and through all the range of doses tested, apoptosis. We herein suggest that at DU low doses O{sub 2}{sup −} may act as the principal mediator of DNA damage while at higher doses the signaling pathway mediated by O{sub 2}{sup −} may be blocked, prevailing damage to DNA by the TNFα route. The study of macrophage functions after uranyl nitrate treatment could provide insights into the pathophysiology of uranium‐related diseases. -- Highlights: ► Uranyl nitrate effect on cultured macrophages is linked to the doses and independent of its solubility. ► At low doses uranyl nitrate induces generation of superoxide anion. ► At high doses uranyl nitrate provokes secretion of TNFα. ► Uranyl nitrate induces apoptosis through

  19. Synthesis and crystal structure of hydrogen selenates K(HSeO4)(H2SeO4) and Cs(HSeO4)(H2SeO4)

    International Nuclear Information System (INIS)

    Troyanov, S.I.; Morozov, I.V.; Zakharov, M.A.; Kemnitz, E.

    1999-01-01

    Hydrogen selenates of the compositions K(HSeO 4 )(H 2 SeO 4 ) and Cs(HSeO 4 )(H 2 SeO 4 ) are synthesized by the reaction of alkali metal carbonates with an excess of the concentrated selenic acid. The X-ray diffraction study showed that both compounds are isostructural to the corresponding hydrogen sulfates. The difference in the systems of hydrogen bonding are caused by various combinations of the acceptor functions of the oxygen atoms in the HSeO 4 and H 2 SeO 4 groups

  20. Uranyl ion sorption mechanisms on titanium oxide: a multi-scale approach

    International Nuclear Information System (INIS)

    Vandenborre, J.; Drot, R.; Simoni, E.; Dong, W.; Du, J.; Dossot, M.; Humbert, B.; Ehrhardt, J.J.

    2005-01-01

    Full text of publication follows: Radionuclides retention mechanisms onto mineral phases is of primary importance for nuclear waste management. The aim of the presented study is to demonstrate that it is possible to predict the retention properties of a methodological powdery substrate from the study of its natural crystallographic orientations. Among the radionuclides of interest, U(VI) can be seen as a model of the radionuclides oxo-cations. The substrate under study is the titanium oxide (TiO 2 ). In fact, rutile can be found as powder and also as manufactured single crystal which allows to study the retention processes on perfectly known crystallographic planes. Since the repartition of the different crystallographic orientations are known for the powder, the results obtained for the single crystals can directly be used to account for the powder retention properties. By using combined spectroscopic techniques such as TRLFS, XPS, DRIFT and SHG, it is possible to determine the nature of the reactive surface sites and also the surface species. XPS and TRLFS measurements allowed to determine that two same uranyl surface species were formed on titania (110) and (001). Only, the relative intensities of these species vary with the surface coverage. Atomic Force Microscopy was carried out to verify that no surface precipitation occurs for the higher surface coverages. Moreover, these analysis have also evidenced that the U(VI) sorption is homogeneous. These observations were corroborated by SHG experiments (mainly for (001)) which have also shown that the sorption occurs, in a first step, onto preferential surface symmetry axis. For rutile powder, the preferential crystallographic orientations are (110), (100) and (101) in the ratio 60/20/20. TRLFS and XPS experiments have shown that two uranyl surface species are formed whatever the pH value ranged from 1 to 5. The spectroscopic characteristics of these species are the same as the ones observed on (110) and (001

  1. A new uranyl phosphate sheet in the crystal structure of furongite

    Energy Technology Data Exchange (ETDEWEB)

    Dal Bo, Fabrice; Hatert, Frederic [Liege Univ. (Belgium). Lab. de Mineralogie; Philippo, Simon [Musee National d' Historie Naturelle, Luxembourg (Luxembourg). Section Mineralogie

    2017-06-15

    The crystal structure of furongite, Al{sub 4}[(UO{sub 2}){sub 4}(PO{sub 4}){sub 6}](OH){sub 2}(H{sub 2}O){sub 19.5}, from the Kobokobo pegmatite, Kivu, Democratic Republic of Congo, was solved for the first time. Furongite is triclinic, the space group P anti 1, Z=2, a = 12.1685(8), b = 14.1579(6), c = 17.7884(6) Aa, α = 79.822(3), β = 77.637(4), γ = 67.293(2) , and V = 2746.2(2)Aa{sup 3}. The crystal structure was refined from single crystal X-ray diffraction data to R{sub 1} = 0.0733 for 7716 unique observed reflections, and to wR{sub 2} = 0.2081 for all 12,538 unique reflections. The structure of furongite contains infinite uranyl phosphate sheets of composition [(UO{sub 2}){sub 4}(PO{sub 4}){sub 6}]{sup 10-} which are parallel to (1 0 1). The sheets are constituted by UrO{sub 5} pentagonal bipyramids and PO{sub 4} tetrahedra which share edges and vertices, and adjacent sheets are linked by a dense network of hydrogen bonds. Running through the sheets and connected mainly to the free apical oxygen atom of PO4 tetrahedra are Al octahedra connected together to form remarkable Al{sub 2}O{sub 5}(OH)(H{sub 2}O){sub 5} and Al{sub 4}O{sub 8}(OH){sub 2}(H{sub 2}O){sub 10} clusters. These Al clusters are only bonded to one sheet, and do not connect two adjacent sheets together. The topology of the uranyl phosphate sheets is related to the uranophane anion topology, and can be described as a new geometrical isomer of the uranophane group. Furongite is the first uranyl phosphate reported in nature with a U:P ratio of 2:3.

  2. How the Starting Precursor Influences the Properties of Polycrystalline CuInGaSe2 Thin Films Prepared by Sputtering and Selenization

    Directory of Open Access Journals (Sweden)

    Greta Rosa

    2016-05-01

    Full Text Available Cu(In,GaSe2 (CIGS/CdS thin-film solar cells have reached, at laboratory scale, an efficiency higher than 22.3%, which is one of the highest efficiencies ever obtained for thin-film solar cells. The research focus has now shifted onto fabrication processes, which have to be easily scalable at an industrial level. For this reason, a process is highlighted here which uses only the sputtering technique for both the absorber preparation and the deposition of all the other materials that make up the cell. Particular emphasis is placed on the comparison between different precursors obtained with either In2Se3 and Ga2Se3 or InSe and GaSe as starting materials. In both cases, the precursor does not require any heat treatment, and it is immediately ready to be selenized. The selenization is performed in a pure-selenium atmosphere and only lasts a few minutes at a temperature of about 803 K. Energy conversion efficiencies in the range of 15%–16% are reproducibly obtained on soda-lime glass (SLG substrates. Similar results are achieved if commercial ceramic tiles are used as a substrate instead of glass. This result is especially useful for the so-called building integrated photovoltaic. Cu(In,GaSe2-based solar cells grown directly on ceramic tiles are ideal for the fabrication of ventilated façades in low impact buildings.

  3. Selenization of mixed metal oxides for dense and ZnSe-free Cu{sub 2}ZnSnSe{sub 4} absorber films

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Yitao; Chen, Guilin; Pan, Bin; Li, JianMin; Jiang, Guoshun; Liu, Weifeng, E-mail: liuwf@ustc.edu.cn; Zhu, Changfei, E-mail: cfzhu@ustc.edu.cn

    2014-04-05

    Highlights: • ZnSe-free CZTSe films with large grains was prepared from mixed oxides nanopraticles. • Appearance of Zn{sub 2}SnO{sub 4} in mixed oxides precursors leads to the absence of ZnSe secondary phrase. • To obtain pure CZTSe phase, different treating temperature was used. -- Abstract: Cu{sub 2}ZnSnSe{sub 4} (CZTSe) films were prepared by direct selenization of Cu{sub 2}O, SnO{sub 2} and Zn{sub 2}SnO{sub 4} precursors. Oxides precursors were prepared by baking hydroxides precipitation. In order to obtain ZnSe-free CZTSe films, Zn{sub 2}SnO{sub 4} was used to replace separated ZnO and SnO{sub 2} as one of the precursors. Through X-ray diffraction (XRD), scanning electron microscopy (SEM), it was found that CZTSe films, with micron-sized dense grains, were obtained in our work. From Raman spectra, it was also found that the ZnSe secondary phase was absent after the selenization. An energy bandgap about 0.86 eV was obtained in our work, which confirmed the Stannite-CZTSe structure.

  4. Contribution to the study of uranyl salts in butyl phosphate solutions; Contribution a l'etude des solutions de sels d'uranyle dans les phosphates butyliques

    Energy Technology Data Exchange (ETDEWEB)

    Coulon, A. [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

    1965-06-01

    A spectroscopic study in the normal infrared region and involving the following associations: tri-alkyl phosphates (tri-butyl, tri-ethyl, tri-methyl), uranyl salts (nitrate, chloride, acetate) has confirmed the existence of an interaction between the phosphoryl group and the uranium atom, as shown by a movement of absorption band for the valency P = 0 from {approx} 1270 cm{sup -1} to {approx} 1180 cm{sup -1}. A study of the preparation, analysis and spectroscopy of the solids obtained by the precipitation of uranyl salts by acid butyl phosphates has been carried out. By infrared spectrophotometry it has been shown that the tri-butyl and di-butyl phosphates are associated in non-polar diluents even before the uranium is introduced. The extraction of uranyl salts from acid aqueous solutions by a diluted mixture of tri-butyl and di-butyl phosphates proceeds by different mechanisms according to the nature of the ion (nitrate or chloride). (author) [French] Une etude spectroscopique dans l'infrarouge moyen portant sur les associations: - phosphates trialcoyliques (tributylique - triethylique - trimethylique) - sels d'uranyle (nitrate, chlorure, acetate) a confirme l'existence d'une interaction entre le groupement phosphoryle et l'atome d'uranium, se manifestant par un deplacement de la bande d'absorption de la vibration de valence P = 0 de {approx} 1270 cm{sup -1} a {approx} 1180 cm{sup -1}. Une etude preparative, analytique et spectroscopique des solides obtenus par precipitation de sels d'uranyle par les phosphates butyliques acides a ete effectuee. La spectrophotomerie infrarouge met en evidence l'association, anterieure a toute introduction d'uranium, des phosphates tributylique et dibutylique dans des diluants non polaires. L'extraction de sels d'uranyle, d'une solution aqueuse acide par un melange dilue de phosphates tributylique et dibutylique, s'effectue suivant des processus differents a la

  5. A study of adsorption equilibrium on quaternary ammonium resin in uranyl sulphate solution

    International Nuclear Information System (INIS)

    Xu Genfu; Xu Jiazhong; Zhu Jinghua

    1986-01-01

    Adsorption equilibrium on quaternary ammonium resin in uranyl sulphate solution, which is similar to composition used in uranium hydrometallurgy, was studied by chemical equivalent method. In the given range, the ratio of HSO 4 - to SO 4 2- on the resin is dependent on concentration of H + and ionic strength (μ) of solution, but it is independent of other anions sorbed on the resin. When the solution has μ of 0.1 to 0.5, pH of 1.5 to 1.9 and 0.5 x 10 -3 to 2.0 x 10 -3 M of uranium, the value of n in complex UO 2 (SO 4 ) n 2-2n is 2.5 to 2.7. The uranium occupies about 30% to 50% of total resin capacity

  6. Development of the process for production of UO2 powder by atomization of uranyl nitrate

    International Nuclear Information System (INIS)

    Oliveira Lainetti, P.E. de.

    1991-01-01

    A method of direct conversion of uranyl nitrate hexahydrate (UNH) solution to ceramic grade uranium dioxide powders by thermal denitration in a furnace that combines atomization nozzle and a gas stirred bed is described. The main purpose of this work is to show that this alternative process is technically viable, specially if the recovery of the scrap generated in the nuclear fuel pellet production is required, without further generation of new liquid wastes. The steps for the development of the denitration unit as well as the characteristics of the final powders are described. Powder production experiments have been carried out for different atomization gas pressures and furnace upper section temperatures. Determination of impurity content, specific surface area, particle size and pore size distribution, density, U content, and O/U rate of uranium dioxide powders have been done; phase identification and morphology studies have also been performed. Sintered pellets have been studied by hydrostatic density determination and microstructure analyses. (author)

  7. Complexes of uranyl nitrate with 2,6-pyridinedicarboxamides: synthesis, crystal structure, and DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Alyapyshev, Mikhail; Babain, Vasiliy [ITMO University, 49, Kronverksky pr., 197101, St. Petersburg (Russian Federation); ThreeArc Mining Ltd., 5, Stary Tolmachevskiy per., 115184, Moscow (Russian Federation); Tkachenko, Lyudmila; Lumpov, Alexander [Khlopin Radium Institute, 28, 2nd Murinskiy pr., 194021, St. Petersburg (Russian Federation); Gurzhiy, Vladislav; Zolotarev, Andrey; Dar' in, Dmitriy [St. Petersburg State University, 7-9, Universitetskaya nab., 199034, St. Petersburg (Russian Federation); Ustynyuk, Yuriy; Gloriozov, Igor [M.V. Lomonosov Moscow State University, 119991, Moscow (Russian Federation); Paulenova, Alena [Department of Nuclear Engineering, Oregon State University, Corvallis, OR (United States)

    2017-05-04

    Two complexes of uranyl nitrate with N,N,N',N'-tetrabutyl-2,6-pyridinedicarboxamide (TBuDPA) and N,N'-diethyl-N,N'-diphenyl-2,6-pyridinedicarboxamide (EtPhDPA) were synthesized and studied. The complex of tetraalkyl-2,6-pyridinedicarboxamide with metal nitrate was synthesized for the first time. XRD analysis revealed the different type of complexation: a 1:1 metal:ligand complex for EtPhDPA and complex with polymeric structure for TBuDPA. The quantum chemical calculations (DFT) confirm that both ligands form the most stable complexes that match the minimal values pre-organization energy of the ligands. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Relationship of the vibrational frequency of the uranyl ion with the uranium electronegativity

    International Nuclear Information System (INIS)

    Rodriguez S, A.; Martinez Q, E.

    1990-07-01

    It has been demonstrated that the vibrational asymmetric frequency of the uranyl ion, it experiences a consistent spectrochemical displacement with the variations of electronegativity of the uranium in their complexes. The values of the electronegativity of the uranium they were dear by means of calculations that it involves measures of those lengths of the connection uranium-oxygen, obtained by vibrational spectroscopy, effective nuclear charges and the Allred and Rochow equation. The results show the evidence of a natural order that relates to the vibrational frequency with the electronegativity of the uranium atom; settling down that if the electronegativity is graph against it bond length to the oxygen or to it frequency value, a simple relationship is obtained as a form to obtain clear responses in absence of complementary information. (Author)

  9. A series of sheet-structured alkali metal uranyl oxalate hydrates: structures and IR spectra

    International Nuclear Information System (INIS)

    Giesting, P.A.; Porter, N.J.; Burns, P.C.

    2006-01-01

    The novel compounds K[(UO 2 ) 2 (C 2 O 4 ) 2 OH] . 2 H 2 O (KUrO x ), Rb[(UO 2 ) 2 (C 2 O 4 ) 2 OH] . 2 H 2 O (RbUrO x ), and Cs[(UO 2 ) 2 (C 2 O 4 ) 2 OH] . H 2 O (CsUrO x ) have been synthesized by mild hydrothermal methods. Single crystal diffraction data collected at 125 K using MoK α radiation and a CCD-based area detector were used to solve and refine the crystal structures by full-matrix least-squares techniques to agreement indices (KUrO x , RbUrO x , CsUrO x ) wR 2 = 0.045, 0.062, 0.042 for all data, and R1 = 0.023, 0.030, 0.022 calculated for 1834, 1863, 1821 unique reflections respectively. The compounds KUrO x , RbUrO x , and CsUrO x are all monoclinic, space group P2 1 /m, Z = 2. The unit cell of KUrO x has the dimensions a = 5.6427(4), b = 13.7123(9), c = 9.2669(6) Aa, β = 98.7490(10) , V = 708.68(8) Aa 3 . The unit cell of RbUrO x has the dimensions a = 5.6225(4), b = 13.8339(9), c = 9.3308(6) Aa, β = 98.1590(10) , V = 718.41(8) Aa 3 . The unit cell of CsUrO x has the dimensions a = 5.4688(3), b = 13.5710(8), c = 9.5408(5) Aa, β = 97.5830(10) , V = 701.90(7) Aa 3 . The structures consist of chains of uranyl pentagonal bipyramids connected by oxalate groups and hydroxyl groups, and are isotypic with the compound NR 4 [(UO 2 ) 2 (C 2 O 4 ) 2 OH] . 2 H 2 O studied by Artem'eva et al. (2003); all four of these compounds are structurally composed of sheets made by polymerizing the chains of UO 2 C 2 O 4 (H 2 O) . 2 H 2 O (Jayadevan and Chackraburtty, 1972; Mikhailov et al., (1999)), this being achieved by removing a H atom from an H 2 O group in the coordination sphere of the uranyl ion to form a hydroxyl vertex that is shared by two uranyl ions. Compensating positive charges are provided by the inclusion of large monovalent cations in channels that run through the sheets; these channels also contain hydrogen-bound H 2 O groups. The positions of the cations and H 2 O groups change in relation to the uranyl oxalate sheets and to each other through the

  10. Preparation of acid deficient solutions of uranyl nitrate and thorium nitrate by steam denitration

    International Nuclear Information System (INIS)

    Yamagishi, Shigeru; Takahashi, Yoshihisa

    1996-01-01

    Acid deficient heavy metal (HM) nitrate solutions are often required in the internal gelation processes for nuclear fuel fabrication. The stoichiometric HM-nitrate solutions are needed in a sol-gel process for fuel fabrication. A method for preparing such nitrate solutions with a controlled molar ratio of nitrate/metal by denitration of acid-excess nitrate solutions was developed. The denitration was conducted by bubbling a nitrate solution with a mixture of steam+Ar. It was found that steam was more effective for the denitration than Ar. The acid deficient uranyl nitrate solution with nitrate/U=1.55 was yielded by steam bubbling, while not by only Ar bubbling. As for thorium nitrate, acid deficient solutions of nitrate/Th≥3.1 were obtained by steam bubbling. (author)

  11. Voltammetry of uranyl chloride in the LiCl - KCl eutectic

    International Nuclear Information System (INIS)

    Fondanaiche, J.C.

    1965-01-01

    Spent UO 2 - PuO 2 fuels can be reprocessed in a molten salt media. Uranium dioxide can easily be dissolved as UO 2 Cl 2 in a molten salt bath using chlorine gas. A study of quantitative analysis of an uranyl chloride solution in the LiCl-KCl eutectic at 400 C has been performed here using voltammetry (a large area-graphite indicator electrode has been employed). The precision which is obtained is around 6 per cent for concentrations below 10 -2 M. Precision decreases slightly for more concentrated solutions. The study of polarization curves allowed to give a reduction mechanism for the UO 2 ++ ion. For dilute solutions, this reduction proceeds through the UO 2 + ion. But interpretation of current-potential curves is made difficult by the dismutation reaction of the UO 2 ion and by the fact that the surface of the indicator electrode is not renewed. (author) [fr

  12. Properties and thermal decomposition of the double salts of uranyl nitrate-ammonium nitrate

    International Nuclear Information System (INIS)

    Notz, K.J.; Haas, R.A.

    1989-01-01

    The formation of ammonium nitrate-uranyl nitrate double salts has important effects on the thermal denitration process for the preparation of UO 3 and on the physical properties of the resulting product. Analyses were performed, and properties and decomposition behavior were determined for three double salts: NH 4 UO 2 (NO 3 ) 3 , (NH 4 ) 2 UO 2 (NO 3 ) 4 , and (NH 4 ) 2 UO 2 (NO 3 ) 4 ·2H 2 O. The tinitrate salt decomposes without melting at 270-300 C to give a γ-UO 3 powder of ∼3-μm average size, with good ceramic properties for fabrication into UO 2 nuclear fuel pellets. The tetranitrate dihydrate melts at 48 C; it also dehydrates to the anhydrous salt. The anhydrous tetranitrate decomposes exothermically, without melting, at 170-270 C by losing one mole of ammonium nitrate to form the trinitrate salt

  13. The extraction and effect in the system uranyl nitrate-dietyl ether-water

    International Nuclear Information System (INIS)

    Perez Luina, A.; Gutierrez Jodra, L.; Rius Miro, A.

    1960-01-01

    The solute transfer of uranyl nitrate from diethyl ether to water has been studied in a spray column using water as dispersed phase and a direction of extraction from ether to water. The column is 102 cm long and has a diameter of 4,7 cm. The entrances of the phases are 77 cm apart. The rates of flow of both phases have been used as variables and the concentration of the continuous phase has been determined at different heights. The curves of logarithm of concentration of the continuous phase vs. distance to interphase show the present of a drop of concentration in the entrance of the continuous phase. This depends on the rates of flow of the phases. No effect in the entrance of the dispersed phase has been found. (Author) 20 refs

  14. Processing of uranyl nitrate hexahydrate (UNH) at DOE's Fernald Site: Success and pitfalls

    International Nuclear Information System (INIS)

    Luken, D.W.; Brettschneider, D.J.; Heck, R.P. III; White, C.A.

    1996-01-01

    After 36 years of operation, uranium production at the Department of Energy Fernald Environmental Management Project (FEMP) was halted in 1989. Uranyl Nitrate Hexahydrate (UNH) had been produced during the uranium refining. In June 1991, DOE determined the UNH to be a mixed hazardous waste under the Resource Conservation and Recovery Act. A UNH Neutralization Project began processing UNH stored in stainless steel tanks located in various areas within the Fernald Plant 2/3 Complex. It was discovered that the valves, flanges, and other fittings of the UNH storage tanks were leaking. This made processing the UNH a high priority and Comprehensive, Environmental, Response, Compensation, and Liability Act Removal Action No. 20, Stabilization of UNH Inventories, was initiated. This report presents the successes and pitfalls of the cleanup of UNH

  15. Relative stability constants of the uranyl tropolonate system with neutral ligands in benzene

    Energy Technology Data Exchange (ETDEWEB)

    Degetto, S; Baracco, L; Marangoni, G [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi; Celon, E

    1976-01-01

    The relative formation constants K*sub(L) of some uranyl tropolonate adducts with neutral ligands L (L = cyclopentanone, pyridine, dimethyl sulphoxide, 4-chloropyridine N-oxide, 4-methylpyridine N-oxide, triphenylphosphine oxide, and triphenylarsine oxide) of general formula (U0/sub 2/(trop)/sub 2/L) (Htrop = tropolone) have been determined spectrophotometrically by studying the equilibria ((UO/sub 2/(trop)/sub 2/)/sub 2/) + 2L = 2 (UO/sub 2/(trop)/sub 2/L) in the benzene at 25/sup 0/C. The K*sub(L) sequence obtained can be used as a quantitative scale of donor ability of the various neutral ligands toward the common substrate. Other attempted qualitative correlations based on i.r., /sup 1/H n.m.r., and thermal measurements are compared and discussed.

  16. Conversion of ammonium uranyl carbonate to UO2 in a fluidized bed

    International Nuclear Information System (INIS)

    Zhao Jun; Qiu Lufu; Zhong Xing; Xu Heqing

    1989-11-01

    The conversion of AUC (Ammonium Uranyl Carbonate) to UO 2 was studied in a fluidized bed of 60 mm inner diameter based on the thermodynamics and kinetics data of decomposition-reduction of AUC. The influence of the reaction temperature, composition of fluidization gas and fluidization velocity on conversion were investigated by using N 2 , Ar and circulation gas (mixing gas of H 2 and CO obtained from the exhaust gas of the decomposition of AUC by catalyst crack-conversion) as the fluidization gas. The throughput is up to the high levels (3.32 kg(wet)/h·L) by using circulation gas or mixing of circulation gas and Ar (< 21%) as the fluidization gas when the reaction temperature exceeds 570 deg C

  17. Synthesis of alumina nano-sheets via supercritical fluid technology with high uranyl adsorptive capacity

    International Nuclear Information System (INIS)

    Jing Yu; Jun Wang; Zhanshuang Li; Qi Liu; Milin Zhang; Hongbin Bai; Caishan Jiao; Jun Wang; Lianhe Liu

    2012-01-01

    Supercritical carbon dioxide is beneficial to the synthesis of superior ultrafine and uniform materials due to its high chemical stability, low viscosity, high diffusivity, and 'zero' surface tension. γ-Alumina nano-sheets were obtained by a simple hydrothermal route in the presence of supercritical carbon dioxide. XRD, FTIR, SEM, TEM and nitrogen sorption isotherm were employed to characterize the samples. Alumina as-prepared has a high specific surface area of up to 200 ± 6 m 2 g -1 , which presents a high adsorption capacity (4.66 ± 0.02 mg g -1 ) for uranyl ions from aqueous solution. Furthermore, the adsorption process was found to be endothermic and spontaneous in nature. (authors)

  18. Sub-critical pulsed neutron experiments with uranyl nitrate solutions in spherical geometry

    International Nuclear Information System (INIS)

    Gurin, Victor N.; Ryazanov, Boris G.; Sviridov, Victor I.; Volnistov, Vladimir V.

    2003-01-01

    The pulse source method is used to study homogeneous solution assemblies. Three sets of sub-critical pulse experiments with spherical tanks filled with water solution of uranyl nitrate (90% enrichment) were carried out at the RF-GS facility, Obninsk, Russia. Seven spherical tanks with the volume within the range of 1.29 L to 19.8 L were used in the experiments. Three uranium concentrations were studied, i.e. 20.7, 29.6 and 37.5 g/L. The sub-critical experiments were analyzed with the MCNP 4A code based on the Monte-Carlo method, and with ENDF/B-V library. (author)

  19. Mixed ligand complexes of uranyl lactate with some simple and heterocyclic amines

    International Nuclear Information System (INIS)

    Jaiswal, S.R.; Rupainwar, D.C.

    1984-01-01

    Mixed ligand complexes of uranyl lactate with simple and heterocyclic amines having a general formula UO 2 (C 3 H 5 O 3 ).nL.xH 2 O, were prepared, where n=1 and x=1 for L=ethylenediamine (En), dimethyl aniline (DMAn), diethyl amine (DEA), orthophenylenediamine (OPDA), pyridine (Py), 2-picoline(2-Pic), 3-picoline(3-Pic), 4-Picoline(4-Pic), piperidine (Pipy), 2,4-lutidine (2,4 Lut), 2-Aminopyridine (2 APy), quinoline (Quin), isoquinoline (Isoquin) but x=0 for the ligands 2,2'-bipyrldyl (Bipy) and 1,10-phenenthroline (Phen). All the compounds are bright yellow coloured with high decomposition temp. (>200deg) and were characterized by electronic and infrared spectral data. (author)

  20. Study of water role during the complexing of uranyl aquanitrate compounds with cyclic polyethers

    International Nuclear Information System (INIS)

    Belomestnykh, V.I.; Sveshnikova, L.B.; Shabel'nik, K.S.

    1990-01-01

    By the method of vibrational spectroscopy and thermogravimetry the determining role of water molecules during complexing of uranyl aquonitrate compounds with macrocyclic polyethers is confirmed. It is ascertained that in the synthesized complexes of the composition UO 2 (NO 3 ) 2 (H 2 O) 2 ·mH 2 O·nL (m=0,1,2; L-18-crown-6, 15-crown-5, dibenzo-18-crown-6; n=1,2) molecules of macrocyclic ligand are joined at the expense of strong hydrogen bonds with participation of protons of crystallographically nonequivalent water molecules. In the compounds hydrogen bonds of water-water and water-nitrato group type are also realized. Energies of the above-mentioned bonds are calculated

  1. Clinico-biochemical studies on acute toxic nephropathy in goats due to uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Dash, P.K.; Joshi, H.C.

    1989-02-01

    Acute toxic nephropathy was produced in 6 healthy goats by injecting intravenously 1% uranyl nitrate (UN) (15 mg/kg body weight). The early painful clinical signs simulating shock progressed with subnormal temperature, slow-shallow respiration and arrhythmic pulse followed by death due to respiratory failure within 96 to 120 hr. All the affected goats had normocytic normochromic anemia, leucocytosis, neutrophilia with left shift eosinopenia, decreased monocytes and presence of 1-2% reticulocytes in the peripheral blood smears. On blood chemical analysis, a uniform and continuous rise was seen in serum creatinine with a concomitant daily increase of serum urea and uric acid. Simultaneous analysis of urine indicated polyuria leading to oliguria, acidic pH, albuminuria, glycosuria with presence of neutrophils, RBC's, epithelial and fatty casts, increase of triple phosphate, and cystine crystals reflecting acute damage of kidneys in the affected goats.

  2. Clinico-biochemical studies on acute toxic nephropathy in goats due to uranyl nitrate

    International Nuclear Information System (INIS)

    Dash, P.K.; Joshi, H.C.

    1989-01-01

    Acute toxic nephropathy was produced in 6 healthy goats by injecting intravenously 1% uranyl nitrate (UN) (15 mg/kg body weight). The early painful clinical signs simulating shock progressed with subnormal temperature, slow-shallow respiration and arrhythmic pulse followed by death due to respiratory failure within 96 to 120 hr. All the affected goats had normocytic normochromic anemia, leucocytosis, neutrophilia with left shift eosinopenia, decreased monocytes and presence of 1-2% reticulocytes in the peripheral blood smears. On blood chemical analysis, a uniform and continuous rise was seen in serum creatinine with a concomitant daily increase of serum urea and uric acid. Simultaneous analysis of urine indicated polyuria leading to oliguria, acidic pH, albuminuria, glycosuria with presence of neutrophils, RBC's, epithelial and fatty casts, increase of triple phosphate, and cystine crystals reflecting acute damage of kidneys in the affected goats

  3. Thermal and X-ray diffraction analysis studies during the decomposition of ammonium uranyl nitrate

    OpenAIRE

    Kim, B. H.; Lee, Y. B.; Prelas, M. A.; Ghosh, T. K.

    2012-01-01

    Two types of ammonium uranyl nitrate (NH4)2UO2(NO3)4?2H2O and NH4UO2(NO3)3, were thermally decomposed and reduced in a TG-DTA unit in nitrogen, air, and hydrogen atmospheres. Various intermediate phases produced by the thermal decomposition and reduction process were investigated by an X-ray diffraction analysis and a TG/DTA analysis. Both (NH4)2UO2(NO3)4?2H2O and NH4UO2(NO3)3 decomposed to amorphous UO3 regardless of the atmosphere used. The amorphous UO3 from (NH4)2UO2(NO3)4?2H2O was crysta...

  4. Cation-Cation Complexes of Pentavalent Uranyl: From Disproportionation Intermediates to Stable Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Mougel, Victor; Horeglad, Pawel; Nocton, Gregory; Pecaut, Jacques; Mazzanti, Marinella [CEA, INAC, SCIB, Laboratoire de Reconnaissance Ionique et Chimie de Coordination, CEA-Grenoble, 38054 GRENOBLE, Cedex 09 (France)

    2010-07-01

    Three new cation cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO{sub 2}py{sub 5})-(KI{sub 2}py{sub 2})]{sub n} (1) with the Schiff base ligands salen{sup 2-}, acacen{sup 2-}, and salophen{sup 2-} (H{sub 2}salen N, N'-ethylene-bis(salicylidene-imine), H{sub 2}acacen=-N, N'-ethylenebis(acetylacetone-imine), H{sub 2}salophen=N, N'-phenylene-bis(salicylidene-imine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen{sup 2-} in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetra-nuclear complexes ([UO{sub 2}-(acacen)]{sub 4}[{mu}{sub 8}-]{sub 2}[K([18]C-6)(py)]{sub 2}) (3) and ([UO{sub 2}(acacen)](4)[{mu}{sub 8}-]).2[K([222])(py)] (4) ([UO{sub 2}(salophen)](4)[{mu}{sub 8}-K]{sub 2}[mu(5)-KI]{sub 2}[(K([18]C-6)]).2 [K([18]C-6)-(thf){sub 2}].2I (5), and ([UO{sub 2}(salen)(4)][{mu}{sub 8}-Rb]{sub 2}[Rb([18]C-6)]{sub 2}) (9) ([222] = [222]cryptand, py =pyridine), presenting a T-shaped cation cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetra-nuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [U{sup V}O{sub 2}(salen)(py)][Cp*{sub 2}Co] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation cation complexes. The nature of the cation plays a key role in the preparation of stable cation cation complexes. Stable tetra-nuclear complexes form in the presence of K

  5. Synthesis and physicochemical properties of uranyl molybdate complexes of ammonium, potassium, rubidium, and cesium ions

    International Nuclear Information System (INIS)

    Fedoseev, A.M.; Budantseva, N.A.; Shirokova, I.B.; Yurik, T.K.; Andreev, G.B.; Krupa, Zh-K.

    2001-01-01

    Effect of experimental conditions on composition and intimacy of yield of crystal phases in the UO 2 MoO 4 -M 2 MoO 4 -H 2 O system, where M is cation of alkali metal or ammonium, is studied. The compounds of morphotropic raw with overall formula M 2 UO 2 (MoO 4 ) 2 ·H 2 O, where M=K, Ru, Cs, NH 4 , are synthesized by hydrothermal method from aqueous solutions at 160-180 Deg C. The dependence of composition and certain physico-chemical properties of the binary uranyl molybdates is investigated from the nature of out-spherical cation as well as IR-spectra and thermal behavior of synthesized compounds are inspected [ru

  6. Sequestering agent for uranyl chelation: a new family of CAMS ligands

    International Nuclear Information System (INIS)

    Leydier, A.; Pellet-Rostaing, S.; Favre-Reguillon, A.; Lemaire, M.; Lecercle, D.; Taran, F.

    2008-01-01

    The synthesis of new dipodal bis-sulfo-catechol-amide uranophiles is presented. Their binding abilities for uranyl cation were determined by UV spectrophotometry in aqueous media under various pH conditions and further studied by 1 H NMR analysis of the resonance signal of both aromatic protons of the sulfo-catechol-amide groups. The results showed that the efficiency of these hydrosoluble chelating agents depends on the nature of the spacers. Each ligand shows a more or less pronounced affinity for uranium. The best receptor is the ligand CYCAMS 5d obtained as a mixture of cis/trans isomers, which achieves the best compromise between rigidity and steric hindrance. (authors)

  7. Study of process parameters for reducing ammonium uranyl carbonate to uranium dioxide in fluidized bed furnace

    International Nuclear Information System (INIS)

    Leitao Junior, C.B.

    1992-01-01

    This work consists of studying the process parameters of AUC (ammonium uranyl carbonate) to U O 2 (uranium dioxide) reduction, with good physical and chemical characteristics, in fluidized bed. Initially, it was performed U O 2 cold fluidization experiments with an acrylic column. Afterward, it was done AUC to U O 2 reduction experiments, in which the process parameters influence in the granulometry, specific surface area, porosity and fluoride amount on the U O 2 powder produced were studied. As a last step, it was done compacting and sintering tests of U O 2 pellets in order to appreciate the U O 2 powder performance, obtained by fluidized bed, in the fuel pellets fabrication. (author)

  8. The final effect of extraction system in the uranyl nitrate-water-diethyl ether

    International Nuclear Information System (INIS)

    Perez Luina, A.; Gutierrez Jodra, L.; Miro, A. R.

    1957-01-01

    The solute transfer of uranyl nitrate from diallylether to water has been studied in a spray column using water as dispersed phase and a direction of extraction from ether to water. The column is 102 cm. long has a diameter of 4. 7 cm. The entrances of the phases are 7 7 cm. apart. The rates of flow of both phases have been used as variables and the concentration of the continuous phase has been determined; at different heights. The curves of logarithm of concentration of the continuous phase vs , distance to interphase show the presence of a drop of concentration in the entrance of the continuous phase. This depends on the rates of flow of the phases. No effect in the entrance of the dispersed phase has been found. (Author)

  9. NMR studies of hydrogen diffusion in hydrogen uranyl phosphate tetrahydrate (HUP)

    International Nuclear Information System (INIS)

    Metcalfe, K.

    1988-01-01

    1 H NMR spin-lattice relaxation times, T 1 (Zeeman) and T 1p (rotating frame) and spin-spin relaxation times, T 2 , and 31 P NMR solid-echoes are reported for phase I and II of hydrogen uranyl phosphate tetrahydrate (HUP) at temperatures in the range 200-323 K. The spectral density functions extracted from the measured relaxation times for phases I and II are consistent with a 2D diffusion mechanism for hydrogen motion. 31 P second moments determined from the solid-echoes show that all the hydrogens diffuse rapidly in phase I, and that the hydrogen-bond site nearest to the phosphate oxygen is not occupied in phase II. The mechanism for diffusion in phase II is discussed. 30 refs.; 6 figs.; 2 tabs

  10. Electrochemical characterization of Uranyl-TODGA complex in a room temperature ionic liquid

    International Nuclear Information System (INIS)

    Sengupta, Arijit; Murali, M.S.; Mohapatra, P.K.

    2014-01-01

    Room temperature ionic liquids are new materials finding extensive use in many applications such as syntheses, catalysis, electrochemistry etc. including separation science. Some of them are known as green solvents set to be environment-friendly. With a view to apply the favourable properties of these neoteric solvents to separation science in nuclear related fields such as reprocessing and waste remediation, electrochemical characterization of the metal ions encountered in above fields e.g. U(VI), Pu(IV), Np(IV), Am(III) etc. their complexes with the ligands often becomes necessary and useful. In the present piece of work, electrochemical characterization has been carried out by cyclic voltammetry of uranyl complex with one of the most promising trivalent actinide extractants, namely, tetraoctyldiglycolamide (TODGA) dissolved/extracted into a room temperature ionic liquid, 1-methyl-3-octyl imidazolium bis(trifluoro methylsulphonyl) imide (C 8 mimNTf 2 )

  11. Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium

    International Nuclear Information System (INIS)

    Serrano V, E. C.

    2011-01-01

    The extraction properties of octa-phosphinoylated para-tert butyl calix[8]arene (prepared in the laboratory) in chloroform towards uranyl ions from an aqueous-acidic-salty medium (HNO 3 -3.5 NaNO 3 ) containing uranyl nitrate salt, was investigated. Two spectroscopic techniques UV/Vis and Luminescence were used for this study. The latter permitted analyze the fluorescence from the uranyl ions influenced by the surrounding medium. Both permitted to learn about the power of this calixarene as extractant towards the mentioned ions. Its extraction ability or capability using this calixarene at 5.91 x 10 -4 M towards the uranyl ions was 400% as determined by UV/Vis while fluorescence revealed 100% of uranyl ion extraction. A closed analysis of the results obtained by using these techniques revealed that the stoichiometry of the main extracted species was 1calixarene:2 uranyl ions. The loading capacity of the calixarene ligand towards the uranyl ions was also investigated using both techniques. UV/Vis resulted to be inadequate for quantifying exactly the loading capacity of the calixarene whereas luminescence was excellent indeed, using a 5.91 x 10 -4 M calixarene concentration, its loading capacity was 0.157 M of free uranyl ions from 0.161 M of uranyl ions present in the aqueous-acidic-salty medium. The extracts from the ability and capacity studies were concentrated to dryness, purified and the dried extracts were analyzed by infrared and neutron activation analysis. By these techniques it was demonstrated that during the extraction of the uranyl ions by the calixarene ligand they form thermodynamically and kinetically stable complexes, since in the solid state, the 1:2, calixarene; uranyl ions stoichiometry was kept with the minimum formula: (UO 2 ) 2 B 8 bL 8 (NO 3 ) 4 (H 2 O) 4 CHCl 3 (CH 3 OH) 3 the methanol molecules come from its purification. It is proposed that B 8 bL 8 calixarene in chloroform medium is a good extractant for the treatment of nuclear wastes or

  12. Comprehensive analysis of the renal transcriptional response to acute uranyl nitrate exposure

    Directory of Open Access Journals (Sweden)

    Argiles Angel

    2006-01-01

    Full Text Available Abstract Background Chemical and radiological toxicities related to uranium acute exposure have been widely studied in nuclear fuel workers and military personnel. It is well known that uranyl nitrate induces acute renal failure (ARF. However, the mechanisms of this metal-induced injury are not well defined at the molecular level. Results Renal function and histology were assessed in mice receiving uranyl nitrate (UN(+ and controls (UN(-. To identify the genomic response to uranium exposure, serial analysis gene expression (SAGE of the kidney was performed in both groups. Over 43,000 mRNA SAGE tags were sequenced. A selection of the differentially expressed transcripts was confirmed by real-time quantitative PCR and Western blotting. UN(+ animals developed renal failure and displayed the characteristic histological lesions of UN nephropathy. Of the >14,500 unique tags identified in both libraries, 224 had a modified expression level; they are known to participate in inflammation, ion transport, signal transduction, oxidative stress, apoptosis, metabolism, and catabolism. Several genes that were identified had not previously been evaluated within the context of toxic ARF such as translationally controlled tumor protein, insulin like growth factor binding protein 7 and ribosomal protein S29, all apoptosis related genes. Conclusion We report a comprehensive description of the UN induced modifications in gene expression levels, including the identification of genes previously unrelated to ARF. The study of these genes and the metabolisms they control should improve our understanding of toxic ARF and enlighten on the molecular targets for potential therapeutic interventions.

  13. Structural investigation of the complexation of uranyl and lanthanide ions by CMPO-functionalized calixarenes

    International Nuclear Information System (INIS)

    Cherfa, S.

    1998-12-01

    A way to reduce the volume of nuclear wastes is to make a simultaneous extraction of actinides and lanthanides for their ulterior separation. Historically, the two first series of extractants used for the reprocessing of these wastes are the phosphine oxides and the CMPO (carbamoyl methyl phosphine oxide). In order to better know the type of complexes formed during the extraction, have been carried out structural studies concerning these two series (uranyl complexes and lanthanide nitrates). These studies have been carried out by X-ray diffraction on monocrystals. More recently, a new series of extracting molecules of lanthanides (III) and actinides (III) have been developed. It has been shown that in functionalizing an organic macrocycle of calixarene type (cyclic oligomer resulting of the poly-condensation of phenolic units) by a ligand of CMPO type, the extracting power of these molecules in terms of yield and selectivity towards the lighter lanthanides was superior to those of the CMPO alone. This study, carried out by X-ray diffraction on monocrystals of complexes formed between these ligands calix[4]arenes-CMPO (with 4 phenolic units) with uranyl and lanthanides nitrates, has allowed to define the type of the formed complexes, that is to say to establish the stoichiometry and the coordination mode (monodentate or bidentate) of the CMPO functions. These different steps of characterization have allowed too to determine the correlations existing between the complexes structures in the one hand and the selectivity and the exacerbation of the extracting power measured in liquid phase on the other hand. (O.M.)

  14. Transuranium element incorporation into the β-U3O8 uranyl sheet

    International Nuclear Information System (INIS)

    Miller, M.L.; Burns, P.C.; Ewing, R.C.; Finch, R.J.

    1997-01-01

    Spent nuclear fuel (SNF) is unstable under oxidizing conditions. Although recent studies have determined the paragenetic sequence for uranium phases that result from the corrosion of SNF, there are only limited data on the potential of alteration phases for the incorporation of transuranium elements. The crystal chemical characteristics of transuranic elements (TUE) are to a certain extent similar to uranium; thus TUE incorporation into the sheets of uranyl oxide hydrate structures can be assessed by examination of the structural details of the β-U 3 O 8 sheet type. The sheets of uranyl polyhedra observed in the crystal structure of β-U 3 O 8 also occur in the mineral billietite, where they alternate with α-U 3 O 8 type sheets. Preliminary crystal structure determinations for the minerals ianthinite, and wyartite, indicate that these phases also contain β-U 3 O 8 type sheets. The β-U 3 O 8 sheet anion topology contains triangular, rhombic, and pentagonal sites in the proportions 2:1:2. In all structures containing β-U 3 O 8 type sheets, the triangular sites are vacant. The pentagonal sites are filled with U 6+ O 2 forming pentagonal bipyramids. The rhombic dipyramids filling the rhombic sites contain U 6+ O 2 in billietite, U 4+ O 2 in β-U 3 O 8 , U 4+ (H 2 O) 2 in ianthinite, and U 4+ O 3 in wyartite-II. Interlayer species include: H 2 O (billietite, wyartite II, and ianthinite), Ba 2+ (billietite) Ca 2+ wyartite II, and Co 3 2- wyartite II; there is no interlayer in β-U 3 O 8 . The similarity of known TUE coordination polyhedra with those of U suggests that the β-U 3 O 8 sheet will accommodate TUE substitution coupled with variations in apical anion configuration and interlayer population providing the required charge balance

  15. Extraction of uranyl nitrate from aqueous solution by dicyclohexyl-18-crown-6

    International Nuclear Information System (INIS)

    Kojima, Takashi; Ohno, Fumiaki; Fukutomi, Hiroshi

    1981-01-01

    The extraction of uranyl nitrate from aqueous solution by dicyclohexyl-18-crown-6(DCC) in cyclohexane, toluene, benzene, chlorobenzene and nitrobenzene has been studied in varying the concentrations of DCC and uranyl nitrate. The extraction equilibria have been discussed in detail based on the law of mass action, and it has been found that the extractions in cyclohexane, toluene and benzene are represented by the equation 2 DCC(org) + UO 2 2+ (aq) + 2 NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org), and the extraction in chlorobenzene is described by the equations DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = DCC UO 2 (NO 3 ) 2 (org) and 2DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org), and the extraction in nitrobenzene is expressed by the equations DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = DCC UO 2 (NO 3 ) 2 (org), 2DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org) and DCC UO 2 (NO 3 ) 2 (org) = DCC UO 2 NO 3 + (org) + NO 3 - (org). The equilibrium constants of the reaction 2DCC(org) + UO 2 2+ (aq) + 2NO 3 - (aq) = (DCC) 2 UO 2 (NO 3 ) 2 (org) increase in the order of cyclohexane < toluene < benzene < chlorobenzene < nitrobenzene. The enthalpy and entropy changes for the extraction reactions into benzene and nitrobenzene were determined from the change of the extraction equilibrium constants with temperature. (author)

  16. Stereognostic coordination chemistry. 1. The design and synthesis of chelators for the uranyl ion

    International Nuclear Information System (INIS)

    Franczyk, T.S.; Czerwinski, K.R.; Raymond, K.N.

    1992-01-01

    A new approach to the molecular recognition of metal oxo cations is introduced based on a ligand design strategy that provides at least one hydrogen bond donor for interaction with oxo group(s) as well as conventional electron pair donor ligands for coordination to the metal center. This concept of stereognostic coordination of oxo metal ions is exemplified in the design of four tripodal ligands-tris[2-(2-carboxyphenoxy)ethyl]amine[NEB],tris[3-(2-carboxyphenoxy)propyl]amine[NPB], tris[3-(2-carboxynaphthyl-3-oxy)propyl]amine [NPN], and tris[3-(2-carboxy=4octadecylphenoxy)propyl]amine[NPodB] - for sequestration of the uranyl ion. The ligands NEB, NPB, and NPN form 1:1 complexes with UO 2 2+ . The bidentate coordination of carboxyl groups of these compounds is indicated by the infrared spectra, which offer some support for the presence of a hydrogen bond to the uranyl group. Mass spectral data corroborate CPK model predictions that more than five intervening atoms between the tertiary nitrogen atom and the carboxylate groups are required for metal ion incorporation and monomeric complex formation. Solvent extractions of aqueous UO 2 2+ into chloroform solutions of the ligands have shown them to be powerful extractants. In the case of the very hydrophobic ligand NPodB the stoichiometry of the complexation reaction is shown to be 1:1 UO 2 /ligand complex formed by the release of 3 protons. The extraction is quantitative at pH 2.5, and an effective extraction coefficient of about 10 11 is estimated for neutral aqueous solutions of UO 2 2+ . 81 refs., 13 figs., 2 tabs

  17. X-ray Absorption Spectroscopy Identifies Calcium-Uranyl-Carbonate Complexes at Environmental Concentrations

    International Nuclear Information System (INIS)

    Kelly, Shelly D.; Kemner, Kenneth M.; Brooks, Scott C.

    2007-01-01

    Current research on bioremediation of uranium-contaminated groundwater focuses on supplying indigenous metal-reducing bacteria with the appropriate metabolic requirements to induce microbiological reduction of soluble uranium(VI) to poorly soluble uranium(IV). Recent studies of uranium(VI) bioreduction in the presence of environmentally relevant levels of calcium revealed limited and slowed uranium(VI) reduction and the formation of a Ca-UO2-CO3 complex. However, the stoichiometry of the complex is poorly defined and may be complicated by the presence of a Na-UO2-CO3 complex. Such a complex might exist even at high calcium concentrations, as some UO2-CO3 complexes will still be present. The number of calcium and/or sodium atoms coordinated to a uranyl carbonate complex will determine the net charge of the complex. Such a change in aqueous speciation of uranium(VI) in calcareous groundwater may affect the fate and transport properties of uranium. In this paper, we present the results from X-ray absorption fine structure (XAFS) measurements of a series of solutions containing 50 lM uranium(VI) and 30 mM sodium bicarbonate, with various calcium concentrations of 0-5 mM. Use of the data series reduces the uncertainty in the number of calcium atoms bound to the UO2-CO3 complex to approximately 0.6 and enables spectroscopic identification of the Na-UO2-CO3 complex. At nearly neutral pH values, the numbers of sodium and calcium atoms bound to the uranyl triscarbonate species are found to depend on the calcium concentration, as predicted by speciation calculations

  18. Reaction of uranyl nitrate with carboxylic di-acids under hydrothermal conditions. Crystal structure of complexes with L(+)-tartaric and oxalic acids

    International Nuclear Information System (INIS)

    Thuery, P.

    2007-01-01

    L(+)-tartaric acid reacts with uranyl nitrate in the presence of KOH, under mild hydrothermal conditions, to give the complex [UO 2 (C 4 H 4 O 6 )(H 2 O)] (1), the first uranyl tartrate to be crystallographically characterized. Each tartrate ligand bridges three uranyl ions, one of them in chelating fashion through proximal carboxylate and hydroxyl groups. The resulting assemblage is two-dimensional, with the uranyl pentagonal bipyramidal coordination polyhedra separated from one another. Prolonged heating of an uranyl tartrate solution resulted in oxidative cleavage of the acid and formation of the oxalate complex [(UO 2 ) 2 (C 2 O 4 ) 2 (OH)Na(H 2 O) 2 ] (2). The bis-bidentate oxalate and bridging hydroxide groups ensure the formation of sheets with corner-sharing uranyl pentagonal bipyramidal coordination polyhedra, in which six-membered metallacycles encompass the sodium ions. These sheets are assembled into a three-dimensional framework through further oxo-bonding of the sodium ions. (authors)

  19. Effect of the temperature and oxalic acid in the uranyl sorption in zircon; Efecto de la temperatura y acido oxalico en la sorcion de uranilo en circon

    Energy Technology Data Exchange (ETDEWEB)

    Ordonez R, E.; Almazan T, M. G.; Garcia G, N. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Hernandez O, R., E-mail: eduardo.ordonez@inin.gob.mx [Instituto Tecnologico de Veracruz, Ingenieria Quimica, Miguel Angel de Quevedo No. 2779, 91860 Veracruz (Mexico)

    2012-10-15

    In this work the results of the temperature effect study are presented on uranyl solutions adsorbed on zirconium silicate (ZrSiO{sub 4}) and also on the compounds formed in surface with oxalic acid. The adsorption isotherms of uranyl on hydrated zircon with NaClO{sub 4} 0.5 M, show an increase of the uranyl sorption efficiency when increasing the temperature from 20 to 4 C with a sudden descent in this efficiency when changing the temperature at 60 C. The uranyl sorption efficiency increases to hydrate the zircon with a solution of oxalic acid 0.1 M, maintaining the same tendency regarding to the temperatures of the sorption in medium NaClO{sub 4} 0.5 M. The complex formation in the zircon surface with organic acids of low molecular weight increases the fixation of the uranyl in solution due to the formation of ternary systems, in the order Zircon/A. Organic/Uranyl, without altering their response to the temperature. (Author)

  20. [UO{sub 2}Cl{sub 2}(phen){sub 2}], a simple uranium(VI) compound with a significantly bent uranyl unit (phen=1,10-phenanthroline)

    Energy Technology Data Exchange (ETDEWEB)

    Schoene, Sebastian; Radoske, Thomas; Maerz, Juliane; Stumpf, Thorsten; Patzschke, Michael; Ikeda-Ohno, Atsushi [Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institute of Resource Ecology, Dresden (Germany)

    2017-10-04

    A simple synthesis based on UO{sub 2}Cl{sub 2}.n H{sub 2}O and 1,10-phenanthroline (phen) resulted in the formation of a new uranyl(VI) complex [UO{sub 2}Cl{sub 2}(phen){sub 2}] (1), revealing a unique dodecadeltahedron coordination geometry around the uranium center with significant bending of the robust linear arrangement of the uranyl (O-U-O) unit. Quantum chemical calculations on complex 1 indicated that the weak but distinct interactions between the uranyl oxygens and the adjacent hydrogens of phen molecules play an important role in forming the dodecadeltahedron geometry that fits to the crystal structure of 1, resulting in the bending the uranyl unit. The uranyl oxygens in 1 are anticipated to be activated as compared with those in other linear uranyl(VI) compounds. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)