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Sample records for actinide iii cations

  1. Actinide cation-cation complexes

    International Nuclear Information System (INIS)

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

    1994-12-01

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

  2. Thermodynamic study on the complexation of Trivalent actinide and lanthanide cation by N-donor ligands in homogeneous conditions; Etude thermodynamique de la complexation des ions actinide (III) et lanthanide (III) par des ligands polyazotes en milieu homogene

    Energy Technology Data Exchange (ETDEWEB)

    Miguirditchian, M

    2004-07-01

    Polydentate N-donor ligands, alone or combined with a synergic acid, may selectively extract minor actinides(III) from lanthanide(III) ions, allowing to develop separation processes of long-live radioelements. The aim of the researches carried out during this thesis was to better understand the chemical mechanisms of the complexation of f-elements by Adptz, a tridentate N-donor ligand, in homogeneous conditions. A thermodynamic approach was retained in order to estimate, from an energetic point of view, the influence of the different contributions to the reaction, and to acquire a complete set of thermodynamic data on this reaction. First, the influence of the nature of the cation on the thermodynamics was considered. The stability constants of the 1/1 complexes were systematically determined by UV-visible spectrophotometry for every lanthanide ion (except promethium) and for yttrium in a mixed solvent methanol/water in volume proportions 75/25%. The thermodynamic parameters ({delta}H{sup 0} {delta}{sup S}) of complexation were estimated by the van't Hoff method and by micro-calorimetry. The trends of the variations across the lanthanide series are compared with similar studies. The same methods were applied to the study of three actinide(III) cations: plutonium, americium and curium. The comparison of these values with those obtained for the lanthanides highlights the increase of stability of these complexes by a factor of 20 in favor of the actinide cations. This gap is explained by a more exothermic reaction and is associated, in the data interpretation, to a higher covalency of the actinide(III)-nitrogen bond. Then, the influence of the change of solvent composition on the thermodynamic of complexation was studied. The thermodynamic parameters of the complexation of europium(III) by Adptz were determined for several fractions of methanol. The stability of the complex formed increases with the percentage of methanol in the mixed solvent, owing to an

  3. Structural characterization of the Actinides (III) and (IV) - DOTA complexes

    International Nuclear Information System (INIS)

    Audras, Matthieu

    2014-01-01

    The polyamino-carboxylate anions have been identified as compounds of interest in the operations of actinide separation, in actinide migration in the environment and in human radio-toxicology. The structural characterization of complexes formed between actinides and polyamino-carboxylates ligands is essential for a better understanding of actinide-ligands interactions. Among the polyamino-carboxylate anions, the DOTA ligand (1,4,7,10-tetraaza-cyclododecane tetraacetic acid) is described as a very strong complexing agent of the lanthanides(III), but has been little studied with actinides. The objective of this thesis is to describe the complexes formed between the actinides (III) and (IV) and the DOTA ligand, and compare them with the lanthanide complexes. For this, an approach has been introduced to characterize the complexes by complementary analytical techniques (spectrophotometry, electro-spray ionization mass spectrometry, NMR, EXAFS, electrochemistry), but also by calculations of theoretical chemistry to help the interpretation of the experimental data. The formation of a 1:1 complex is observed with the actinides(III) (plutonium and americium) as for lanthanides(III): rapid formation of intermediate species which evolves slowly towards the formation of a limit complex. Within this complex, the cation is located inside the cavity formed by the ligand. Four nitrogen atoms and four oxygen atoms from the carboxylate functions are involved in the coordination sphere of the cation. However, differences were observed in the bond lengths formed between the cation and the nitrogen atoms (the bonds are somewhat shorter in the case of actinide complexes) as well as the complexation kinetics, which is slightly faster for the actinides(III) than for lanthanide(III) ions of equivalent radius. The same behavior was observed in solution upon complexation of actinides(IV) (uranium, plutonium and neptunium): slow formation of a 1:1 complex (actinide(IV):ligand) in wherein the

  4. Basic research on solvent extraction of actinide cations with diamide compounds

    Energy Technology Data Exchange (ETDEWEB)

    Sasaki, Yuji [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    1998-11-01

    Newly synthesized 4 diamide compounds were tested for solvent extraction of actinide cations. It is obvious that N,N`-dimethyl-N,N`-dihexyl-3-oxapentanediamide (DMDHOPDA) can extract Eu(III), Th(IV), U(VI), Np(V), and Am(III) into organic solvent. Other 3 diamides hardly extract actinide ions, which is supposed that the reasons come from the difference of their chemical structures. In the synergistic extraction with a diamide and thenoyltrifluoroacetone (TTA), all diamides work as a extractant. Furthermore, by examining extracted species, it was confirmed that there are 4 kinds of chemical species of actinides with diamide and TTA. Finally, the mutual separation method of actinide (III), (IV), (V) and (VI) ions by solvent extraction using DMDHOPDA and TTA were developed. (author). 147 refs.

  5. Spin–orbit coupling in actinide cations

    DEFF Research Database (Denmark)

    Bagus, Paul S.; Ilton, Eugene S.; Martin, Richard L.

    2012-01-01

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

  6. Extraction chemistry of actinide cations by N,N-dialkylamides

    International Nuclear Information System (INIS)

    Condamines, N.; Musikas, C.

    1990-01-01

    N,N-dialkylamides are alternate extractants to tributylphosphate, TBP, for the actinides separation in nuclear fuel reprocessing. Extraction mechanisms of UO 2 2+ and Pu 4+ from nitric acid media are investigated for the amides DOBA and DOiBA. For low acidities, amides are neutral extractants. The stoechiometries of UO 2 (NO 3 ) 2 (Amide) 2 (Amide = DOBA or DOiBA), Pu(NO 3 ) 4 (DOBA) 2 are established. A bond between the oxygen of the carbonyl group and the metallic cation is the driving force of the transfer

  7. Site preferences of actinide cations in [NZP] compounds

    Science.gov (United States)

    Hawkins, H. T.; Spearing, D. R.; Smith, D. M.; Hampel, F. G.; Veirs, D. K.; Scheetz, B. E.

    2000-07-01

    Compounds adopting the sodium dizirconium tris(phosphate) (NaZr2(PO4)3) structure type belong to the [NZP] structural family of compounds. [NZP] compounds possess desirable properties that would permit their application as hosts for the actinides. These properties include compositional flexibility (i.e., three structural sites that can accommodate a variety of different cations), high thermal stability, negligible thermal expansion, and resistance to radiation damage. Experimental data indicate that [NZP] compounds resist dissolution and release of constituents over a wide range of experimental conditions. Moreover, [NZP] compounds may be synthesized by both conventional and novel methods and may be heat treated or sintered at modest temperatures (800 °C-1350 °C) in open or restricted systems.

  8. Static and dynamic modelling of lanthanide and actinide cations in solution

    International Nuclear Information System (INIS)

    Marjolin, A.

    2012-01-01

    We propose a theoretical approach, based on both quantum analyses (energy decomposition analysis and topological analysis of the chemical bond) and classical molecular dynamics, for the study of f-element complexes. First, we introduce the different QM methods adapted to the study of f-elements and use them for geometry optimization and interaction energy calculations of the model system [M-(OH 2 )] m+ where M is a lanthanide or actinide cation. We then perform energy decomposition analysis to quantify the physical nature of the metal-ligand interaction in terms of the different contributions. Furthermore, the different energy contributions will be used as reference curves for the parameterization of the polarizable force fields AMOEBA and SIBFA. Next, starting from the optimized geometries, we establish the reference diabatic dissociation curves at high level of theory so as to take into account the multi-reference nature of the systems. These dissociation curves will also be used for parameterization of the AMOEBA potential. We then propose a three step validation protocol as well as a first application, it being the computation of Gibbs hydration free energies for the f-element cations. We also propose an extension of the SIBFA force field to trivalent lanthanide ions and tetravalent actinide ions. Last, we use the topological analysis approaches of ELF and NCI to investigate the nature of the different interactions in Gadolinium(III) model and real systems. The aim of the whole study was to develop and apply different theoretical approaches so as to be able to discriminate between lanthanide and actinide cations. Indeed, despite their similar chemical behavior, they still feature a selective character that we wish to be able to both explain and predict. (author) [fr

  9. Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium.

    Science.gov (United States)

    Dau, Phuong D; Vasiliu, Monica; Peterson, Kirk A; Dixon, David A; Gibson, John K

    2017-12-06

    Actinyl chemistry is extended beyond Cm to BkO 2 + and CfO 2 + through transfer of an O atom from NO 2 to BkO + or CfO + , establishing a surprisingly high lower limit of 73 kcal mol -1 for the dissociation energies, D[O-(BkO + )] and D[O-(CfO + )]. CCSD(T) computations are in accord with the observed reactions, and characterize the newly observed dioxide ions as linear pentavalent actinyls; these being the first Bk and Cf species with oxidation states above IV. Computations of actinide dioxide cations AnO 2 + for An=Pa to Lr reveal an unexpected minimum for D[O-(CmO + )]. For CmO 2 + , and AnO 2 + beyond EsO 2 + , the most stable structure has side-on bonded η 2 -(O 2 ), as An III peroxides for An=Cm and Lr, and as An II superoxides for An=Fm, Md, and No. It is predicted that the most stable structure of EsO 2 + is linear [O=Es V =O] + , einsteinyl, and that FmO 2 + and MdO 2 + , like CmO 2 + , also have actinyl(V) structures as local energy minima. The results expand actinide oxidation state chemistry, the realm of the distinctive actinyl moiety, and the non-periodic character towards the end of the periodic table. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. X-ray study of chemical bonding in actinides(IV) and lanthanides(III) hexa-cyanoferrates

    International Nuclear Information System (INIS)

    Dumas, T.

    2011-01-01

    Bimetallic cyanide molecular solids derived from Prussian blue are well known to foster long-range magnetic ordering and show an intense inter-valence charge transfer band resulting from an exchange interaction through the cyanide-bridge. For those reasons the ferrocyanide and ferricyanide building blocks have been chosen to study electronic delocalization and covalent character in actinide bonding using an experimental and theoretical approach based on X-ray absorption spectroscopy. In 2001, the actinide (IV) and early lanthanides (III) hexacyanoferrate have been found by powder X-ray diffraction to be isostructural (hexagonal, P6 3 /m group). Here, extended X-ray Absorption Fine Structure (EXAFS) at the iron K-edge and actinide L 3 -edge have been undertaken to probe the local environment of both actinides and iron cations. In an effort to describe the cyano bridge, a double edge fitting procedure including both iron and actinide edges and based on multiple scattering approach has been developed. We have also investigated the electronic properties of these molecular solids. Low energy electronic transitions have been used iron L 2,3 edge, nitrogen and carbon K-edge and also actinides N 4,5 edge to directly probe the valence molecular orbitals of the complex. Using a phenomenological approach, a clear distinctive behaviour between actinides and lanthanides has been shown. Then a theoretical approach using quantum chemistry calculation has shown more specifically the effect of covalency in the actinide-ferrocyanide bond. More specifically, π interactions were underlined by both theoretical and experimental methods. Finally, in agreement with the ionic character of the lanthanide bonding no inter-valence charge transfer has been observed in the corresponding optical spectra of these compounds. On the contrary, optical spectra for actinides adducts (except for thorium) show an intense inter-valence charge transfer band like in the transition metal cases which is

  11. Separation by liquid-liquid extraction of actinides(III) from lanthanides(III) using new molecules: the picolinamides; Separation par extraction liquide-liquide des actinides(III) des lanthanides(III) par de nouvelles molecules: les picolinamides

    Energy Technology Data Exchange (ETDEWEB)

    Cordier, P Y [CEA Marcoule, Departement de Recherche en Retraitement et en Vitrification, 30 - Bagnols-sur-Ceze (France); [Clermont-Ferrand-2 Univ., 63 - Aubiere (France)

    1996-07-01

    In the field of long-lived radionuclides separation from waste generated during spent fuel reprocessing, the picolinamides have been chosen as potential extractants for the selective extraction of actinides (III) from lanthanides (III). The first studies initiated on the most simple molecule of the picolinamide family, namely 2-pyridinecarboxamide, pointed out that in an aqueous media the complexation stability constant between this ligand and Am(III) is roughly 10 times higher than the ones corresponding to Ln(III). The synthesis of lipophilic derivatives of 2-pyridinecarboxamide leaded to extraction experiments. The extraction of metallic cation by lipophilic picolinamides, according to a solvatation mechanism, is strongly dependent on the nature of the amide function: a primary amide function (group I) leads to a good extraction; on the contrary, there is a decrease for secondary (group II) and tertiary (group III) amide functions. From a theoretical point of view, this work leads finally to the following conclusions: confirmation of the importance of the presence of soft donor atoms within the extractants (nitrogen in our case) for An(III)/Ln(III). Also, sensitivity of this soft donor atom regarding the protonation reaction; prevalence in our case of the affinity of the extractant for the metallic cation over the lipophilia of the extractant to ensure good distribution coefficients. The extraction and Am(III)/Ln(III) separation performances of the picolinamides from pertechnetic media leads to the design of a possible flowsheet for the reprocessing of high level liquid waste, with the new idea of an integrated technetium reflux. (author) 105 refs.

  12. Separation by liquid-liquid extraction of actinides(III) from lanthanides(III) using new molecules: the picolinamides

    International Nuclear Information System (INIS)

    Cordier, P.Y.

    1996-07-01

    In the field of long-lived radionuclides separation from waste generated during spent fuel reprocessing, the picolinamides have been chosen as potential extractants for the selective extraction of actinides (III) from lanthanides (III). The first studies initiated on the most simple molecule of the picolinamide family, namely 2-pyridinecarboxamide, pointed out that in an aqueous media the complexation stability constant between this ligand and Am(III) is roughly 10 times higher than the ones corresponding to Ln(III). The synthesis of lipophilic derivatives of 2-pyridinecarboxamide leaded to extraction experiments. The extraction of metallic cation by lipophilic picolinamides, according to a solvatation mechanism, is strongly dependent on the nature of the amide function: a primary amide function (group I) leads to a good extraction; on the contrary, there is a decrease for secondary (group II) and tertiary (group III) amide functions. From a theoretical point of view, this work leads finally to the following conclusions: confirmation of the importance of the presence of soft donor atoms within the extractants (nitrogen in our case) for An(III)/Ln(III). Also, sensitivity of this soft donor atom regarding the protonation reaction; prevalence in our case of the affinity of the extractant for the metallic cation over the lipophilia of the extractant to ensure good distribution coefficients. The extraction and Am(III)/Ln(III) separation performances of the picolinamides from pertechnetic media leads to the design of a possible flowsheet for the reprocessing of high level liquid waste, with the new idea of an integrated technetium reflux. (author)

  13. Towards an interpretation of the mechanism of the actinides(III)/lanthanides(III) separation by synergistic solvent extraction with nitrogen-containing polydendate ligands

    International Nuclear Information System (INIS)

    Francois, N.

    2000-01-01

    In the field of the separation of long-lived radionuclides from the wastes produced by nuclear fuel reprocessing, aromatic nitrogen-containing polydendate ligands are potential candidates for the selective extraction, alone or in synergistic mixture with acidic extractants, of trivalent actinides from trivalent lanthanides. The first part of this work deals with the complexation of trivalent f cations with various nitrogen-containing ligands (poly-pyridine analogues). Time-resolved laser-induced fluorimetry (TRLIF) and UV-visible spectrophotometry were used to determine the nature and evaluate the stability of each complex. Among the ligands studied, the least basic Me-Btp proved to be highly selective towards americium(III) in acidic solution. In the second part, two synergistic systems (nitrogen-containing polydendate ligand and lipophilic carboxylic acid) are studied and compared in regard to the extraction and separation of lanthanides(III) and actinides(III). TRLIF and gamma spectrometry allowed the nature of the extracted complexes and the optimal conditions of efficiency of both systems to be determined. Comparison between these different studies showed that the selectivity of complexation of trivalent f cations by a given nitrogen-containing polydendate ligand could not always be linked to the Am(III)Eu(III) selectivity reached in synergistic extraction. The latter depends on the 'balance' between the acid-basic properties on the one hand, and on the hard-soft characteristics on the other hand, of both components of synergistic system. (author)

  14. Calix[6]arenes functionalized with malondiamides at the upper rim as possible extractants for lanthanide and actinide cations

    International Nuclear Information System (INIS)

    Almaraz, M.; Esperanza, S.; Magrans, O.; Mendoza, J. de; Pradus, P.

    2001-01-01

    Lipophilic malondiamides have been recently employed successfully as extractants for lanthanide and actinide cations from strongly acidic media. Many complexes between malondiamides and lanthanide-actinides cations have been studied by different techniques. For many of these complexes it has been observed that more than one malondiamide ligand participates in the complexation of each metallic cation. Incorporation of two or three malondiamide moieties into a calixarene platform would probably improve both extraction and selectivity with respect to the already tested malondiamides. According to CPK examination, a calix[6]arene substituted at the upper rim with two or three malondiamide moieties should constitute a promising ligand for lanthanide and actinide cations due to co-operative complexation with the malondiamides. Based on these considerations, we synthesised calix[6]arenes functionalized with malonic acid derivatives. (author)

  15. Synthesis and structural characterisation of mixed An(IV)-An(III) actinide oxalates used as precursors for dedicated fuel or target

    International Nuclear Information System (INIS)

    Tamain, Christelle; Grandjean, Stephane; Arab Chapelet, Benedicte; Abraham, Francis

    2010-01-01

    Oxalic co-conversion process plays an important role by producing mixed-actinide compounds used as starting materials as they are particularly suitable precursors of actinide oxide solid solutions. In these oxalate compounds, a mixed crystallographic site which accommodates both elements in spite of their different oxidation states has been established. The charge compensation is ensured by monovalent cations present in the acidic solution. This communication reviews the various mixed-actinide oxalates obtained by crystallization from acidic solution. First, crystallographic structures determined by X-ray diffraction from single crystals are described. Then completing data obtained by powder X-ray diffraction are presented on various systems. The different supramolecular arrangements underline the complexity of An(IV)-An(III)/Ln(III) oxalate system and the need to pursue studies on single crystals. (authors)

  16. Towards an interpretation of the mechanism of the actinides(III)/lanthanides(III) separation by synergistic solvent extraction with nitrogen-containing polydendate ligands; Vers une interpretation des mecanismes de la separation actinides(III)/lanthanides(III) par extraction liquide-liquide synergique impliquant des ligands polyazotes

    Energy Technology Data Exchange (ETDEWEB)

    Francois, N [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification, (DRRV), 30 - Marcoule (France); Universite Henri Poincare, 54 - Vandoeuvre-les-Nancy (France)

    2000-07-01

    In the field of the separation of long-lived radionuclides from the wastes produced by nuclear fuel reprocessing, aromatic nitrogen-containing polydendate ligands are potential candidates for the selective extraction, alone or in synergistic mixture with acidic extractants, of trivalent actinides from trivalent lanthanides. The first part of this work deals with the complexation of trivalent f cations with various nitrogen-containing ligands (poly-pyridine analogues). Time-resolved laser-induced fluorimetry (TRLIF) and UV-visible spectrophotometry were used to determine the nature and evaluate the stability of each complex. Among the ligands studied, the least basic Me-Btp proved to be highly selective towards americium(III) in acidic solution. In the second part, two synergistic systems (nitrogen-containing polydendate ligand and lipophilic carboxylic acid) are studied and compared in regard to the extraction and separation of lanthanides(III) and actinides(III). TRLIF and gamma spectrometry allowed the nature of the extracted complexes and the optimal conditions of efficiency of both systems to be determined. Comparison between these different studies showed that the selectivity of complexation of trivalent f cations by a given nitrogen-containing polydendate ligand could not always be linked to the Am(III)Eu(III) selectivity reached in synergistic extraction. The latter depends on the 'balance' between the acid-basic properties on the one hand, and on the hard-soft characteristics on the other hand, of both components of synergistic system. (author)

  17. Towards an interpretation of the mechanism of the actinides(III)/lanthanides(III) separation by synergistic solvent extraction with nitrogen-containing polydendate ligands; Vers une interpretation des mecanismes de la separation actinides(III)/lanthanides(III) par extraction liquide-liquide synergique impliquant des ligands polyazotes

    Energy Technology Data Exchange (ETDEWEB)

    Francois, N. [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification, (DRRV), 30 - Marcoule (France); Universite Henri Poincare, 54 - Vandoeuvre-les-Nancy (France)

    2000-07-01

    In the field of the separation of long-lived radionuclides from the wastes produced by nuclear fuel reprocessing, aromatic nitrogen-containing polydendate ligands are potential candidates for the selective extraction, alone or in synergistic mixture with acidic extractants, of trivalent actinides from trivalent lanthanides. The first part of this work deals with the complexation of trivalent f cations with various nitrogen-containing ligands (poly-pyridine analogues). Time-resolved laser-induced fluorimetry (TRLIF) and UV-visible spectrophotometry were used to determine the nature and evaluate the stability of each complex. Among the ligands studied, the least basic Me-Btp proved to be highly selective towards americium(III) in acidic solution. In the second part, two synergistic systems (nitrogen-containing polydendate ligand and lipophilic carboxylic acid) are studied and compared in regard to the extraction and separation of lanthanides(III) and actinides(III). TRLIF and gamma spectrometry allowed the nature of the extracted complexes and the optimal conditions of efficiency of both systems to be determined. Comparison between these different studies showed that the selectivity of complexation of trivalent f cations by a given nitrogen-containing polydendate ligand could not always be linked to the Am(III)Eu(III) selectivity reached in synergistic extraction. The latter depends on the 'balance' between the acid-basic properties on the one hand, and on the hard-soft characteristics on the other hand, of both components of synergistic system. (author)

  18. Gas-Phase Energetics of Actinide Oxides: An Assessment of Neutral and Cationic Monoxides and Dioxides from Thorium to Curium

    Science.gov (United States)

    Marçalo, Joaquim; Gibson, John K.

    2009-09-01

    An assessment of the gas-phase energetics of neutral and singly and doubly charged cationic actinide monoxides and dioxides of thorium, protactinium, uranium, neptunium, plutonium, americium, and curium is presented. A consistent set of metal-oxygen bond dissociation enthalpies, ionization energies, and enthalpies of formation, including new or revised values, is proposed, mainly based on recent experimental data and on correlations with the electronic energetics of the atoms or cations and with condensed-phase thermochemistry.

  19. Actinides

    International Nuclear Information System (INIS)

    Martinot, L.; Fuger, J.

    1985-01-01

    The oxidation behavior of the actinides is explained on the basis of their electronic structure. The actinide elements, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, and laurencium are included. For all except the last three elements, the points of discussion are oxidation states, Gibbs energies and potentials, and potential diagram for the element in acid solution; and thermodynamic properties of these same elements are tabulated. References are cited following discussion of each element with a total of 97 references being cited. 13 tables

  20. Actinide partitioning-transmutation program final report. III. Transmutation studies

    International Nuclear Information System (INIS)

    Wachter, J.W.; Croff, A.G.

    1980-07-01

    Transmutation of the long-lived nuclides contained in fuel cycle wastes has been suggested as a means of reducing the long-term toxicity of the wastes. A comprehensive program to evaluate the feasibility and incentives for recovering the actinides from wastes (partitioning) and transmuting them to short-lived or stable nuclides has been in progress for 3 years under the direction of Oak Ridge National Laboratory (ORNL). This report constitutes the final assessment of transmutation in support of this program. Included are (1) a summary of recent transmutation literature, (2) a generic evaluation of actinide transmutation in thermal, fast, and other transmutation devices, (3) a preliminary evaluation of 99 Tc and 129 I transmutation, and (4) a characterization of a pressurized-water-reactor fuel cycle with and without provisions for actinide recovery and transmutation for use in other parts of the ORNL program. The principal conclusion of the report is that actinide transmutation is feasible in both thermal and fast reactors, subject to demonstrating satisfactory fuel performance, with relatively little impact on the reactor. It would also appear that additional transmutation studies are unwarranted until a firm decision to proceed with actinide transmutation has been made by the responsible authorities

  1. Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants

    International Nuclear Information System (INIS)

    Toulemonde, V.; CEA Centre d'Etudes de la Vallee du Rhone, 30 -Marcoule

    1995-01-01

    The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author)

  2. Separation of macro-quantities of actinide elements at Savannah River by high-pressure cation exchange

    International Nuclear Information System (INIS)

    Burney, G.A.

    1980-01-01

    Large-scale separation of actinides from fission products and from each other by pressurized cation exchange chromatography at Savannah River is reviewed. Several kilograms of 244 Cm have been separated, with each run containing as much as 150 g of 244 Cm. Dowex 50W-X8 (Dow Chemical Co.) cation resin, graded to 30-70 micron size range, is used, and separation is made by eluting with 0.05M diethylenetriamine pentaacetic acid (DTPA) at a pH of 3. The effluent from the column is continuously monitored by a BF 3 detector, a NaI detector, and a lithium-drifted germanium detector and gamma spectrometer to guide collection of product fractions. Operating the columns at 300 to 1000 psi pressure eliminates resin bed disruption caused by radiolytically produced gases, and operating at increased flow rates decreases the radiolytic degradation of the resin per unit of product processed. A portion of the hot canyon of a production radiochemical separation plant was converted from a remote crane-operated facility to a master-slave manipulator-operated facility for separation and purification of actinide elements by pressurized cation exchange. It also contains an evaporator, furnaces, a calorimeter, and several precipitators and associated tanks. Actinide processing from target dissolution to packaging of purified product is planned in this facility

  3. Computer simulation of displacement cation exchange chromatography: separation of trivalent actinides and lanthanides

    International Nuclear Information System (INIS)

    Forsberg, C.W.

    1980-05-01

    A first-generation mathematical model of displacement cation exchange chromatography (CES) was constructed. The model incorporated the following phenomena: diffusion of cations up and down the column, diffusion of cations from the bulk liquid to the resin surface, and equilibrium of cations between liquid and solid resin beads. A limited number of experiments with rare earths using DTPA as the separation agent were undertaken to increase the current understanding of the processes involved in cation exchange chromatography. The numerical computer program based on the mathematical model was written in FORTRAN IV for use on the IBM 360 series of computers

  4. Separation of lanthanides (III) and actinides (III) by calixarenes containing acetamide-phosphine oxides functions

    International Nuclear Information System (INIS)

    Garcia Carrera, A.; Dozol, J.F.; Rouquette, H.

    2001-01-01

    The carbamoyl methyl phosphine oxide CMPO is the well known extractant of the TRUEX process for extraction of actinides from highly salted acidic wastes. In the framework of an European research contract coordinated by CEA/DDCC. V. Boehmer (Mainz, Germany) synthesized calix(4)arenes bearing CMPO moieties either on the wide rim, or on the narrow rim. Some of these calixarenes used at a concentration 10 -3 M are more efficient than CMPO used at a two hundred fifty fold higher concentration. Moreover, calixarene skeleton leads to a strong selectivity among lanthanides, this selectivity is much less obvious for CMPO. Selectivity order is reversed according to whether CMPO unit is borne by the wide rim or the narrow rim. The most efficient calixarenes allow actinides to be separated from most of the lanthanides except the lightest ones. (authors)

  5. Complexation of f elements by tripodal ligands containing aromatic nitrogens. Application to the selective extraction of actinides(III)

    International Nuclear Information System (INIS)

    Wietzke, Raphael

    1999-01-01

    This work initiates a research project, whose aim is the actinides(lll)/lanthanides(III) separation by liquid-liquid extraction. We were interested in the study of the coordination chemistry of lanthanides(III) and uranium(III) (uranium(III) as model for the actinides(III)), with the aim to show differences between the two families and to better understand the coordination properties involved in the extraction process. We studied the lanthanide(III) and uranium(III) complexation with tripodal ligands containing aromatic nitrogens. Several tripodal ligands were synthesized varying the type and the number of the donor atoms. The lanthanide(III) complexes have been characterized in the solid state and in solution (by several techniques: "1H NMR, ESMS, luminescence, UV spectrophotometry, conductometry). Differences in the coordination were found depending on the nature of the donor atoms. The new ligands, tris(2-pyrazinylmethyl)amine (tpza) et tris(N,N-diethyl-2-carbamoyl-6- pyridylmethyl)amine (tpaa), have shown a selectivity for the actinides(III) with promising results in liquid-liquid extraction. The comparison between the lanthanum(III) and uranium(III) complexes with the ligand tpza showed differences in the bonding nature, which could be attributed to a covalent contribution to the metal-ligand bond. (author) [fr

  6. Study of the chemical interactions of actinide cations in solution at macroscopic concentrations

    International Nuclear Information System (INIS)

    Maurice, C.

    1983-01-01

    The aim of this work was to study the interactions of pentavalent neptunium in dodecane-diluted tributyl phosphate with other metallic cations, especially uranium VI and ruthenium present in reprocessing solutions. Pentavalent neptunium on its own was shown to exist in several forms complexed by water and TBP and also to dimerise. In the complex it forms with uranium VI the interaction via the neptunyl oxygen is considerably enhanced in organic solution. Dibutyl phosphoric acid strengthens the interaction between neptunium and uranium. The Np V-ruthenium interaction reveals the existence of a new cation-cation complex; the process takes place in two successive stage and leads to the formation, reinforced and accelerated by HDBP, of a highly to the formation, reinforced and accelerated by HDBP, of a highly stable complex. These results contribute towards a better knowledge of the behaviour of neptunium in the reprocessing operation [fr

  7. Complexation of Eu(III) with a polymeric cement additive as a potential carrier of actinides

    Energy Technology Data Exchange (ETDEWEB)

    Lippold, Holger; Becker, Michael [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Reactive Transport

    2017-06-01

    In the long term, cementitious materials in a final repository will be exposed to leaching processes generating highly alkaline solutions. Polymeric additives, so-called superplasticizers, are considered as potential mobilizing agents for released radionuclides, since it is uncertain whether complete degradation will take place under the evolving aqueous conditions. Regarding the complexing properties of superplasticizers, there are only indirect assessments so far. In this study, first systematic investigations on complexation with Eu(III) as an analogue of trivalent actinides were performed at variable pH and electrolyte content (NaCl, CaCl{sub 2}) using ultrafiltration as a separation method. A stability constant was derived according to the charge neutralization model. For this purpose, the proton exchange capacity was determined by potentiometric titration.

  8. Complexation of the actinides (III, IV and V) with organic acids

    International Nuclear Information System (INIS)

    Leguay, S.

    2012-01-01

    A thorough knowledge of the chemical properties of actinides is now required in a wide variety of fields: extraction processes involved in spent fuel reprocessing, groundwater in the vicinity of radioactive waste packages, environmental and biological media in the case of accidental release of radionuclides. In this context, the present work has been focused on the complexation of Am(III), Cm(III), Cf(III), Pu(IV) and Pa(V) with organic ligands: DTPA, NTA and citric acid. The complexation of pentavalent protactinium with citric and nitrilotriacetic acids was studied using liquid-liquid extraction with the element at tracer scale (C Pa ≤ 10 -10 M). The order and the mean charge of each complex were determined from the analysis of the systematic variations of the distribution coefficient of Pa(V) as function of ligand and proton concentration. Then, the apparent formation constants related of the so-identified complexes were calculated. The complexation of trivalent actinides with DTPA was studied by fluorescence spectroscopy (TRLFS) and capillary electrophoresis (CE-ICP-MS). The coexistence of the mono-protonated and non-protonated complexes (AnHDTPA - and AnDTPA 2- ) in acidic media (1.5 ≤ pH ≤ 3.5) was shown unambiguously. Literature data have been reinterpreted by taking into account both complexes and a consistent set of formation constants of An(III)-DTPA has been obtained. The experimental study was completed by theoretical calculations (DFT) on Cm-DTPA system. The coordination geometry of Cm in CmDTPA 2- and CmHDTPA - including water molecules in the first coordination sphere has been determined as well as interatomic distances. Finally, a study on the complexation of Pu(IV) with DTPA was initiated in order to more closely mimic physiological conditions. A three-step approach was proposed to avoid plutonium hydrolysis: i/ complexation of Pu(IV) with (NTA) in order to protect Pu(IV) from hydrolysis (at low pH) ii/ increase of pH toward neutral conditions

  9. Recovery of actinides from actinide-aluminium alloys by chlorination: Part III - Chlorination with HCl(g)

    Science.gov (United States)

    Meier, Roland; Souček, Pavel; Walter, Olaf; Malmbeck, Rikard; Rodrigues, Alcide; Glatz, Jean-Paul; Fanghänel, Thomas

    2018-01-01

    Two steps of a pyrochemical route for the recovery of actinides from spent metallic nuclear fuel are being investigated at JRC-Karlsruhe. The first step consists in electrorefining the fuel in molten salt medium implying aluminium cathodes. The second step is a chlorination process for the separation of actinides (An) from An-Al alloys formed on the cathodes. The chlorination process, in turn, consists of three steps; the distillation of adhered salt (1), the chlorination of An-Al by HCl/Cl2 under formation of AlCl3 and An chlorides (2), and the subsequent sublimation of AlCl3 (3). In the present work UAl2, UAl3, NpAl2, and PuAl2 were chlorinated with HCl(g) in a temperature range between 300 and 400 °C forming UCl4, NpCl4 or PuCl3 as the major An containing phases, respectively. Thermodynamic calculations were carried out to support the experimental work. The results showed a high chlorination efficiency for all used starting materials and indicated that the sublimation step may not be necessary when using HCl(g).

  10. Extraction of lanthanides and actinides (III) by DI-2 ethyl dithiophosphoric acid and DI-2 ethyl hexyl monothiophosphoric acid. Structure of the complexes in the organic phase

    International Nuclear Information System (INIS)

    Pattee, D.; Musikas, C.; Faure, A.; Chachaty, C.

    1986-09-01

    To operate a trivalent actinide-lanthanide (III) group chemical separation from low pH nitric solutions we studied the extractive properties of the di-2 ethyl hexyl dithiophosphoric acid (HDEHDTP); this bidentate ligand which possesses a sulfur donor atom is a good extractant of soft acids. We so expect a better selectivity for the actinides (III) extraction. We also have investigated extractive properties of di-2 ethyl hexyl monothiophosphoric acid (HDEHTP) for trivalent actinides and lanthanides; HDEHDTP is a bidentate ligand with one oxygen donor atom and so is a better extractant for hard acids like actinides and lanthanides (III); but its selectivity is weak. The addition of TBP (tri-n butyl phosphate) to HDEHDTP deals to strong synergistic organic complexes with a great selectivity for Am(III). We explicited this phenomenon. When the metal is macroconcentrated the organic complexes aggregate and form inverted micelles

  11. TAILORING INORGANIC SORBENTS FOR SRS STRONTIUM AND ACTINIDE SEPARATIONS: MODIFIED MONOSODIUM TITANATE PHASE III FINAL REPORT

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, K.; Hobbs, D.

    2010-09-01

    This document provides a final report of Phase III testing activities for the development of modified monosodium titanate (mMST), which exhibits improved strontium and actinide removal characteristics compared to the baseline MST material. The activities included characterization of the crystalline phases present at varying temperatures, solids settling characteristics, quantification of the peroxide content; evaluation of the post-synthesis gas release under different conditions; the extent of desorption of {sup 85}Sr, Np, and Pu under washing conditions; and the effects of age and radiation on the performance of the mMST. Key findings and conclusions include the following. The peroxide content of several mMST samples was determined using iodometric titration. The peroxide content was found to decrease with age or upon extended exposure to elevated temperature. A loss of peroxide was also measured after exposure of the material to an alkaline salt solution similar in composition to the simulated waste solution. To determine if the loss of peroxide with age affects the performance of the material, Sr and actinide removal tests were conducted with samples of varying age. The oldest sample (4 years and 8 months) did show lower Sr and Pu removal performance. When compared to the youngest sample tested (1 month), the oldest sample retained only 15% of the DF for Pu. Previous testing with this sample indicated no decrease in Pu removal performance up to an age of 30 months. No loss in Np removal performance was observed for any of the aged samples, and no uptake of uranium occurred at the typical sorbent loading of 0.2 g/L. Additional testing with a uranium only simulant and higher mMST loading (3.0 g/L) indicated a 10% increase of uranium uptake for a sample aged 3 years and 8 months when compared to the results of the same sample measured at an age of 1 year and 5 months. Performance testing with both baseline-MST and mMST that had been irradiated in a gamma source to

  12. Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants; Cinetique d`extraction liquide-liquide du nitrate d`uranyle et des nitrates d`actinides (III) et de lanthanides (III) par des extractants a fonction amide

    Energy Technology Data Exchange (ETDEWEB)

    Toulemonde, V [CEA Centre d` Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France); [CEA Centre d` Etudes de la Vallee du Rhone, 30 -Marcoule (France). Dept. d` Exploitation du Retraitement et de Demantelement

    1995-12-20

    The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author). 89 refs.

  13. Study of actinide paramagnetism in solution

    International Nuclear Information System (INIS)

    Autillo, Matthieu

    2015-01-01

    The physiochemical properties of actinide (An) solutions are still difficult to explain, particularly the behavioral differences between An(III) and Ln(III). The study of actinide paramagnetic behavior may be a 'simple' method to analyze the electronic properties of actinide elements and to obtain information on the ligand-actinide interaction. The objective of this PhD thesis is to understand the paramagnetic properties of these elements by magnetic susceptibility measurements and chemical shift studies. Studies on actinide electronic properties at various oxidation states in solution were carried out by magnetic susceptibility measurements in solution according to the Evans method. Unlike Ln(III) elements, there is no specific theory describing the magnetic properties of these ions in solution. To obtain accurate data, the influence of experimental measurement technique and radioactivity of these elements was analyzed. Then, to describe the electronic structure of their low energy states, the experimental results were complemented with quantum chemical calculations from which the influence of the ligand field was studied. Finally, these interpretations were applied to better understand the variations in the magnetic properties of actinide cations in chloride and nitrate media. Information about ligand-actinide interactions may be determined from an NMR chemical shift study of actinide complexes. Indeed, modifications induced by a paramagnetic complex can be separated into two components. The first component, a Fermi contact contribution (δ_c) is related to the degree of covalency in coordination bonds with the actinide ions and the second, a dipolar contribution (δ_p_c) is related to the structure of the complex. The paramagnetic induced shift can be used only if we can isolate these two terms. To achieve this study on actinide elements, we chose to work with the complexes of dipicolinic acid (DPA). Firstly, to characterize the geometrical parameters, a

  14. Liquid-liquid extraction kinetics of uranyl nitrate and actinides (III)-lanthanides nitrates by extractants with amide function

    International Nuclear Information System (INIS)

    Toulemonde, V.

    1995-01-01

    Nowadays, the most important part of electric power is generated by fission energy. But spent fuels have then to be reprocessed. The production of these reprocessed materials separately and with a high purity level is done according to a liquid-liquid extraction process (Purex process) with the use of tributyl phosphate as solvent. Optimization studies concerning the extracting agent have been undertaken. This work gives the results obtained for the uranyl nitrate and the actinides (III)-lanthanides (III) nitrates extraction by extractants with amide function (monoamide for U(VI) and diamide for actinides (III) and lanthanides (III)). The extraction kinetics have been studied in the case of a metallic specie transfer from the aqueous phase towards the organic phase. The experiments show that the nitrates extraction kinetics is limited by the complexation chemical reaction of the species at the interface between the two liquids. An adsorption-desorption interfacial reactional mechanism (Langmuir theory) is proposed for the uranyl nitrate. (O.M.)

  15. Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine

    International Nuclear Information System (INIS)

    Riviere, Ch.

    2000-01-01

    The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

  16. Study of extraction kinetics of lanthanides(III) and actinides(III) nitrates by the molecule N, N'-dimethyl-N, N'-dibutyl, tetradecylmalonamide

    International Nuclear Information System (INIS)

    Daldon, M.

    1999-01-01

    The kinetics of extraction of lanthanides (III) and actinides (III) nitrates by the molecule N, N'-dimethyl - N, N'-dibutyl tetra-decyl malonamide has been investigated. This study was realised with a new constant interfacial-area-stirred cell. During the qualification step of the device it appears that the reduction of the device can lead to hydrolytic perturbations. The main conclusions are: - after the determination of conditions which provide kinetics regime (diffusion of species neglectable), partial orders of the kinetics law have been obtained and lead to the establishment of the law J = k [Nd 3+ ] [NO 3 - ] 3 [diamide] 1 , - interfacial tension measurements and kinetics study in presence of surface-active compounds proved that the chemical limiting reaction for Nd(III) is interfacial, - the results allow to propose an adsorption-desorption reaction mechanism, - a comprehensive study of the extraction kinetics of the lanthanides(III) series and also Am(III) and Cm(III) nitrates has been realised. The lighter lanthanides (La, Ce and Pr) exhibit higher kinetics rate of extraction than the others, which differs from the tendency observed with distribution coefficients which exhibit tetrad effect. The kinetics rate of extraction of Am(III) and Cm(III) is closed to the value of Eu(III). (author)

  17. Actinide complexation kinetics: rate and mechanism of dioxoneptunium (V) reaction with chlorophosphonazo III

    International Nuclear Information System (INIS)

    Fugate, G.; Feil-Jenkins, J.F.; Sullivan, J.C.; Nash, K.L.

    1996-12-01

    Rates of complex formation and dissociation in NpO 2 + - Chlorophosphonazo III (2,7-bis(4-chloro-2-phosphonobenzeneazo)-1,8- dihydroxynapthalene-3,6-disulfonic acid)(CLIII) were investigated by stopped-flow spectrophotometry. Also, limited studies were made of the rates of reaction of La 3+ , Eu 3+ , Dy 3+ , and Fe 3+ with CLIII. Rate determining step in each system is an intramolecular process, the NpO 2 + -CLIII reaction proceeding by a first order approach to equilibrium in the acid range from 0.1 to 1.0 M. Complex formation occurs independent of acidity, while both acid dependent and independent dissociation pathways are observed. Activation parameters for the complex formation reaction are ΔH=46.2±0.3 kJ/m and ΔS=7± J/mK (I=1.0 M); these for the acid dependent and independent dissociation pathways are ΔH=38.8±0.6 kJ/m, ΔS=-96±18 J/mK, ΔH=70.0± kJ/m, and ΔS=17±1 J/mK, respectively. An isokinetic relationship is observed between the activation parameters for CLIII complex formation with NpO 2 + , UO 2 2+ , Th 4+ , and Zr 4+ . Rates of CLIII complex formation reactions for Fe 3+ , Zr 4+ , NpO 2 + , UO 2 2+ , Th 4+ , La 3+ , Eu 3+ , and Dy 3+ correlate with cation radius rather than charge/radius ratio

  18. Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine; Etude de la selectivite de molecules extractantes polyazotees dans la complexation des actinides (III) et des lanthanides (III) en solution dans la pyridine anhydre

    Energy Technology Data Exchange (ETDEWEB)

    Riviere, Ch

    2000-10-05

    The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

  19. Electro-spray Ionization Mass Spectrometry Investigation of BTBP - Lanthanide(III) and Actinide(III) Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Retegan, T.; Ekberg, Ch. [Chalmers, Dept Chem and Biol Engn, SE-41296 Gothenburg, (Sweden); Berthon, L.; Zorz, N. [DEN DRCP SCPS LCSE, CEA Marcoule, Bagnols Sur Ceze, (France)

    2009-07-01

    In the framework of nuclear waste reprocessing, the separation processes of minor actinides from fission products are developed using liquid-liquid extraction. To gain an understanding of the mechanism involved in the extraction process, a complex formation of actinides and lanthanides with BTBPs (6, 6'-bis(5, 6-dialkyl-1, 2, 4-triazin-3-yl)-2, 2'-bipyridines) was characterized using the Electro-spray Ionization Mass Spectrometry (ESI-MS) technique. This study was carried out to compare the influence of diluents and side groups of the extractants on complex formation. Three different diluents, nitrobenzene, octanol and cyclohexanone, and two extractants, C5-BTBP and CyMe{sub 4}-BTBP, were selected for this experiment. It was found that the change of the diluent and of the substituent on the BTBP moiety does not modify the stoichiometry of the complexes which is L{sub 2}M(NO{sub 3}){sub 3}. It is proposed that one nitrate is directly coordinated to the metal ion, the two other anions probably remaining in the outer coordination sphere. The difference observed in extracting properties is probably due to the solvation of the complexes by the diluent. The noncovalent force that holds complexes together are likely to be largely governed by electrostatic interactions even if the hydrophobic exterior of the complexes plays an important role in the complexation/extraction mechanism. The study of the stability of the ions in the gas phase shows that the C5-BTBP ligand has a labile hydrogen atom, which is a fragility point of C5-BTBP. (authors)

  20. Study of extraction kinetics of lanthanides(III) and actinides(III) nitrates by the molecule N, N'-dimethyl-N, N'-dibutyl, tetradecylmalonamide; Etude des cinetiques d'extraction des nitrates de lanthanides (III) et d'actinides (III) par le malonamide N, N'-dimethyl-N, N'-dibutyl, tetradecylmalonamide

    Energy Technology Data Exchange (ETDEWEB)

    Daldon, M

    1999-07-01

    The kinetics of extraction of lanthanides (III) and actinides (III) nitrates by the molecule N, N'-dimethyl - N, N'-dibutyl tetra-decyl malonamide has been investigated. This study was realised with a new constant interfacial-area-stirred cell. During the qualification step of the device it appears that the reduction of the device can lead to hydrolytic perturbations. The main conclusions are: - after the determination of conditions which provide kinetics regime (diffusion of species neglectable), partial orders of the kinetics law have been obtained and lead to the establishment of the law J = k [Nd{sup 3+}] [NO{sub 3}{sup -}]{sup 3} [diamide]{sup 1}, - interfacial tension measurements and kinetics study in presence of surface-active compounds proved that the chemical limiting reaction for Nd(III) is interfacial, - the results allow to propose an adsorption-desorption reaction mechanism, - a comprehensive study of the extraction kinetics of the lanthanides(III) series and also Am(III) and Cm(III) nitrates has been realised. The lighter lanthanides (La, Ce and Pr) exhibit higher kinetics rate of extraction than the others, which differs from the tendency observed with distribution coefficients which exhibit tetrad effect. The kinetics rate of extraction of Am(III) and Cm(III) is closed to the value of Eu(III). (author)

  1. Complexation of trivalent actinides and lanthanides with hydrophilic N-donor ligands for Am(III)/Cm(III) and An(III)/Ln(III) separation; Komplexierung von trivalenten Actiniden und Lanthaniden mit hydrophilen N-Donorliganden zur Am(III)/Cm(III)- bzw. An(III)/Ln(III)-Trennung

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, Christoph

    2017-07-24

    The implementation of actinide recycling processes is considered in several countries, aiming at the reduction of long-term radiotoxicity and heat load of used nuclear fuel. This requires the separation of the actinides from the fission and corrosion products. The separation of the trivalent actinides (An(III)) Am(III) and Cm(III), however, is complicated by the presence of the chemically similar fission lanthanides (Ln(III)). Hydrophilic N-donor ligands are employed as An(III) or Am(III) selective complexing agents in solvent extraction to strip An(III) or Am(III) from an organic phase loaded with An(III) and Ln(III). Though they exhibit excellent selectivity, the complexation chemistry of these ligands and the complexes formed during solvent extraction are not sufficiently characterized. In the present thesis the complexation of An(III) and Ln(III) with hydrophilic N-donor ligands is studied by time resolved laser fluorescence spectroscopy (TRLFS), UV/Vis, vibronic sideband spectroscopy and solvent extraction. TRLFS studies on the complexation of Cm(III) and Eu(III) with the Am(III) selective complexing agent SO{sub 3}-Ph-BTBP (tetrasodium 3,3{sup '},3'',3{sup '''}-([2,2{sup '}-bipyridine]-6,6{sup '}-diylbis(1,2,4-triazine-3,5,6-triyl)) tetrabenzenesulfonate) revealed the formation of [M(SO{sub 3}-Ph-BTBP){sub n}]{sup (4n-3)-} complexes (M = Cm(III), Eu(III); n = 1, 2). The conditional stability constants were determined in different media yielding two orders of magnitude larger β{sub 2}-values for the Cm(III) complexes, independently from the applied medium. A strong impact of ionic strength on the stability and stoichiometry of the formed complexes was identified, resulting from the stabilization of the pentaanionic [M(SO{sub 3}-Ph-BTBP){sub 2}]{sup 5-} complex with increasing ionic strength. Thermodynamic studies of Cm(III)-SO{sub 3}-Ph-BTBP complexation showed that the proton concentration of the applied medium impacts

  2. Adsorption of Cr(III) on ozonised activated carbon. Importance of Cpi-cation interactions.

    Science.gov (United States)

    Rivera-Utrilla, J; Sánchez-Polo, M

    2003-08-01

    The adsorption of Cr(III) in aqueous solution was investigated on a series of ozonised activated carbons, analysing the effect of oxygenated surface groups on the adsorption process. A study was carried out to determine the adsorption isotherms and the influence of the pH on the adsorption of this metal. The adsorption capacity and affinity of the adsorbent for Cr(III) increased with the increase in oxygenated acid groups on the surface of the activated carbon. These findings imply that electrostatic-type interactions predominate in the adsorption process, although the adsorption of Cr(III) on the original (basic) carbon indicates that other forces also participate in the adsorption process. Thus, the ionic exchange of protons in the -Cpi-H3O(+) interaction for Cr(III) accounts for the adsorption of cationic species in basic carbons with positive charge density. Study of the influence of pH on the adsorption of Cr(III) showed that, in each system, the maximum adsorption occurred when the charge of the carbon surface was opposite that of the species of Cr(III) present at the pH of the experiment. These results confirmed that electrostatic interactions predominate in the adsorption process.

  3. PRODUCTION OF ACTINIDE METAL

    Science.gov (United States)

    Knighton, J.B.

    1963-11-01

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

  4. Development and demonstration of a new SANEX Partitioning Process for selective actinide(III)/lanthanide(III) separation using a mixture of CyMe{sub 4}BTBP and TODGA

    Energy Technology Data Exchange (ETDEWEB)

    Modolo, G.; Wilden, A.; Daniels, H. [Forschungszentrum Juelich GmbH (Germany). Institute for Energy and Climate Research, IEK-6, Nuclear Waste Management and Reactor Safety; Geist, A.; Magnusson, D. [Karlsruher Institut fuer Technologie, Karlsruhe (Germany). Inst. fuer Nukleare Entsorgung; Malmbeck, R. [European Commission, JRC, Karlsruhe (Germany). Inst. for Transuranium Elements (ITU)

    2013-05-01

    Within the framework of the European collaborative project ACSEPT, a new SANEX partitioning process was developed at Forschungszentrum Juelich for the separation of the trivalent minor actinides americium, curium and californium from lanthanide fission products in spent nuclear fuels. The development is based on batch solvent extraction studies, single-centrifugal contactor tests and on flow-sheet design by computer code calculations. The used solvent is composed of 6,6{sup '}-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenzo-[1,2-4]trizazin-3-yl)-[2,2{sup '}]-bipyridine (CyMe{sub 4}BTBP) and N,N,N{sup '},N{sup '}-tetraoctyldiglycolamide (TODGA) dissolved in n-octanol. A spiked continuous counter-current test was carried out in miniature centrifugal contactors with the aid of a 20-stage flow-sheet consisting of 12 extraction, 4 scrubbing and 4 stripping stages. A product fraction containing more than 99.9% of the trivalent actinides Am(III), Cm(III) and Cf(III) was obtained. High product/feed decontamination factors >1000 were achieved for these actinides. The trivalent lanthanides were directed to the raffinate of the process with the actinide (III) product stream being contaminated with less than 0.5 mass-% in the initial lanthanides. (orig.)

  5. Actinide metals

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Paul L. [Geochem Australia, Kiama, NSW (Australia); Ekberg, Christian [Chalmers Univ. of Technology, Goeteborg (Sweden). Nuclear Chemistry/Industrial Materials Recycling

    2016-07-01

    All isotopes of actinium are radioactive and exist in aqueous solution only in the trivalent state. There have been very few studies on the hydrolytic reactions of actinium(III). The hydrolysis reactions for uranium would only be important in alkaline pH conditions. Thermodynamic parameters for the hydrolysis species of uranium(VI) and its oxide and hydroxide phases can be determined from the stability and solubility constants. The hydrolytic behaviour of neptunium(VI) is quite similar to that of uranium(VI). The solubility constant of NpO{sub 2}OH(am) has been reported a number of times for both zero ionic strength and in fixed ionic strength media. Americium can form four oxidation states in aqueous solution, namely trivalent, tetravalent, pentavalent and hexavalent. Desire, Hussonnois and Guillaumont determined stability constants for the species AmOH{sup 2+} for the actinides, plutonium(III), americium(III), curium(III), berkelium(III) and californium(III) using a solvent extraction technique.

  6. Actinide metals

    International Nuclear Information System (INIS)

    Brown, Paul L.; Ekberg, Christian

    2016-01-01

    All isotopes of actinium are radioactive and exist in aqueous solution only in the trivalent state. There have been very few studies on the hydrolytic reactions of actinium(III). The hydrolysis reactions for uranium would only be important in alkaline pH conditions. Thermodynamic parameters for the hydrolysis species of uranium(VI) and its oxide and hydroxide phases can be determined from the stability and solubility constants. The hydrolytic behaviour of neptunium(VI) is quite similar to that of uranium(VI). The solubility constant of NpO 2 OH(am) has been reported a number of times for both zero ionic strength and in fixed ionic strength media. Americium can form four oxidation states in aqueous solution, namely trivalent, tetravalent, pentavalent and hexavalent. Desire, Hussonnois and Guillaumont determined stability constants for the species AmOH 2+ for the actinides, plutonium(III), americium(III), curium(III), berkelium(III) and californium(III) using a solvent extraction technique.

  7. A data base for thermodynamic modeling of +III actinide solubility in concentrated Na-Cl-SO4-CO3-PO4 electrolytes

    International Nuclear Information System (INIS)

    Novak, C.F.; Crafts, C.C.; Dhooge, N.J.

    1995-01-01

    The literature contains thermodynamic parameters for describing the chemical behavior of the following: Am(III) in dilute NaHCO 3 media; Nd(III) in dilute to concentrated Na 2 CO 3 and NaHCO 3 media; Pu(III) in dilute to concentrated NaCl media; Nd(III)/Am(III) in dilute to concentrated Na 2 SO 4 media; and Am(III) in NaH 2 PO 4 media. We have combined this information into a thermodynamic data base for the general +III actinide, An(III), using the analogy for chemical behavior of f-elements in the same oxidation state. This internally consistent data base is based on equilibrium thermodynamics and the specific ion interaction activity coefficient formalism of Pitzer. This data base forms the basis for the prediction of potential Am(III) and Pu(III) dissolved concentrations in the concentrated natural brines associated with the Waste Isolation Pilot Plant (WIPP) in Southeastern New Mexico, USA

  8. Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions

    International Nuclear Information System (INIS)

    Gruner, B.; Plesek, J.; Baca, J.; Cisarova, I.; Dozol, J.F.; Rouquette, H.; Vinas, C.; Selucky, P.; Rais, J.

    2002-01-01

    A new series of boron substituted cobalt bis(dicarbollide)(1-) ion (1) derivatives of the general formula [(8-CMPO-(CH 2 -CH 2 O) 2 -1,2-C 2 B 9 H 10 )(1',2'-C 2 B 9 H 11 )-3,3'-Co] - (CMPO = Ph 2 P(O)-CH 2 C(O)NR, R = C 4 H 9 (3b), -C 12 H 25 (4b), -CH 2 -C 6 H 5 (5b)) was prepared by ring cleavage of the 8-dioxane-cobalt bis(dicarbollide) (2) bi-polar compound by the respective primary amines and by subsequent reaction of the resulting amino derivatives (3a-5a) with the nitrophenyl ester of diphenyl-phosphoryl-acetic acid. The compounds were synthesized with the aim to develop a new class of more efficient extraction agents for liquid/liquid extraction of polyvalent cations, i.e. lanthanides and actinides, from high-level activity nuclear waste. All compounds were characterized by a combination of 11 B NMR, 1 H high field NMR, Mass Spectrometry with Electro-spray and MALDI TOF ionisation, HPLC and other techniques. The molecular structure of the supramolecular Ln 3+ complex of the anion 5b was determined by single crystal X-ray diffraction analysis. Crystallographic results proved that the Ln(m) atom is bonded to three functionalized cobalt bis(dicarbollide) anions in a charge compensated complex. The cation is tightly coordinated by six oxygen atoms of the CMPO terminal groups (two of each ligand) and by three water molecules completing the metal coordination number to 9. Atoms occupying the primary coordination sphere form a tri-capped trigonal prismatic arrangement. Very high liquid-liquid extraction efficiency of all anionic species was observed. Moreover, less polar toluene can be applied as an auxiliary solvent replacing the less environmentally friendly nitro- and chlorinated solvents used in the current dicarbollide liquid-liquid extraction process. The extraction coefficients are sufficiently high for possible technological applications. (authors)

  9. Environmentally-relevant concentrations of Al(III) and Fe(III) cations induce aggregation of free DNA by complexation with phosphate group.

    Science.gov (United States)

    Qin, Chao; Kang, Fuxing; Zhang, Wei; Shou, Weijun; Hu, Xiaojie; Gao, Yanzheng

    2017-10-15

    Environmental persistence of free DNA is influenced by its complexation with other chemical species and its aggregation mechanisms. However, it is not well-known how naturally-abundant metal ions, e.g., Al(III) and Fe(III), influence DNA aggregation. This study investigated aggregation behaviors of model DNA from salmon testes as influenced by metal cations, and elucidated the predominant mechanism responsible for DNA aggregation. Compared to monovalent (K + and Na + ) and divalent (Ca 2+ and Mg 2+ ) cations, Al(III) and Fe(III) species in aqueous solution caused rapid DNA aggregations. The maximal DNA aggregation occurred at 0.05 mmol/L Al(III) or 0.075 mmol/L Fe(III), respectively. A combination of atomic force microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy revealed that Al(III) and Fe(III) complexed with negatively charged phosphate groups to neutralize DNA charges, resulting in decreased electrostatic repulsion and subsequent DNA aggregation. Zeta potential measurements and molecular computation further support this mechanism. Furthermore, DNA aggregation was enhanced at higher temperature and near neutral pH. Therefore, DNA aggregation is collectively determined by many environmental factors such as ion species, temperature, and solution pH. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Structural organization and spectroscopy of peptide-actinide(IV) complexes

    International Nuclear Information System (INIS)

    Dahou, S.

    2010-01-01

    The contamination of living organisms by actinide elements is at the origin of both radiological and chemical toxicity that may lead to severe dysfunction. Most of the data available on the actinide interaction with biological systems are macroscopic physiological measurements and are lacking a molecular description of the systems. Because of the intricacy of these systems, classical biochemical methods are difficult to implement. Our strategy consisted in designing simplified biomimetic peptides, and describing the corresponding intramolecular interactions with actinides. A carboxylic pentapeptide of the form DDPDD has been at the starting point of this work in order to further assess the influence of the peptide sequence on the topology of the complexes.To do so, various linear (Asp/Ala permutations, peptoids) and cyclic analogues have been synthesized. Furthermore, in order to include the hydroxamic function (with a high affinity for Fe(III)) in the peptide, both desferrioxamine and acetohydroxamic acid have been investigated. However because of difficulties in synthesis, we have not been able to test these peptides. Three actinide cations have been considered at oxidation state +IV (Th, Np, Pu) and compared to Fe(III), often considered as a biological surrogate of Pu(IV). The spatial arrangement of the peptide around the cation has been probed by spectrophotometry and X-ray Absorption Spectroscopy. The spectroscopic data and EXAFS data adjustment lead us to rationalize the topology of the complexes as a function of the peptide sequence: mix hydroxy polynuclear species for linear and cyclic peptides, mononuclear for the desferrioxamine complexes. Furthermore, significant differences have appeared between Fe(III) and actinide(IV), related to differences of reactivity in aqueous medium. (author)

  11. Titanium (III) cation selective electrode based on synthesized tris(2pyridyl) methylamine ionophore and its application in water samples

    Science.gov (United States)

    Rezayi, Majid; Karazhian, Reza; Abdollahi, Yadollah; Narimani, Leila; Sany, Seyedeh Belin Tavakoly; Ahmadzadeh, Saeid; Alias, Yatimah

    2014-04-01

    The introduction of low detection limit ion selective electrodes (ISEs) may well pave the way for the determination of trace targets of cationic compounds. This research focuses on the detection of titanium (III) cation using a new PVC-membrane sensor based on synthesized tris(2pyridyl) methylamine (tpm) ionophore. The application and validation of the proposed sensor was done using potentiometric titration, inductively coupled plasma atomic emission spectrometry (ICP-AES), and atomic absorption spectrometry (AAS). The membrane sensor exhibited a Nernstian response to the titanium (III) cation over a concentration range of 1.0 × 10-6-1.0 × 10-2 M and pH range from 1-2.5. The Nernstian slope, the lower of detection (LOD), and the response time (t95%) of the proposed sensor were 29.17 +/- 0.24 mV/dec, 7.9 × 10-7 M, and 20 s, respectively. The direct determination of 4-39 μg/ml of titanium (III) standard solution showed an average recovery of 94.60 and a mean relative standard deviation of 1.8 at 100.0 μg/ml. Finally, the utilization of the electrodes as end-point indicators for potentiometric titration with EDTA solutions for titanium (III) sensor was successfully carried out.

  12. 2-(2′-Pyridyl)-4,6-diphenylphosphinine versus 2-(2′-Pyridyl)-4,6-diphenylpyridine: Synthesis, Characterization, and Reactivity of Cationic RhIII and IrIII Complexes Based on Aromatic Phosphorus Heterocycles

    NARCIS (Netherlands)

    de Krom, I.; Broeckx, L.E.E.; Lutz, M.; Müller, Christian

    2013-01-01

    The bidentate P,N hybrid ligand 1 allows access for the first time to novel cationic phosphinine-based RhIII and IrIII complexes, broadening significantly the scope of low-coordinate aromatic phosphorus heterocycles for potential applications. The coordination chemistry of 1 towards RhIII and IrIII

  13. Electrorecovery of actinides at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Stoll, Michael E [Los Alamos National Laboratory; Oldham, Warren J [Los Alamos National Laboratory; Costa, David A [Los Alamos National Laboratory

    2008-01-01

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

  14. Factors influencing the transport of actinides in the groundwater environment. Final report

    International Nuclear Information System (INIS)

    Sheppard, J.C.; Kittrick, J.A.

    1983-01-01

    This report summarizes investigations of factors that significantly influence the transport of actinide cations in the groundwater environment. Briefly, measurements of diffusion coefficients for Am(III), Cm(III), and Np(V) in moist US soils indicated that diffusion is negligible compared to mass transport in flowing groundwater. Diffusion coefficients do, however, indicate that, in the absence of flowing water, actinide elements will migrate only a few centimeters in a thousand years. The remaining investigations were devoted to the determination of distribution ratios (K/sub d/s) for representative US soils, factors influencing them, and chemical and physical processes related to transport of actinides in groundwaters. The computer code GARD was modified to include complex formation to test the importance of humic acid complexing on the rate of transport of actinides in groundwaters. Use of the formation constant and a range of humic acid, even at rather low concentrations of 10 -5 to 10 -6 molar, significantly increases the actinide transport rate in a flowing aquifer. These computer calculations show that any strong complexing agent will have a similar effect on actinide transport in the groundwater environment. 32 references, 9 figures

  15. Warm White Light-Emitting Diodes Based on a Novel Orange Cationic Iridium(III) Complex.

    Science.gov (United States)

    Tang, Huaijun; Meng, Guoyun; Chen, Zeyu; Wang, Kaimin; Zhou, Qiang; Wang, Zhengliang

    2017-06-16

    A novel orange cationic iridium(III) complex [(TPTA)₂Ir(dPPOA)]PF₆ (TPTA: 3,4,5-triphenyl-4 H -1,2,4-triazole, dPPOA: N,N-diphenyl-4-(5-(pyridin-2-yl)-1,3,4-oxadiazol-2-yl)aniline) was synthesized and used as a phosphor in light-emitting diodes (LEDs). [(TPTA)₂Ir(dPPOA)]PF₆ has high thermal stability with a decomposition temperature ( T d ) of 375 °C, and its relative emission intensity at 100 °C is 88.8% of that at 25°C. When only [(TPTA)₂Ir(dPPOA)]PF₆ was used as a phosphor at 6.0 wt % in silicone and excited by a blue GaN (GaN: gallium nitride) chip (450 nm), an orange LED was obtained. A white LED fabricated by a blue GaN chip (450 nm) and only yellow phosphor Y₃Al₅O 12 :Ce 3+ (YAG:Ce) (1.0 wt % in silicone) emitted cold white light, its CIE (CIE: Commission International de I'Eclairage ) value was (0.32, 0.33), color rendering index (CRI) was 72.2, correlated color temperature (CCT) was 6877 K, and luminous efficiency ( η L ) was 128.5 lm∙W -1 . Such a cold white LED became a neutral white LED when [(TPTA)₂Ir(dPPOA)]PF₆ was added at 0.5 wt %; its corresponding CIE value was (0.35, 0.33), CRI was 78.4, CCT was 4896 K, and η L was 85.2 lm∙W -1 . It further became a warm white LED when [(TPTA)₂Ir(dPPOA)]PF₆ was added at 1.0 wt %; its corresponding CIE value was (0.39, 0.36), CRI was 80.2, CCT was 3473 K, and η L was 46.1 lm∙W -1 . The results show that [(TPTA)₂Ir(dPPOA)]PF₆ is a promising phosphor candidate for fabricating warm white LEDs.

  16. Structure and stability of hexa-aqua V(III) cations in vanadium redox flow battery electrolytes.

    Science.gov (United States)

    Vijayakumar, M; Li, Liyu; Nie, Zimin; Yang, Zhenguo; Hu, JianZhi

    2012-08-07

    The vanadium(III) cation structure in mixed acid based electrolyte solution from vanadium redox flow batteries is studied by (17)O and (35/37)Cl nuclear magnetic resonance (NMR) spectroscopy, electronic spectroscopy and density functional theory (DFT) based computational modelling. Both computational and experimental results reveal that the V(III) species can complex with counter anions (sulfate/chlorine) depending on the composition of its solvation sphere. By analyzing the powder precipitate it was found that the formation of sulfate complexed V(III) species is the crucial process in the precipitation reaction. The precipitation occurs through nucleation of neutral species formed through deprotonation and ion-pair formation process. However, the powder precipitate shows a multiphase nature which warrants multiple reaction pathways for precipitation reaction.

  17. Advanced Aqueous Separation Systems for Actinide Partitioning

    Energy Technology Data Exchange (ETDEWEB)

    Nash, Ken [Washington State Univ., Pullman, WA (United States); Martin, Leigh [Idaho National Lab. (INL), Idaho Falls, ID (United States); Lumetta, Gregg [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2015-04-02

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

  18. A time-resolved laser fluorescence spectroscopy (TRLFS) study of the interaction of trivalent actinides (curium(III)) with calcite

    International Nuclear Information System (INIS)

    Stumpf, Th.; Fanghaenel, Th.

    2002-01-01

    Cm(III) interaction with calcite was investigated in the trace concentration range. Two different Cm(III)/calcite sorption species were found. The first Cm(III) sorption species consists of a curium ion that is bonded onto the calcite surface. The second Cm(III) sorption species has lost its complete hydration sphere and is incorporated into the calcite bulk structure /1/. (orig.)

  19. Actinides-1981

    International Nuclear Information System (INIS)

    1981-09-01

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

  20. Actinides-1981

    Energy Technology Data Exchange (ETDEWEB)

    1981-09-01

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

  1. Extraction of actinides from chloride medium using pentaalkylpropanediamides

    International Nuclear Information System (INIS)

    Cuillerdier, C.; Musikas, C.

    1991-01-01

    Pyrometallurgical processes for the purification of plutonium create waste solutions containing actinides, mainly americium, in chloride medium. Studies have been undertaken to study the extraction of actinides in chloride medium (hydrochloric acid mixed with concentrated salts such as LiCl, CaCl 2 , MgCl 2 , KCl) using pentaalkylpropanediamides as extractants. Plutonium (IV) is very easily extracted, Am (III) needs a salting out agent such as LiCl. Back extraction of trivalent cations is easy in HCl <5M. Plutonium(IV) and (VI) can be stripped by reduction either with ascorbic acid or hydroxylammonium salts in weak acid medium. Several diluents can be used (aromatic, chlorinated or even aliphatic) with addition of decanol to prevent third phase formation. In conclusion diamides can be used for various wastes declassification, they are potentially completely incinerable, and, as the synthesis has been optimized, they appear to be promising extractants

  2. A contribution to the study of the extraction of mineral acids and of actinide (IV) and (VI) cations by N,N-dialkylamides

    International Nuclear Information System (INIS)

    Condamines, N.

    1990-03-01

    N,N-dialkylamides are alternate extractants to tributylphosphate, TBP, for the actinides separation in nuclear fuel reprocessing. N,N-di (2-ethyl hexyl) butyramide and N,N-di (2 ethyl hexyl) isobutyramide are selected for their sufficient extraction and partition ability towards actinides (IV) and (VI) without coextracting fission products. Mechanisms of HNO 3 , UO 2 2+ , Pu 4+ , Th 4+ are investigated. Nitric acid extraction is due to the competitive formation of the species (HNO 3 )L 2 , (HNO 3 )L, (HNO 3 ) 2 L (L: DOBA or DOiBA). An hydrogen bond is the driving force of the transfer. For low acidity media, amides are neutral extractants. Physical interactions, between free ligand and metallic complex, arise for high amide concentrations. Taking into account the non-ideality of the organic medium by a hard spheres mixture model, we estimate that such interactions are far from negligible and very specific to the amide group. Unlike TBP, when increasing acidity, amides behave as anionic extractants. DOBA and DOiBA appear to be satisfactory extractants for fuel reprocessing [fr

  3. Photochemical reactions of actinide ions

    International Nuclear Information System (INIS)

    Tomiyasu, Hiroshi

    1995-01-01

    This paper reviews the results of photochemical studies of actinide ions, which have been performed in our research group for past several years as follows: I) behavior of the excited uranyl(VI) ion; II) photo-reductions of the uranyl ion with organic and inorganic compounds; III) photo-oxidations of uranium(IV) and plutonium(III) in nitric acid solutions. (author)

  4. Formation of environmentally persistent free radical (EPFR) in iron(III) cation-exchanged smectite clay.

    Science.gov (United States)

    Nwosu, Ugwumsinachi G; Roy, Amitava; dela Cruz, Albert Leo N; Dellinger, Barry; Cook, Robert

    2016-01-01

    Environmentally persistent free radicals (EPFRs) have been found at a number of Superfund sites, with EPFRs being formed via a proposed redox process at ambient environmental conditions. The possibility of such a redox process taking place at ambient environmental conditions is studied utilizing a surrogate soil system of phenol and iron(III)-exchanged calcium montmorillonite clay, Fe(III)CaM. Sorption of phenol by the Fe(III)CaM is demonstrated by Fourier-transformed infra-red (FT-IR) spectroscopy, as evidenced by the peaks between 1345 cm(-1) and 1595 cm(-1), and at lower frequencies between 694 cm(-1) and 806 cm(-1), as well as X-ray diffraction (XRD) spectroscopy, as shown by an increase in interlayer spacing within Fe(III)CaM. The formation and characterization of the EPFRs is determined by electron paramagnetic resonance (EPR) spectroscopy, showing phenoxyl-type radical with a g-factor of 2.0034 and ΔHP-P of 6.1 G at an average concentration of 7.5 × 10(17) spins per g. EPFRs lifetime data are indicative of oxygen and water molecules being responsible for EPFR decay. The change in the oxidation state of the iron redox center is studied by X-ray absorption near-edge structure (XANES) spectroscopy, showing that 23% of the Fe(III) is reduced to Fe(II). X-ray photoemission spectroscopy (XPS) results confirm the XANES results. These findings, when combined with the EPFR concentration data, demonstrate that the stoichiometry of the EPFR formation under the conditions of this study is 1.5 × 10(-2) spins per Fe(II) atom.

  5. Th(As(III)4As(V)4O18): a mixed-valent oxoarsenic(III)/arsenic(V) actinide compound obtained under extreme conditions.

    Science.gov (United States)

    Yu, Na; Klepov, Vladislav V; Kegler, Philip; Bosbach, Dirk; Albrecht-Schmitt, Thomas E; Alekseev, Evgeny V

    2014-08-18

    A high-temperature/high-pressure method was employed to investigate phase formation in the Th(NO3)4·5H2O-As2O3-CsNO3 system. It was observed that an excess of arsenic(III) in starting system leads to the formation of Th(As(III)4As(V)4O18), which is representative of a rare class of mixed-valent arsenic(III)/arsenic(V) compounds. This compound was studied with X-ray diffraction, energy-dispersive X-ray, and Raman spectroscopy methods. Crystallographic data show that Th(As(III)4As(V)4O18) is built from (As(III)4As(V)4O18)(4-) layers connected through Th atoms. The arsenic layers are found to be isoreticular to those in previously reported As2O3 and As3O5(OH), and the geometric differences between them are discussed. Bands in the Raman spectrum are assigned with respect to the presence of AsO3 and AsO4 groups.

  6. Actinide recycle

    Energy Technology Data Exchange (ETDEWEB)

    Till, C; Chang, Y [Argonne National Laboratory, Argonne, IL (United States)

    1990-07-01

    A multitude of studies and assessments of actinide partitioning and transmutation were carried out in the late 1970s and early 1980s. Probably the most comprehensive of these was a study coordinated by Oak Ridge National Laboratory. The conclusions of this study were that only rather weak economic and safety incentives existed for partitioning and transmuting the actinides for waste management purposes, due to the facts that (1) partitioning processes were complicated and expensive, and (2) the geologic repository was assumed to contain actinides for hundreds of thousands of years. Much has changed in the few years since then. A variety of developments now combine to warrant a renewed assessment of the actinide recycle. First of all, it has become increasingly difficult to provide to all parties the necessary assurance that the repository will contain essentially all radioactive materials until they have decayed. Assurance can almost certainly be provided to regulatory agencies by sound technical arguments, but it is difficult to convince the general public that the behavior of wastes stored in the ground can be modeled and predicted for even a few thousand years. From this point of view alone there would seem to be a clear benefit in reducing the long-term toxicity of the high-level wastes placed in the repository.

  7. Actinide recycle

    International Nuclear Information System (INIS)

    Till, C.; Chang, Y.

    1990-01-01

    A multitude of studies and assessments of actinide partitioning and transmutation were carried out in the late 1970s and early 1980s. Probably the most comprehensive of these was a study coordinated by Oak Ridge National Laboratory. The conclusions of this study were that only rather weak economic and safety incentives existed for partitioning and transmuting the actinides for waste management purposes, due to the facts that (1) partitioning processes were complicated and expensive, and (2) the geologic repository was assumed to contain actinides for hundreds of thousands of years. Much has changed in the few years since then. A variety of developments now combine to warrant a renewed assessment of the actinide recycle. First of all, it has become increasingly difficult to provide to all parties the necessary assurance that the repository will contain essentially all radioactive materials until they have decayed. Assurance can almost certainly be provided to regulatory agencies by sound technical arguments, but it is difficult to convince the general public that the behavior of wastes stored in the ground can be modeled and predicted for even a few thousand years. From this point of view alone there would seem to be a clear benefit in reducing the long-term toxicity of the high-level wastes placed in the repository

  8. Extraction characteristics of trivalent lanthanides and actinides in mixtures of dinonylnaphthalenesulfonic acid and carboxylic acids

    International Nuclear Information System (INIS)

    West, M.H.

    1983-03-01

    Dinonylnaphthalenesulfonic acid (HDNNS) has been shown to be an effective liquid cation exchanger for the extraction of metal ions. This extractant has proven to be successful in the extraction of trivalent lanthanides and actinides in the pH range of 2.0 to 3.0, although it shows little selectivity for individual ions because of its strong acid character. In an effort to improve the selectivity of HDNNS between trivalent lanthanides and actinides, carboxylic acids were added to the organic phase and the effects on the extraction characteristics of HDNNS were investigated. Three carboxylic acids - nonanoic, cyclohexanecarboxylic, and cyclohexanebutyric - were studied with the following metals: Am(III), Cm(III), Ce(III), Eu(III), and Tm(III). The distributions of the metal ions were studied holding the HDNNS concentration constant while varying the carboxylic acid concentrations over a range of 1.0 x 10 -5 M to 1.0 M. Results indicated that the greatest enhancement of the extraction occurred at a carboxylic acid concentration of 1.0 x 10 -2 M with negative effects occurring at 0.5 M and 1.0 M. The effects on the extraction of the trivalent lanthanides and actinides were interpreted in terms of the structural differences of the carboxylic acids, the effect of the carboxylic acids on the HDNNS extraction mechanism, and the ionic properties of the metals studied

  9. Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

    Science.gov (United States)

    Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

    2011-01-01

    Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

  10. Actinides(3)/lanthanides(3) separation by nano-filtration assisted by complexation; Separation actinides(3)lanthanides(3) par nanofiltration assistee par complexation

    Energy Technology Data Exchange (ETDEWEB)

    Sorin, A

    2006-07-01

    In France, one of the research trend concerning the reprocessing of spent nuclear fuel consists to separate selectively the very radio-toxic elements with a long life to be recycled (Pu) or transmuted (Am, Cm, Np). The aim of this thesis concerns the last theme about actinides(III)/lanthanides(III) separation by a process of nano-filtration assisted by complexation. Thus, a pilot of tangential membrane filtration was designed and established in a glove box at the ATALANTE place of CEA-Marcoule. Physico-chemical characterisation of the Desal GH membrane (OSMONICS), selected to carry out actinides(III)/lanthanides(III) separation, was realized to determine the zeta potential of the active layer and its resistance to ionizing radiations. Moreover, a parametric study was also carried out to optimize the selectivity of complexation, and the operating conditions of complex retention (influences of the transmembrane pressure, solute concentration, tangential velocity and temperature). Finally, the separation of traces of Am(III) contained in a mixture of lanthanides(III), simulating the real load coming from a reprocessing cycle, was evaluated with several chelating agents such as poly-amino-carboxylic acids according to the solution acidity and the [Ligand]/[Cation(III)] ratio. (author)

  11. The actinides

    International Nuclear Information System (INIS)

    Bagnall, K.W.

    1987-01-01

    This chapter of coordination compound chemistry is devoted to the actinides and starts with a general survey. Most of the chapter relates to thorium and uranium but protactinium, neptunium and plutonium are included. There are sections on nitrogen, phosphorus, sulfur, selenium, tellurium and halogen ligands of the metals in their +3, +4, +5 and +6 oxidation states and of the transplutonium elements in their +2, +3, +4, and +5 oxidation states. (UK)

  12. Angular overlap model in actinides

    International Nuclear Information System (INIS)

    Gajek, Z.; Mulak, J.

    1991-01-01

    Quantitative foundations of the Angular Overlap Model in actinides based on ab initio calculations of the crystal field effect in the uranium (III) (IV) and (V) ions in various crystals are presented. The calculations justify some common simplifications of the model and fix up the relations between the AOM parameters. Traps and limitations of the AOM phenomenology are discussed

  13. Angular overlap model in actinides

    Energy Technology Data Exchange (ETDEWEB)

    Gajek, Z.; Mulak, J. (Polska Akademia Nauk, Wroclaw (PL). Inst. Niskich Temperatur i Badan Strukturalnych)

    1991-01-01

    Quantitative foundations of the Angular Overlap Model in actinides based on ab initio calculations of the crystal field effect in the uranium (III) (IV) and (V) ions in various crystals are presented. The calculations justify some common simplifications of the model and fix up the relations between the AOM parameters. Traps and limitations of the AOM phenomenology are discussed.

  14. Aqueous complexes of lanthanides(III) and actinides(III) with the carbonate and sulphate ions. Thermodynamic study by time-resolved laser-induced fluorescence spectroscopy and electro-spray-ionisation mass spectrometry

    International Nuclear Information System (INIS)

    Vercouter, Th.

    2005-03-01

    The prediction of the environmental impact of a possible geological disposal of radioactive wastes is supported by the thermodynamic modelling of the radionuclides behaviour in the groundwater. In this framework, the analogy between lanthanides and actinides(III) is confirmed by a critical analysis of the literature and the comparison with experimental results obtained here. The limiting complex, Eu(CO 3 ) 3 3- , is identified by solubility measurements in Na 2 CO 3 solutions. Then the formation constants of the complexes Eu(CO 3 ) i 3-2i (i=1-3) and Eu(SO 4 ) i 3-2i (i=1-2) are measured by TRLFS. The formation of aqueous LaSO 4 + is studied by ESI-MS and is in good agreement with the expected speciation. The enthalpy and entropy of the reaction Cm(CO 3 ) 2 - + CO 3 2- ↔ Cm(CO 3 ) 3 3- are deduced from TRLFS measurements of the equilibrium constant between 10 and 70 C. The ionic strength effect is calculated using the SIT formula. (author)

  15. Multiscale structural characterizations of mixed U(iv)-An(iii) oxalates (An(iii) = Pu or Am) combining XAS and XRD measurements.

    Science.gov (United States)

    Arab-Chapelet, B; Martin, P M; Costenoble, S; Delahaye, T; Scheinost, A C; Grandjean, S; Abraham, F

    2016-04-28

    Mixed actinide(III,IV) oxalates of the general formula M2.2UAn(C2O4)5·nH2O (An = Pu or Am and M = H3O(+) and N2H5(+)) have been quantitatively precipitated by oxalic precipitation in nitric acid medium (yield >99%). Thorough multiscale structural characterization using XRD and XAS measurements confirmed the existence of mixed actinide oxalate solid solutions. The XANES analysis confirmed that the oxidation states of the metallic cations, tetravalent for uranium and trivalent for plutonium and americium, are maintained during the precipitation step. EXAFS measurements show that the local environments around U(+IV), Pu(+III) and Am(+III) are comparable, and the actinides are surrounded by ten oxygen atoms from five bidentate oxalate anions. The mean metal-oxygen distances obtained by XAS measurements are in agreement with those calculated from XRD lattice parameters.

  16. A contribution to the study of the extraction of mineral acids and of actinide (IV) and (VI) cations by N,N-dialkylamides; Contribution a l'etude de l'extraction d'acides mineraux et de cations actinides aux degres d'oxydation (IV) et (VI) par des N,N-dialkylamides

    Energy Technology Data Exchange (ETDEWEB)

    Condamines, N

    1990-03-15

    N,N-dialkylamides are alternate extractants to tributylphosphate, TBP, for the actinides separation in nuclear fuel reprocessing. N,N-di (2-ethyl hexyl) butyramide and N,N-di (2 ethyl hexyl) isobutyramide are selected for their sufficient extraction and partition ability towards actinides (IV) and (VI) without coextracting fission products. Mechanisms of HNO{sub 3}, UO{sub 2}{sup 2+}, Pu{sup 4+}, Th{sup 4+} are investigated. Nitric acid extraction is due to the competitive formation of the species (HNO{sub 3})L{sub 2}, (HNO{sub 3})L, (HNO{sub 3}){sub 2}L (L: DOBA or DOiBA). An hydrogen bond is the driving force of the transfer. For low acidity media, amides are neutral extractants. Physical interactions, between free ligand and metallic complex, arise for high amide concentrations. Taking into account the non-ideality of the organic medium by a hard spheres mixture model, we estimate that such interactions are far from negligible and very specific to the amide group. Unlike TBP, when increasing acidity, amides behave as anionic extractants. DOBA and DOiBA appear to be satisfactory extractants for fuel reprocessing.

  17. Purification of Anthocyanins with o-Dihydroxy Arrangement by Sorption in Cationic Resins Charged with Fe(III

    Directory of Open Access Journals (Sweden)

    Araceli Castañeda-Ovando

    2014-01-01

    Full Text Available In the present work, a new purification method of anthocyanins with o-dihydroxy arrangement is proposed. This method is based on a ligand-exchange mechanism, using a cationic exchange resin loaded with metallic ions in order to increase the affinity of the resin to the anthocyanin(s with o-dihydroxy arrangement. This method was used to purify the main anthocyanin (cyanidin-3-glucoside; Cy-3-glc from the anthocyanic methanolic extract of blue corn. The best sorption result was using Fe(III in its ion form. The purification procedure begins with the formation of a metal-anthocyanin complex (Cy-3-glc-Fe which was optimal at pH 5, followed by a NaOH 0.1 M elution process in order to eliminate anthocyanins without o-dihydroxy arrangement, sugars, and organic acids. Finally, the pure anthocyanin is obtained by adding HCl 0.1 M which breaks the metal-anthocyanin complex.

  18. Aqueous complexes of lanthanides(III) and actinides(III) with the carbonate and sulphate ions. Thermodynamic study by time-resolved laser-induced fluorescence spectroscopy and electro-spray-ionisation mass spectrometry; Complexes aqueux de lanthanides (3) et actinides (3) avec les ions carbonate et sulfate. Etude thermodynamique par spectrofluorimetrie laser resolue en temps et spectrometrie de masse a ionisation electrospray

    Energy Technology Data Exchange (ETDEWEB)

    Vercouter, Th

    2005-03-15

    The prediction of the environmental impact of a possible geological disposal of radioactive wastes is supported by the thermodynamic modelling of the radionuclides behaviour in the groundwater. In this framework, the analogy between lanthanides and actinides(III) is confirmed by a critical analysis of the literature and the comparison with experimental results obtained here. The limiting complex, Eu(CO{sub 3}){sub 3}{sup 3-}, is identified by solubility measurements in Na{sub 2}CO{sub 3} solutions. Then the formation constants of the complexes Eu(CO{sub 3}){sub i}{sup 3-2i} (i=1-3) and Eu(SO{sub 4}){sub i}{sup 3-2i} (i=1-2) are measured by TRLFS. The formation of aqueous LaSO{sub 4}{sup +} is studied by ESI-MS and is in good agreement with the expected speciation. The enthalpy and entropy of the reaction Cm(CO{sub 3}){sub 2}{sup -} + CO{sub 3}{sup 2-} {r_reversible} Cm(CO{sub 3}){sub 3}{sup 3-} are deduced from TRLFS measurements of the equilibrium constant between 10 and 70 C. The ionic strength effect is calculated using the SIT formula. (author)

  19. TUCS/phosphate mineralization of actinides

    Energy Technology Data Exchange (ETDEWEB)

    Nash, K.L. [Argonne National Lab., IL (United States)

    1997-10-01

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

  20. Actinide separation by electrorefining

    International Nuclear Information System (INIS)

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

    1995-01-01

    TRUMP-S is a pyrochemical process being developed for the recovery of actinides from PUREX wastes. This paper describes development of the electrochemical partitioning step for recovery of actinides in the TRUMP-S process. The objectives are to remove 99 % of each actinide from PUREX wastes, with a product that is > 90 % actinides. Laboratory tests indicate that > 99 % of actinides can be removed in the electrochemical partitioning step. A dynamic (not equilibrium) process model predicts that 90 wt % product actinide content can be achieved through 99 % actinide removal. Accuracy of model simulation results were confirmed in tests with rare earths. (authors)

  1. Actinide-Aluminate Speciation in Alkaline Radioactive Waste

    International Nuclear Information System (INIS)

    Clark, David L.; Fedosseev, Alexander M.

    2001-01-01

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

  2. Ordered perovskites with cationic vacancies. 9. Compounds of the type Sr/sub 2/Srsub(1/4)Bsub(1/2)sup(III)vacantsub(1/4)WO/sub 6/ equivalent to Sr/sub 8/SrB/sub 2/sup(III)vacantW/sub 4/O/sub 24/ (Bsup(III) = La, Pr, Nd, Sm - Tm, Y)

    Energy Technology Data Exchange (ETDEWEB)

    Kemmler-Sack, S; Ehmann, A [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

    1981-08-01

    The compounds Sr/sub 2/Srsub(1/4)Bsub(1/2)sup(III)vacantsub(1/4)WO/sub 6/ equivalent to Sr/sub 8/SrB/sub 2/sup(III)vacantW/sub 4/O/sub 24/ belong to the group of perovskites with octahedral cationic vacancies (cation/vacancy ratio (CN 6) = 7:1). For the larger Bsup(III) ions (La, Pr, Nd, Sm-Dy) different ordering effects are observed. The perovskites with Bsup(III) = Sm, Eu, Gd are polymorphic too (HT modification: higher ordered cubic perovskite (Bsup(III) = Gd: a = 2 x 8.23/sub 4/ A); LT modification: hexagonal perovskite stacking polytype (Bsup(III) = Gd: a = 9.95/sub 4/ A; c = 19.0/sub 4/ A)). With the smaller Bsup(III) ions (Ho, Er, Tm and Y) a cubic, 1:1 ordered perovskite type is observed.

  3. Research for actinides extractants from various wastes

    International Nuclear Information System (INIS)

    Musikas, C.; Cuillerdier, C.; Condamines, N.

    1990-01-01

    This paper is an overview of the actinides solvent extraction research undertaken in Fontenay-aux-Roses. Two kinds of extractants are investigated; those usable for the improvement of the nowadays nuclear fuels reprocessing and those necessary for advanced fuels cycles which include the minor actinides (Np, Am) recovery for a further elimination through nuclear reactions. In the first class the mono and diamides, alternative to the organophosphorus extractants, TBP and polyfunctional phosphonates, showed promising properties. The main results are discussed. For the future efficient extractants for trivalent actinides-lanthanides group separations are suitable. The point about the actinides (III) - lanthanides (III) group separation chemistry and the development of some of these extractants are given

  4. Actinide speciation in the environment

    International Nuclear Information System (INIS)

    Choppin, G.R.

    2007-01-01

    Nuclear test explosions and nuclear reactor wastes and accidents have released large amounts of radioactivity into the environment. Actinide ions in waters often are not in a state of thermodynamic equilibrium and their solubility and migration behavior is related to the form in which the nuclides are introduced into the aquatic system. Chemical speciation, oxidation state, redox reactions, and sorption characteristics are necessary in predicting solubility of the different actinides, their migration behaviors and their potential effects on marine biota. The most significant of these variables is the oxidation state of the metal ion as the simultaneous presence of more than one oxidation state for some actinides in a solution complicates actinide environmental behavior. Both Np(V)O 2 + and Pu(V)O 2 + , the most significant soluble states in natural oxic waters, are relatively noncomplexing and resistant to hydrolysis and subsequent precipitation. The solubility of NpO 2 + can be as high as 10 -4 M while that of PuO 2 + is much more limited by reduction to the insoluble tetravalent species, Pu(OH) 4 , (pK sp ≥56) but which can be present in the pentavalent form in aqautic phases as colloidal material. The solubility of hexavalent UO 2 2+ in sea water is relatively high due to formation of carbonate complexes. The insoluble trivalent americium hydroxocarbonate, Am(OH)(CO 3 ) is the limiting species for the solubility of Am(III) in sea water. Thorium(IV) is present as Th(OH) 4 , in colloidal form. The chemistry of actinide ions in the environment is reviewed to show the spectrum of reactions that can occur in natural waters which must be considered in assessing the environmental behavior of actinides. Much is understood about sorption of actinides on surfaces, the mode of migration of actinides in such waters and the potential effects of these radioactive species on marine biota, but much more understanding of the behavior of the actinides in the environment is

  5. Actinide metal processing

    International Nuclear Information System (INIS)

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

    1992-01-01

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

  6. Rare earths and actinides

    International Nuclear Information System (INIS)

    Coqblin, B.

    1982-01-01

    This paper reviews the different properties of rare-earths and actinides, either as pure metals or as in alloys or compounds. Three different cases are considered: (i) First, in the case of 'normal' rare-earths which are characterized by a valence of 3, we discuss essentially the magnetic ordering, the coexistence between superconductivity and magnetism and the properties of amorphous rare-earth systems. (ii) Second, in the case of 'anomalous' rare-earths, we distinguish between either 'intermediate-valence' systems or 'Kondo' systems. Special emphasis is given to the problems of the 'Kondo lattice' (for compounds such as CeAl 2 ,CeAl 3 or CeB 6 ) or the 'Anderson lattice' (for compounds such as TmSe). The problem of neutron diffraction in these systems is also discussed. (iii) Third, in the case of actinides, we can separate between the d-f hybridized and almost magnetic metals at the beginning of the series and the rare-earth like the metals after americium. (orig.)

  7. Mechanisms for the reduction of actinide ions by Geobacter sulfurreducens

    International Nuclear Information System (INIS)

    Renshaw, J.C.; Livens, F.R.; May, I.; Lloyd, J.R.

    2005-01-01

    Full text of publication follows: Three of the most problematic radioactive contaminants are the actinide elements uranium, neptunium and plutonium. All three pose considerable long-term environmental risks. The most stable environmental oxidation states of uranium and neptunium are VI and V, respectively, as the di-oxo cations [UO 2 ] 2+ and [NpO 2 ] + ; both are highly soluble and so are relatively mobile and biologically available in the environment. In similar conditions, plutonium mainly exists as Pu(IV), which forms a highly insoluble hydrous oxide, although is also environmentally stable in the more soluble III, V and VI oxidation states. The bio-reduction of U(VI) by anaerobic subsurface microorganisms has been the focus of much recent interest. Both Fe(III)- and sulfate-reducing bacteria have been shown to reduce soluble [U VI O 2 ] 2+ to insoluble U IV O 2 , with c-type cytochromes involved in electron transfer to the actinide. Such transformations offer a strategy for the bio-remediation of uranium contaminated groundwater and a potential mechanism for the bio-deposition of uranium ores. The mechanism of U(VI). reduction has important implications for the potential microbial reduction of transuranic elements with environmentally stable lower oxidation states. Reduction of mobile 237 Np(V) to Np(IV) and subsequent precipitation may be advantageous whilst remobilization of immobile Pu(IV) as more soluble Pu(III) species could have important environmental implications. Conversely, selective reduction might allow targeting of particular radionuclide species. The model anaerobic bacterium Geobacter sulfurreducens is typical of those found in contaminated subsurface environments and has been shown to reduce soluble [U VI O 2 ] 2+ to insoluble U IV O 2 . In the course of this study we use X-ray absorption spectroscopy (XAS) to show that G. sulfurreducens reduces U(VI) by a one-electron reduction, forming an unstable [UO 2 ] + species which subsequently

  8. NMR and TRLFS studies of Ln(iii) and An(iii) C5-BPP complexes.

    Science.gov (United States)

    Adam, Christian; Beele, Björn B; Geist, Andreas; Müllich, Udo; Kaden, Peter; Panak, Petra J

    2015-02-01

    C5-BPP is a highly efficient N-donor ligand for the separation of trivalent actinides, An(iii), from trivalent lanthanides, Ln(iii). The molecular origin of the selectivity of C5-BPP and many other N-donor ligands of the BTP-type is still not entirely understood. We present here the first NMR studies on C5-BPP Ln(iii) and An(iii) complexes. C5-BPP is synthesized with 10% 15 N labeling and characterized by NMR and LIFDI-MS methods. 15 N NMR spectroscopy gives a detailed insight into the bonding of C5-BPP with lanthanides and Am(iii) as a representative for trivalent actinide cations, revealing significant differences in 15 N chemical shift for coordinating nitrogen atoms compared to Ln(iii) complexes. The temperature dependence of NMR chemical shifts observed for the Am(iii) complex indicates a weak paramagnetism. This as well as the observed large chemical shift for coordinating nitrogen atoms show that metal-ligand bonding in Am(C5-BPP) 3 has a larger share of covalence than in lanthanide complexes, confirming earlier studies. The Am(C5-BPP) 3 NMR sample is furthermore spiked with Cm(iii) and characterized by time-resolved laser fluorescence spectroscopy (TRLFS), yielding important information on the speciation of trace amounts of minor complex species.

  9. Synthesis of a 3D lanthanum(III) MOFs as a multi-chemosensor to Cr(VI)-containing anion and Fe(III) cation based on a flexible ligand

    Science.gov (United States)

    Ma, Yang-Min; Liu, Tong; Huang, Wen-Huan

    2018-02-01

    Based on La(NO3)3·6H2O and 4,4‧-((5-carboxy-1,3-phenylene)bis(oxy))dibenzoic acid (H3cpbda), a 3D porous MOFs, [La(cpbda)(H2O)1.5]n (1), was synthesized by hydrothermal method and further characterized by single-crystal X-ray diffraction, power X-ray diffraction, IR spectroscopy, thermal-gravimetric analysis and fluorescence spectroscopy. Owing to its good stabilities and fluorescence property, the sensing experiments on sixteen cations and eleven anions were implemented. Moreover, the further titration processes show 1 can sensitively detect the Fe(III) cation and Cr(VI)-containing anions by quenching responses.

  10. Actinide extractants for the nuclear industry of the future

    International Nuclear Information System (INIS)

    Musikas, C.; Morisseau, J.C.; Hoel, P.; Guillaume, B.

    1987-06-01

    Non organo-phosphorus extractants properties regarding the extractions of actinides in nuclear fuels reprocessing are presented. N,N-dialkylamides are proposed as alternatives to TBP.N,N'-tetraalkylamides or pentaalkyl propane diamides properties are reported. They show that those bidentate extractants are alternatives to bidentate organophosphorus extractants for actinides (III) extraction from concentrated nitric acid. 11 figs, 15 refs

  11. Recent progress in actinide and lanthanide solvent extraction

    International Nuclear Information System (INIS)

    Musikas, C.; Hubert, H.; Benjelloun, N.; Vitorge, P.; Bonnin, M.; Forchioni, A.; Chachaty, C.

    1983-04-01

    Work in progress on actinide solvent extraction is briefly reviewed in this paper. 1 H and 31 P NMR are used to elucidate several fundamental unsolved problems concerning organophosphorous extractants often used in actinides extraction: determination of site of dialkylthiophosphate protonation and addition of basic phosphine oxide to dibutylthiophosphoric acid dimer. Extraction of Am III and Eu from high radioactivity level wastes by tetrasubsituted methylene diamides is investigated. Trivalent actinide-lanthanide group are separated by solvent extraction using soft donor ligand complexes which are more stable. The synergism of dinonylnaphtalene sulfonic acid (HDNNS) associated with several neutral donors like TBP, TOPO, amides are examined in the trivalent and tetravalent actinide extraction

  12. The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory.

    Science.gov (United States)

    Dumas, Thomas; Guillaumont, Dominique; Fillaux, Clara; Scheinost, Andreas; Moisy, Philippe; Petit, Sébastien; Shuh, David K; Tyliszczak, Tolek; Den Auwer, Christophe

    2016-01-28

    The electronic properties of actinide cations are of fundamental interest to describe intramolecular interactions and chemical bonding in the context of nuclear waste reprocessing or direct storage. The 5f and 6d orbitals are the first partially or totally vacant states in these elements, and the nature of the actinide ligand bonds is related to their ability to overlap with ligand orbitals. Because of its chemical and orbital selectivities, X-ray absorption spectroscopy (XAS) is an effective probe of actinide species frontier orbitals and for understanding actinide cation reactivity toward chelating ligands. The soft X-ray probes of the light elements provide better resolution than actinide L3-edges to obtain electronic information from the ligand. Thus coupling simulations to experimental soft X-ray spectral measurements and complementary quantum chemical calculations yields quantitative information on chemical bonding. In this study, soft X-ray XAS at the K-edges of C and N, and the L2,3-edges of Fe was used to investigate the electronic structures of the well-known ferrocyanide complexes K4Fe(II)(CN)6, thorium hexacyanoferrate Th(IV)Fe(II)(CN)6, and neodymium hexacyanoferrate KNd(III)Fe(II)(CN)6. The soft X-ray spectra were simulated based on quantum chemical calculations. Our results highlight the orbital overlapping effects and atomic effective charges in the Fe(II)(CN)6 building block. In addition to providing a detailed description of the electronic structure of the ferrocyanide complex (K4Fe(II)(CN)6), the results strongly contribute to confirming the actinide 5f and 6d orbital oddity in comparison to lanthanide 4f and 5d.

  13. Methods for separating actinides from reprocessing and refabrication plant wastes

    International Nuclear Information System (INIS)

    Tedder, D.W.; Finney, B.C.; Blomeke, J.O.

    1979-01-01

    Chemical processing flowsheets have been developed to partition actinides from all actinide-bearing LWR fuel reprocessing and refabrication plant wastes. These wastes include high-activity-level liquids, scrap recovery liquors, HEPA filters and incinerator ashes, and chemical salt wastes such as sodium carbonate scrub solutions, detergent cleanup streams, and alkaline off-gas scrubber liquors. The separations processes that were adopted for this study are based on solvent extraction, cation exchange chromatography, and leaching with Ce 4+ -HNO 3 solution

  14. Actinide uptake by transferrin and ferritin metalloproteins

    International Nuclear Information System (INIS)

    Den Auwer, C.; Llorens, I.; Moisy, Ph.; Vidaud, C.; Goudard, F.; Barbot, C.; Solari, P.L.; Funke, H.

    2005-01-01

    In order to better understand the mechanisms of actinide uptake by specific biomolecules, it is essential to explore the intramolecular interactions between the cation and the protein binding site. Although this has long been done for widely investigated transition metals, very few studies have been devoted to complexation mechanisms of actinides by active chelation sites of metalloproteins. In this field, X-ray absorption spectroscopy has been extensively used as a structural and electronic metal cation probe. The two examples that are presented here are related to two metalloproteins in charge of iron transport and storage in eukaryote cells: transferrin and ferritin. U(VI)O 2 2+ , Np(IV) and Pu(IV) have been selected because of their possible role as contaminant from the geosphere. (orig.)

  15. Synthesis of tetravalent actinide chlorides. Versatile compounds for actinide chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Maerz, Juliane [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Chemistry of the F-Elements

    2016-07-01

    Anhydrous actinide tetrachlorides (AnCl{sub 4}) were synthesized under mild conditions to provide versatile compounds for actinide chemistry. They enable a direct access to actinide complexes with organic and inorganic ligands.

  16. Effect of alkali cations on two-dimensional networks of two new quaternary thioarsenates (III) prepared by a facile surfactant-thermal method

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Dongming [School of Civil and Architectural Engineering, Zhejiang University, Hangzhou 310058 (China); Hou, Peipei; Liu, Chang [State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Chai, Wenxiang [College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Zheng, Xuerong [State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Zhang, Luodong [School of Civil and Architectural Engineering, Zhejiang University, Hangzhou 310058 (China); Zhi, Mingjia; Zhou, Chunmei [State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Liu, Yi, E-mail: liuyimse@zju.edu.cn [State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China)

    2016-09-15

    Two new quaternary thioarsenates(III) NaAg{sub 2}AsS{sub 3}·H{sub 2}O (1) and KAg{sub 2}AsS{sub 3} (2) with high yields have been successfully prepared through a facile surfactant-thermal method. It is interesting that 2 can only be obtained with the aid of ethanediamine (en), which indicates that weak basicity of solvent is beneficial to the growth of 2 compared with 1. Both 1 and 2 feature the similar two-dimensional (2D) layer structures. However, the distortion of the primary honeycomb-like nets in 2 is more severe than that of 1, which demonstrates that Na{sup +} and K{sup +} cations have different structure directing effects on these two thioarsenates(III). Both experimental and theoretical studies confirm 1 and 2 are semiconductors with band gaps in the visible region. Our success in preparing these two quaternary thioarsenates(III) proves that surfactant-thermal technique is a powerful yet facile synthetic method to explore new complex chalcogenides. - Graphical abstract: Two new quaternary thioarsenates(III) NaAg{sub 2}AsS{sub 3}·H{sub 2}O (1) and KAg{sub 2}AsS{sub 3} (2) with high yields have been successfully prepared through a facile surfactant-thermal method. X-ray single crystal diffraction analyses demonstrate that Na{sup +} and K{sup +} cations have different structure directing effects on these two thioarsenates(III). Both experimental and theoretical studies confirm 1 and 2 are semiconductors with band gaps in the visible region. Display Omitted - Highlights: • NaAg{sub 2}AsS{sub 3}⋅H{sub 2}O (1) and KAg{sub 2}AsS{sub 3} (2) were prepared through surfactant-thermal method. • Crystal structures show Na{sup ±} and K{sup ±} have different structure directing effects. • The weak basicity of solvent is benefit to the growth of 2 compared with 1. • Experimental and theoretical studies confirm 1 and 2 are semiconductors.

  17. Cationic Amphiphilic Tris-Cyclometalated Iridium(III) Complexes Induce Cancer Cell Death via Interaction with Ca2+-Calmodulin Complex.

    Science.gov (United States)

    Hisamatsu, Yosuke; Suzuki, Nozomi; Masum, Abdullah-Al; Shibuya, Ai; Abe, Ryo; Sato, Akira; Tanuma, Sei-Ichi; Aoki, Shin

    2017-02-15

    In our previous paper, we reported on the preparation of some cationic amphiphilic Ir complexes (2c, 2d) containing KKGG peptides that induce and detect cell death of Jurkat cells. Mechanistic studies suggest that 2c interacts with anionic molecules and/or membrane receptors on the cell surface to trigger an intracellular Ca 2+ response, resulting in the induction of cell death, accompanied by membrane disruption. We have continued the studies of cell death of Jurkat cells induced by 2c and found that xestospongin C, a selective inhibitor of an inositol 1,4,5-trisphosphate receptor located on the endoplasmic reticulum (ER), reduces the cytotoxicity of 2c, suggesting that 2c triggers the release of Ca 2+ from the ER, leading to an increase in the concentration of cytosolic Ca 2+ , thus inducing cell death. Moreover, we synthesized a series of new amphiphilic cationic Ir complexes 5a-c containing photoreactive 3-trifluoromethyl-3-phenyldiazirine (TFPD) groups, in an attempt to identify the target molecules of 2c. Interestingly, it was discovered that a TFPD group functions as a triplet quencher of Ir complexes. It was also found that 5b is useful as a turn-on phosphorescent probe of acidic proteins such as bovine serum albumin (BSA) (pI = 4.7) and their complexation was confirmed by luminescence titrations and SDS-PAGE of photochemical products between them. These successful results allowed us to carry out photoaffinity labeling of the target biomolecules of 5b (2c and analogues thereof) in Jurkat cells. A proteomic analysis of the products obtained by the photoirradiation of 5b with Jurkat cells suggests that the Ca 2+ -binding protein "calmodulin (CaM)" is one of target proteins of the Ir complexes. Indeed, 5b was found to interact with the Ca 2+ -CaM complex, as evidenced by luminescence titrations and the results of photochemical reactions of 5b with CaM in the presence of Ca 2+ (SDS-PAGE). A plausible mechanism for cell death induced by a cationic amphiphilic Ir

  18. Photocatalysis of the homogeneous water-gas shift reaction under ambient conditions by cationic iridium (III) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Ziessel, R [Ecole Europeenne des Hautes Etudes des Industries Chimiques, 67 - Strasbourg (France)

    1991-07-01

    We describe here our results and mechanistic analysis of the first highly efficient light-assisted WGSR, which takes place under extremely mild conditions (room temperature, ambient pressure, neutral pH, visible light) and is catalyzed by novel Ir{sup III} pentamethylcyclopentadienyl complexes containing novel 4,4'-substituted bipyridine ligands. (orig./EF).

  19. Heteroleptic and Homoleptic Iron(III Spin-Crossover Complexes; Effects of Ligand Substituents and Intermolecular Interactions between Co-Cation/Anion and the Complex

    Directory of Open Access Journals (Sweden)

    Wasinee Phonsri

    2017-08-01

    Full Text Available The structural and magnetic properties of a range of new iron(III bis-tridentate Schiff base complexes are described with emphasis on how intermolecular structural interactions influence spin states and spin crossover (SCO in these d5 materials. Three pairs of complexes were investigated. The first pair are the neutral, heteroleptic complexes [Fe(3-OMe-SalEen(thsa] 1 and [Fe(3-MeOSalEen(3-EtOthsa] 2, where 3-R-HSalEen = (E-2-(((2-(ethylaminoethyliminomethyl-6-R-phenol and 3-R-H2thsa = thiosemicarbazone-3-R-salicylaldimine. They display spin transitions above room temperature. However, 2 shows incomplete and gradual change, while SCO in 1 is complete and more abrupt. Lower cooperativity in 2 is ascribed to the lack of π–π interactions, compared to 1. The second pair, cationic species [Fe(3-EtOSalEen2]NO3 3 and [Fe(3-EtOSalEen2]Cl 4 differ only in the counter-anion. They show partial SCO above room temperature with 3 displaying a sharp transition at 343 K. Weak hydrogen bonds from cation to Cl− probably lead to weaker cooperativity in 4. The last pair, CsH2O[Fe(3-MeO-thsa2] 5 and Cs(H2O2[Fe(5-NO2-thsa2] 6, are anionic homoleptic chelates that have different substituents on the salicylaldiminate rings of thsa2−. The Cs cations bond to O atoms of water and the ligands, in unusual ways thus forming attractive 1D and 3D networks in 5 and 6, respectively, and 5 remains HS (high spin at all temperatures while 6 remains LS (low spin. Comparisons are made to other literature examples of Cs salts of [Fe(5-R-thsa2]− (R = H and Br.

  20. The human red cell voltage-dependent cation channel. Part III: Distribution homogeneity and pH dependence

    DEFF Research Database (Denmark)

    Bennekou, P.; Barksmann, T. L.; Christophersen, P.

    2006-01-01

    The homogeneity of the distribution of the non-selective voltage-dependent cation channel (the NSVDC channel) in the human erythrocyte, and the pH dependence was investigated. Activation of this channel caused a uniform cellular dehydration, which was characterized by the changes in the erythrocyte...... osmotic resistance profiles: After 1/2 h of activation, the osmolarity at 50% hemolysis changed from 73 mM (control) to 34 mM NaCl, corresponding to 0.48% and 0.21% NaCl respectively. Unchanging standard deviations show participation of the entire erythrocyte population, which implies an even distribution...... of the NSVDC channel among the cells. Inactivation of the NSVDC channel with N-ethyl-maleimide (NEM) or blocking of the Cl- conductance with NS1652 retarded the migration of the resistance profiles towards lower osmolarities. The NSVDC channel activation was blocked by a decrease of the intracellular...

  1. Ion exchange removal of chromium (iii) from tannery wastes by using a strong acid cation exchange resin amberlite ir-120 h+ and its hybrids

    International Nuclear Information System (INIS)

    Ahmad, T.

    2014-01-01

    A strong acid cation exchange resin Amberlite IR-120 H+ and its hybrids with Mn(OH)/sub 2/, Cu(OH)/sub 2/ and Fe(OH)/sub 3/ are used for the removal of chromium (III) from spent tannery bath. The experimental data give good fits with the Langmuir sorption model. The thermodynamic parameters entropy (delta S), enthalpy (delta H) and free energy (delta G) changes are computed, which reveal that the chromium removal from tannery wastes by ion exchangers is an endothermic, physical sorption and entropically driven process. The rate of sorption is found to increase with the increase of resin dosage, stirring speed and temperature. Different kinetic models such as film diffusion, particle diffusion and Lagergren pseudo first order are used to evaluate the mechanism of the process. It is found that the hybrid ion exchange resins have better removal capacity as compared to the parent ion exchanger. The increase in the removal capacity is found to be in the order of the corresponding PZC values of the hybrid ion exchangers. Further, it is suggested that the higher exchange capacity is the result of Donnan effect and specific adsorption of chromium by the oxides / hydroxides present inside the matrix of the organic cation exchanger. (author)

  2. Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III Reaction Intermediate Models of Peroxidase Enzymes

    Directory of Open Access Journals (Sweden)

    Samuel Hernández Anzaldo

    2016-06-01

    Full Text Available The spectroscopic and kinetic characterization of two intermediates from the H2O2 oxidation of three dimethyl ester [(proto, (meso, (deuteroporphyrinato (picdien]Fe(III complexes ([FePPPic], [FeMPPic] and [FeDPPic], respectively pinch-porphyrin peroxidase enzyme models, with s = 5/2 and 3/2 Fe(III quantum mixed spin (qms ground states is described herein. The kinetic study by UV/Vis at λmax = 465 nm showed two different types of kinetics during the oxidation process in the guaiacol test for peroxidases (1–3 + guaiacol + H2O2 → oxidation guaiacol products. The first intermediate was observed during the first 24 s of the reaction. When the reaction conditions were changed to higher concentration of pinch-porphyrins and hydrogen peroxide only one type of kinetics was observed. Next, the reaction was performed only between pinch-porphyrins-Fe(III and H2O2, resulting in only two types of kinetics that were developed during the first 0–4 s. After this time a self-oxidation process was observed. Our hypotheses state that the formation of the π-cation radicals, reaction intermediates of the pinch-porphyrin-Fe(III family with the ligand picdien [N,N’-bis-pyridin-2-ylmethyl-propane-1,3-diamine], occurred with unique kinetics that are different from the overall process and was involved in the oxidation pathway. UV-Vis, 1H-NMR and ESR spectra confirmed the formation of such intermediates. The results in this paper highlight the link between different spectroscopic techniques that positively depict the kinetic traits of artificial compounds with enzyme-like activity.

  3. Actinides and rare earths complexation with adenosine phosphate nucleotides

    International Nuclear Information System (INIS)

    Mostapha, Sarah

    2013-01-01

    Organophosphorus compounds are important molecules in both nuclear industry and living systems fields. Indeed, several extractants of organophosphorus compounds (such as TBP, HDEHP) are used in the nuclear fuel cycle reprocessing and in the biological field. For instance, the nucleotides are organophosphates which play a very important role in various metabolic processes. Although the literature on the interactions of actinides with inorganic phosphate is abundant, published studies with organophosphate compounds are generally limited to macroscopic and / or physiological approaches. The objective of this thesis is to study the structure of several organophosphorus compounds with actinides to reach a better understanding and develop new specific buildings blocks. The family of the chosen molecules for this procedure consists of three adenine nucleotides mono, bi and triphosphate (AMP, adenosine monophosphate - ADP, adenosine diphosphate - ATP, adenosine triphosphate) and an amino-alkylphosphate (AEP O-phosphoryl-ethanolamine). Complexes synthesis was conducted in aqueous and weakly acidic medium (2.8-4) for several lanthanides (III) (Lu, Yb, Eu) and actinides (U (VI), Th (IV) and Am (III)). Several analytical and spectroscopic techniques have been used to describe the organization of the synthesized complexes: spectrometric analysis performed by FTIR and NMR were used to identify the functional groups involved in the complexation, analysis by ESI-MS and pH-metric titration were used to determine the solution speciation and EXAFS analyzes were performed on Mars beamline of the SOLEIL synchrotron, have described the local cation environment, for both solution and solid compounds. Some theoretical approaches of DFT were conducted to identify stable structures in purpose of completing the experimental studies. All solid complexes (AMP, ADP, ATP and AEP) have polynuclear structures, while soluble ATP complexes are mononuclear. For all synthesized complexes, it has been

  4. A spectroscopic and computational study of Al(III) complexes in cryolite melts: Effect of cation nature

    International Nuclear Information System (INIS)

    Nazmutdinov, Renat R.; Zinkicheva, Tamara T.; Vassiliev, Sergey Yu.; Glukhov, Dmitrii V.; Tsirlina, Galina A.; Probst, Michael

    2013-01-01

    Highlights: ► We investigate Li, Na and K cryolite melts by Raman spectroscopy and dft. ► A slight red shift of main Raman peaks is observed in the row Li + , Na + , K + . ► A decrease of the half-widths of peaks is observed in the same row. ► Fluoroaluminates and their complexation kinetics play an important role. - Abstract: Lithium, sodium and potassium cryolite melts are probed by Raman spectroscopy in a wide range of the melt composition. The experimental data demonstrate a slight red shift of main peaks and a decrease of their half-widths in the row Li + , Na + , K + . Quantum chemical modelling of the systems is performed at the density functional theory level. The ionic environment is found to play a crucial role in the energy of fluoroaluminates. Potential energy surfaces describing the formation/dissociation of certain complex species, as well as model Raman spectra are constructed and compared with those obtained recently for sodium containing cryolite melts (R.R. Nazmutdinov, et al., Spectrochim, Acta A 75 (2010) 1244.). The calculations show that the cation nature affects the geometry of the ionic associates as well as the equilibrium and kinetics of the complexation processes. This enables to interpret both original experimental data and those reported in literature

  5. Thermodynamic Properties of Actinides and Actinide Compounds

    Science.gov (United States)

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

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

  6. Research in actinide chemistry

    International Nuclear Information System (INIS)

    Choppin, G.R.

    1993-01-01

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

  7. Hybrid conducting polymer materials incorporating poly-oxo-metalates for extraction of actinides; Materiaux polymeres conducteurs hybrides incorporant des polyoxometallates pour l'extraction d'actinides

    Energy Technology Data Exchange (ETDEWEB)

    Racimor, D

    2003-09-15

    The preparation and characterization of hybrid conducting polymers incorporating poly-oxo-metalates for extracting actinides is discussed. A study of the coordination of various lanthanide cations (Ce(III), Ce(IV), Nd(III)) by the mono-vacant poly-oxo-metalate {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} showed significant differences according to the cation.. Various {alpha}-A-[PW{sub 9}O{sub 34}(RPO){sub 2}]{sup 5-} hybrids were synthesized and their affinity for actinides or lanthanides was demonstrated through complexation. The first hybrid poly-oxo-metallic lanthanide complexes were then synthesized, as was the first hybrid functionalized with a pyrrole group. The electro-polymerization conditions of this pyrrole remain still to be optimized. Poly-pyrrole materials incorporating {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} or its neodymium or cerium complexes as doping agents proved to be the first conducting polymer incorporating poly-oxo-metalates capable of extracting plutonium from nitric acid. (author)

  8. Uptake Of Trivalent Actinides (Cm(III)) And Lanthanides (Eu(III)) By Cement-Type Minerals: A Wet Chemistry And Time-Resolved Laser Fluorescence Spectroscopy (TRLFS) Study

    Energy Technology Data Exchange (ETDEWEB)

    Tits, J.; Stumpf, T; Wieland, E.; Fanghaenel, T

    2003-03-01

    The interaction of the two chemical homologues Cm (III) and Eu(III) with calcium silicate hydrates at pH 13.3 has been investigated in batch-type sorption studies using Eu(III), and complemented with time-resolved laser fluorescence spectroscopy using Cm(III). The sorption data for Eu(III) reveal fast sorption kinetics, and a strong uptake by CSH phases, with distribution ratios of 6({+-}3)*105 L kg-1. Three different types of sorbed Cm(III) species have been identified: a non-fluorescing species, which was identified as Cm cluster present either as surface precipitate or as Cm(III) colloid in solution, and two sorbed fluorescing species. The sorbed fluorescing species have characteristic emission spectra (main peak maxima at 618.9 nm and 620.9 nm) and fluorescence emission lifetimes (289 {+-} 11 ms and 1482{+-} 200 ms). From the fluorescence lifetimes, it appears that the two fluorescing Cm(III) species have, respectively, one to two or no water molecules left in their first coordination sphere, suggesting that these species are incorporated into the CSH structure. A structural model for Cm(III) and Eu(III) incorporation into CSH phases is proposed based on the substitution of Ca at two different types of sites in the CSH structure. (author)

  9. Physico-chemistry of actinides and other radioelements in solutions and at the interfaces

    International Nuclear Information System (INIS)

    2000-01-01

    This document provides the 61 papers (transparencies used during the presentations and posters) presented at the 1999 PRACTIS days, held February 17-18, 2000 in Villeneuve-les-Avignon. The content comprises 9 conferences dealing with 1)simulation of solvation, coordination and liquid-liquid extraction of rare earth and uranyl cations 2)overview on the complexation selectivity of actinides(III) and rare earths(III) by aromatic poly-nitrogenous ligands 3)detection, characterization and interaction between supramolecular aggregates of extractants: macroscopic consequences on the stability and on the macroscopic behaviour 4)chemistry of technetium in reducing medium: application to researches on radioactive waste management 5) separations by pyro-chemistry (CEA program) 6)overview on the Goethite operation 7)use of time-resolved luminescence spectroscopy to the determination of sorption sites at the interfaces 8)dissolution of uranium dioxide in an argillaceous water: results in oxidizing and reducing conditions 9)treatment and storage of radioactive wastes from weapon-grade plutonium production in Russia and other countries. A large part of the conference was devoted to poster sessions on the following topics: physico-chemistry in homogeneous solutions (22 posters), transfer kinetics of actinides and rare earths between liquid phases and separations (9 posters), physico-chemistry of the solid-solution interface (9 posters), simulation and molecular dynamics (5 posters), uranium dioxide and other oxides (1 poster), long-lived fission products (6 posters). (O.M.)

  10. Advanced Extraction Methods for Actinide/Lanthanide Separations

    International Nuclear Information System (INIS)

    Scott, M.J.

    2005-01-01

    high level liquid wastes and a general actinide clean-up procedure. The selectivity of the standard extractant for tetravalent actinides, (N,N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide (CMPO), was markedly improved by the attachment of three CMPO-like functions onto a triphenoxymethane platform, and a ligand that is both highly selective and effective for An(IV) ions was isolated. A 10 fold excess of ligand will remove virtually all of the 4+ actinides from the acidic layer without extracting appreciable quantities of An(III) and Ln(III) unlike simple CMPO ligands. Inspired by the success of the DIAMEX industrial process for extractions, three new tripodal chelates bearing three diglycolamide and thiodiglycolamide units precisely arranged on a triphenoxymethane platform have been synthesized for an highly efficient extraction of trivalent f-element cations from nitric acid media. A single equivalent of ligand will remove 80% of the Ln(III) ion from the acidic layer since the ligand is perfectly suited to accommodate the tricapped trigonal prismatic geometry preferred by the metal center. The ligand is perhaps the most efficient binder available for the heavier lanthanides and due to this unique attribute, the extraction event can be easily followed by 1H NMR spectroscopy confirming the formation of a TPP complex. The most lipophilic di-n-butyl tris-diglycolamide was found to be a significantly weaker extractant in comparison to the di-isopropyl analogs. The tris-thiodiglycolamide derivative proved to be an ineffective chelate for f-elements and demonstrated the importance of the etheric oxygens in the metal binding. The results presented herein clearly demonstrate a cooperative action of these three ligating groups within a single molecule, confirmed by composition and structure of the extracted complexes, and since actinides prefer to have high coordination numbers, the ligands should be particularly adept at binding with three arms. The use of such an

  11. Advanced Extraction Methods for Actinide/Lanthanide Separations

    Energy Technology Data Exchange (ETDEWEB)

    Scott, M.J.

    2005-12-01

    high level liquid wastes and a general actinide clean-up procedure. The selectivity of the standard extractant for tetravalent actinides, (N,N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide (CMPO), was markedly improved by the attachment of three CMPO-like functions onto a triphenoxymethane platform, and a ligand that is both highly selective and effective for An(IV) ions was isolated. A 10 fold excess of ligand will remove virtually all of the 4+ actinides from the acidic layer without extracting appreciable quantities of An(III) and Ln(III) unlike simple CMPO ligands. Inspired by the success of the DIAMEX industrial process for extractions, three new tripodal chelates bearing three diglycolamide and thiodiglycolamide units precisely arranged on a triphenoxymethane platform have been synthesized for an highly efficient extraction of trivalent f-element cations from nitric acid media. A single equivalent of ligand will remove 80% of the Ln(III) ion from the acidic layer since the ligand is perfectly suited to accommodate the tricapped trigonal prismatic geometry preferred by the metal center. The ligand is perhaps the most efficient binder available for the heavier lanthanides and due to this unique attribute, the extraction event can be easily followed by 1H NMR spectroscopy confirming the formation of a TPP complex. The most lipophilic di-n-butyl tris-diglycolamide was found to be a significantly weaker extractant in comparison to the di-isopropyl analogs. The tris-thiodiglycolamide derivative proved to be an ineffective chelate for f-elements and demonstrated the importance of the etheric oxygens in the metal binding. The results presented herein clearly demonstrate a cooperative action of these three ligating groups within a single molecule, confirmed by composition and structure of the extracted complexes, and since actinides prefer to have high coordination numbers, the ligands should be particularly adept at binding with three arms. The use of such an

  12. Actinide science. Fundamental and environmental aspects

    International Nuclear Information System (INIS)

    Choppin, Gregory R.

    2005-01-01

    Nuclear test explosions and reactor wastes have deposited an estimated 16x10 15 Bq of plutonium into the world's aquatic systems. However, plutonium concentration in open ocean waters is orders of magnitude less, indicating that most of the plutonium is quite insolvable in marine waters and has been incorporated into sediments. Actinide ions in waters often are not in a state of thermodynamic equilibrium and their solubility and migration behavior is related to the form in which the nuclides were introduced into the aquatic system. Actinide solubility depends on such factors as pH(hydrolysis), E H (oxidation state), reaction with complexants (e.g. carbonate, phosphate, humic acid, etc.) sorption to surfaces of minerals and/or colloids, etc., in the water. The most significant of these variables is the oxidation sate of the metal ion. The simultaneous presence of more than one oxidation state for some actinides (e.g. plutonium) in a solution complicates actinide environmental behavior. Both Np(V)O 2 + and Pu(V)O 2 + , the most significant soluble states in natural oxic waters are relatively noncomplexing and resistant to hydrolysis and subsequent precipitation but can undergo reduction to the Pu(IV) oxidation state with its different elemental behavior. The solubility of NpO 2 + can be as high as 10 -4 M while that of PuO 2 + is more limited by reduction to the insoluble tetravalent species, Pu(OH) 4 , (pK SP - 56). The net solubility of hexavalent UO 2 2+ in sea water is also limited by hydrolysis; however, it has a relatively high concentration due to formation of carbonate complexes. The insoluble trivalent americium hydroxocarbonate, Am(CO) 3 (OH), is the limiting species for the solubility of Am(III) in sea water. Thorium is found exclusively as the tetravalent species and its solubility is limited by the formation of quite insoluble Th(OH) 4 . The chemistry of actinide ions in the environment is reviewed to show the spectrum of reactions that can occur in

  13. Rapid ion-exchange separations of actinides

    International Nuclear Information System (INIS)

    Usuda, Shigekazu

    1988-01-01

    For the purpose of studying short-lived actinide nuclides, three methods for rapid ion exchange separation of actinide elements with mineral acid-alcohol mixed media were developed: anion exchange with nitric acid-methyl alcohol mixed media to separate the transplutonium and rare earth elements from target material, U or Pu and Al catcher foils; anion exchange with hydrochloric acid-methyl alcohol media to separate Am+Cm, Bk and Cf+Fm from the target, catcher foils and major fission products; and cation exchange with hydrochloric acid-methyl alcohol media and with concentrated hydrochloric acid to separate the transplutonium elements as a group from the rare earths after eliminating the large amounts of U, Al, Cu, Fe etc. The methods enable one to perform rapid and effective separation at elevated temperature (90 deg C) and immediate source preparation for alpha-ray spectrometry. (author) 47 refs.; 10 figs

  14. Seventeen-coordinate actinide helium complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kaltsoyannis, Nikolas [School of Chemistry, The University of Manchester (United Kingdom)

    2017-06-12

    The geometries and electronic structures of molecular ions featuring He atoms complexed to actinide cations are explored computationally using density functional and coupled cluster theories. A new record coordination number is established, as AcHe{sub 17}{sup 3+}, ThHe{sub 17}{sup 4+}, and PaHe{sub 17}{sup 4+} are all found to be true geometric minima, with the He atoms clearly located in the first shell around the actinide. Analysis of AcHe{sub n}{sup 3+} (n=1-17) using the quantum theory of atoms in molecules (QTAIM) confirms these systems as having closed shell, charge-induced dipole bonding. Excellent correlations (R{sup 2}>0.95) are found between QTAIM metrics (bond critical point electron densities and delocalization indices) and the average Ac-He distances, and also with the incremental He binding energies. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Superconductivity in the actinides

    International Nuclear Information System (INIS)

    Smith, J.L.; Lawson, A.C.

    1985-01-01

    The trends in the occurrence of superconductivity in actinide materials are discussed. Most of them seem to show simple transition metal behavior. However, the superconductivity of americium proves that the f electrons are localized in that element and that ''actinides'' is the correct name for this row of elements. Recently the superconductivity of UBe 13 and UPt 3 has been shown to be extremely unusual, and these compounds fall in the new class of compounds now known as heavy fermion materials

  16. Minor actinide transmutation using minor actinide burner reactors

    International Nuclear Information System (INIS)

    Mukaiyama, T.; Yoshida, H.; Gunji, Y.

    1991-01-01

    The concept of minor actinide burner reactor is proposed as an efficient way to transmute long-lived minor actinides in order to ease the burden of high-level radioactive waste disposal problem. Conceptual design study of minor actinide burner reactors was performed to obtain a reactor model with very hard neutron spectrum and very high neutron flux in which minor actinides can be fissioned efficiently. Two models of burner reactors were obtained, one with metal fuel core and the other with particle fuel core. Minor actinide transmutation by the actinide burner reactors is compared with that by power reactors from both the reactor physics and fuel cycle facilities view point. (author)

  17. Subsurface Biogeochemistry of Actinides

    Energy Technology Data Exchange (ETDEWEB)

    Kersting, Annie B. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Univ. Relations and Science Education; Zavarin, Mavrik [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Glenn T. Seaborg Inst.

    2016-06-29

    A major scientific challenge in environmental sciences is to identify the dominant processes controlling actinide transport in the environment. It is estimated that currently, over 2200 metric tons of plutonium (Pu) have been deposited in the subsurface worldwide, a number that increases yearly with additional spent nuclear fuel (Ewing et al., 2010). Plutonium has been shown to migrate on the scale of kilometers, giving way to a critical concern that the fundamental biogeochemical processes that control its behavior in the subsurface are not well understood (Kersting et al., 1999; Novikov et al., 2006; Santschi et al., 2002). Neptunium (Np) is less prevalent in the environment; however, it is predicted to be a significant long-term dose contributor in high-level nuclear waste. Our focus on Np chemistry in this Science Plan is intended to help formulate a better understanding of Pu redox transformations in the environment and clarify the differences between the two long-lived actinides. The research approach of our Science Plan combines (1) Fundamental Mechanistic Studies that identify and quantify biogeochemical processes that control actinide behavior in solution and on solids, (2) Field Integration Studies that investigate the transport characteristics of Pu and test our conceptual understanding of actinide transport, and (3) Actinide Research Capabilities that allow us to achieve the objectives of this Scientific Focus Area (SFA and provide new opportunities for advancing actinide environmental chemistry. These three Research Thrusts form the basis of our SFA Science Program (Figure 1).

  18. The Photoluminescent Properties of New Cationic Iridium(III Complexes Using Different Anions and Their Applications in White Light-Emitting Diodes

    Directory of Open Access Journals (Sweden)

    Hui Yang

    2015-09-01

    Full Text Available Three cationic iridium(III complexes [Ir(ppy2(phen][PF6] (C1, [Ir(ppy2(phen]2SiF6 (C2 and [Ir(ppy2(phen]2TiF6 (C3 (ppy: 2-phenylpyridine, phen: 1, 10-phenanthroline using different anions were synthesized and characterized by 1H Nuclear magnetic resonance (1HNMR, mass spectra (MS, Fourier transform infrared (FTIR spectra and element analysis (EA. After the ultraviolet visible (UV-vis absorption spectra, photoluminescent (PL properties and thermal properties of the complexes were investigated, complex C1 and C3 with good optical properties and high thermal stability were used in white light-emitting diodes (WLEDs as luminescence conversion materials by incorporation with 460 nm-emitting blue GaN chips. The integrative performances of the WLEDs fabricated with complex C1 and C3 are better than those fabricated with the widely used yellow phosphor Y3Al5O12:Ce3+ (YAG. The color rendering indexes of the WLEDs with C1 and C3 are 82.0 and 82.6, the color temperatures of them are 5912 K and 3717 K, and the maximum power efficiencies of them are 10.61 Lm·W−1 and 11.41 Lm·W−1, respectively.

  19. The Photoluminescent Properties of New Cationic Iridium(III) Complexes Using Different Anions and Their Applications in White Light-Emitting Diodes.

    Science.gov (United States)

    Yang, Hui; Meng, Guoyun; Zhou, Yayun; Tang, Huaijun; Zhao, Jishou; Wang, Zhengliang

    2015-09-14

    Three cationic iridium(III) complexes [Ir(ppy)₂(phen)][PF₆] (C1), [Ir(ppy)₂(phen)]₂SiF₆ (C2) and [Ir(ppy)₂(phen)]₂TiF₆ (C3) (ppy: 2-phenylpyridine, phen: 1, 10-phenanthroline) using different anions were synthesized and characterized by ¹H Nuclear magnetic resonance (¹HNMR), mass spectra (MS), Fourier transform infrared (FTIR) spectra and element analysis (EA). After the ultraviolet visible (UV-vis) absorption spectra, photoluminescent (PL) properties and thermal properties of the complexes were investigated, complex C1 and C3 with good optical properties and high thermal stability were used in white light-emitting diodes (WLEDs) as luminescence conversion materials by incorporation with 460 nm-emitting blue GaN chips. The integrative performances of the WLEDs fabricated with complex C1 and C3 are better than those fabricated with the widely used yellow phosphor Y₃Al₅O 12 :Ce 3+ (YAG). The color rendering indexes of the WLEDs with C1 and C3 are 82.0 and 82.6, the color temperatures of them are 5912 K and 3717 K, and the maximum power efficiencies of them are 10.61 Lm·W -1 and 11.41 Lm·W -1 , respectively.

  20. Combined techniques for studying actinide complexes in room temperature ionic liquids

    International Nuclear Information System (INIS)

    Gaillard, C.; Billard, I.; Mekki, S.; Ouadi, A.; Hennig, Ch.; Denecke, M.A.

    2007-01-01

    Room temperature ionic liquids (RTILs) are a new class of solvents. Their main interest is related to their 'green' properties (non-volatile, non-flammable, etc.), but also from the variability of their physico-chemical properties (stability, hydrophobicity, viscosity) as a function of the RTIL cationic and anionic components. In the frame of the nuclear fuel reprocessing, RTILs are particularly attractive in order to improve existing processes or to develop new ones for actinide and lanthanide partitioning, in replacement of toxic solvents used nowadays, for metal electrodeposition or for liquid/liquid extraction by the use of task specific ionic liquids. However, despite the increasing number of publications devoted to ionic liquids, the solvation effects, the solute-solvent and solvent-solvent interactions are still hardly known. These fundamental aspects are of tremendous importance to the understanding of the solvating properties of these new solvents. In this frame, we have undertaken studies on the solvation and complexation of lanthanides (III) and actinides in RTILs, by the use of spectroscopic techniques. Experiments were led in various ionic liquids in order to highlight the role of the anionic part of the RTILs on the reactivity of the studied cations. Results have clearly shown that solvation phenomena in RTILs are not as 'simple' as in classical solvents. The dissolution of a Ln/An salt, even if complete, does not imply dissociation and solvation of the metal cation by the RTILs anions only. The nature of first co-ordination sphere of Ln/An depends on the competition between its counter-anions and the RTIL anions, which, in turn, influence the complexation reaction with other added anions such as chlorides. (authors)

  1. Actinide colloid generation in groundwater

    International Nuclear Information System (INIS)

    Kim, J.I.

    1990-05-01

    The progress made in the investigation of actinide colloid generation in groundwaters is summarized and discussed with particular examples relevant to an understanding of the migration behaviour of actinides in natural aquifer systems. The first part deals with the characterization of colloids: groundwater colloids, actinide real-colloids and actinide pseudocolloids. The second part concentrates on the generation processes and migration behaviour of actinide pseudocolloids, which are discussed with some notable experimental examples. Importance is stressed more on the chemical aspects of the actinide colloid generation in groundwater. This work is a contribution to the CEC project MIRAGE II, particularly, to research area: complexation and colloids. (orig.)

  2. Actinide isotopic analysis systems

    International Nuclear Information System (INIS)

    Koenig, Z.M.; Ruhter, W.D.; Gunnink, R.

    1990-01-01

    This manual provides instructions and procedures for using the Lawrence Livermore National Laboratory's two-detector actinide isotope analysis system to measure plutonium samples with other possible actinides (including uranium, americium, and neptunium) by gamma-ray spectrometry. The computer program that controls the system and analyzes the gamma-ray spectral data is driven by a menu of one-, two-, or three-letter options chosen by the operator. Provided in this manual are descriptions of these options and their functions, plus detailed instructions (operator dialog) for choosing among the options. Also provided are general instructions for calibrating the actinide isotropic analysis system and for monitoring its performance. The inventory measurement of a sample's total plutonium and other actinides content is determined by two nondestructive measurements. One is a calorimetry measurement of the sample's heat or power output, and the other is a gamma-ray spectrometry measurement of its relative isotopic abundances. The isotopic measurements needed to interpret the observed calorimetric power measurement are the relative abundances of various plutonium and uranium isotopes and americium-241. The actinide analysis system carries out these measurements. 8 figs

  3. Extraction chromatography of actinides

    International Nuclear Information System (INIS)

    Muller, W.

    1978-01-01

    Extraction chromatography of actinides in the oxidation state from 2 to 6 is reviewed. Data on using neutral (tbp), basic (substituted ammonium salts) and acidic [di-(2-ethylhexyl)-phosphoric acid (D2EHPA)] extracting agents ketones, esters, alcohols and β-diketones in this method are given. Using the example of actinide separation using D2EHPA, discussed are factors influencing the efficiency of their chromatography separation (nature and particle size of the carrier materials, extracting agents amount on the carrier, temperature and elution rate)

  4. Actinide nanoparticle research

    International Nuclear Information System (INIS)

    Kalmykov, Stepan N.; Denecke, Melissa A.

    2011-01-01

    This is the first book to cover actinide nano research. It is of interest both for fundamental research into the chemistry and physics of f-block elements as well as for applied researchers such as those studying the long-term safety of nuclear waste disposal and developing remediation strategies. The authors cover important issues of the formation of actinide nano-particles, their properties and structure, environmental behavior of colloids and nanoparticles related to the safe disposal of nuclear wastes, modeling and advanced methods of characterization at the nano-scale. (orig.)

  5. Radiochemistry and actinide chemistry

    International Nuclear Information System (INIS)

    Guillaumont, R.; Peneloux, A.

    1989-01-01

    The analysis of trace amounts of actinide elements by means of radiochemistry, is discussed. The similarities between radiochemistry and actinide chemistry, in the case of species amount by cubic cm below 10 12 , are explained. The parameters which allow to define what are the observable chemical reactions, are given. The classification of radionuclides in micro or macrocomponents is considered. The validity of the mass action law and the partition function in the definition of the average number of species for trace amounts, is investigated. Examples illustrating the results are given

  6. Investigations of actinides in the context of final disposal of high-level radioactive waste. Trivalent actinides in aqueous solution

    International Nuclear Information System (INIS)

    Banik, N.L.; Boris Brendebach; Marquardt, Ch.M.

    2014-01-01

    The speciation of redox sensitive trivalent actinides Pu(III), Np(III), and U(III) has been studied in aqueous solution. The redox preparation, stabilization, and speciation of these trivalent actinides in aqueous systems are discussed here. The reductants investigated were rongalite, hydroxylamine hydrochloride, and acetohydroxamic acid and the An(III) species have been characterized by UV-Vis and XANES spectroscopy. The results show that the effectiveness of stabilization decreases generally in the order Pu(III) > Np(III) > U(III) and that the effectiveness of each reducing agent depends on the experimental conditions. More than 80 % of Pu(III) aquo species have been stabilized up to pH 5.5, whereas the Np(III) aquo ion could be stabilized in a pH range 0-2.5, and U(III) aquo ion is sufficiently stable at pH 1.0 and below over time periods suitable for experiments. However, this study gives a basis for the characterisation of the trivalent lighter actinides involved in complexation, sorption, and solid formation reactions in the future. (author)

  7. Actinides, the narrowwest bands

    International Nuclear Information System (INIS)

    Smith, J.L.; Riseborough, P.S.

    1984-01-01

    A table of elements is shown that demonstrates the crossover from superconductivity to magnetism as well as regions of mixed valence. In particular, the actinides must eventually show 4f-electron like mixed valence, after the 5f-electrons become localized. There also seems to be an adiabatic continuation between heavy fermion and mixed valence behavior

  8. Molecular and electronic structure of actinide hexa-cyanoferrates; Structure moleculaire et electronique des hexacyanoferrates d'actinides

    Energy Technology Data Exchange (ETDEWEB)

    Bonhoure, I

    2001-07-01

    The goal of this work is to improve our knowledge on the actinide-ligand bond properties. To this end, the hexacyanoferrate entities have been used as pre-organized ligand. We have synthesized, using mild chemistry, the following series of complexes: An{sup IV}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Th, U, Np, Pu); Am{sup III}[Fe{sup III}(CN){sub 6}].xH{sub 2}O; Pu {sup III}[Co{sup III}(CN){sub 6}].xH{sub 2}O and K(H?)An{sup III}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Pu, Am). The metal oxidation states have been obtained thanks to the {nu}{sub CN}, stretching vibration and to the actinide L{sub III} absorption edge studies. As Prussian Blue, the An{sup IV}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Np, Pu) are class II of Robin and Day compounds. X-ray Diffraction has shown besides that these complexes crystallize in the P6{sub 3}/m space group, as the isomorphic LaKFe(CN){sub 6}.4H{sub 2}O complex used as structural model. The EXAFS oscillations at the iron K edge and at the An L{sub III} edge allowed to determine the An-N, An-O, Fe-C and Fe-N distances. The display of the multiple scattering paths for both edges explains the actinide contribution absence at the iron edge, whereas the iron signature is present at the actinide edge. We have shown that the actinide coordination sphere in actinides hexa-cyanoferrates is comparable to the one of lanthanides. However, the actinides typical behavior towards the lanthanides is brought to the fore by the An{sup IV} versus Ln{sup III} ions presence in this family of complexes. Contrarily to the 4f electrons, the 5f electrons influence the electronic properties of the compounds of this family. However, the gap between the An-N and Ln-N distances towards the corresponding metals ionic radii do not show any covalence bond evolution between the actinide and lanthanide series. (author)

  9. Uranium and lanthanide complexes with the 2-mercapto benzothiazolate ligand: Evidence for a specific covalent binding site in the differentiation of isostructural lanthanide(III) and actinide(III) compounds

    Energy Technology Data Exchange (ETDEWEB)

    Roger, M.; Arliguie, T.; Thuery, P.; Ephritikhine, M. [CEA Saclay, DSM, DRECAM, Serv Chim Mol, CNRS URA 331, F-91191 Gif Sur Yvette, (France); Belkhiri, L. [Univ Mentouri Constantine, Fac Sci, Dept Chim, Lab Chim Mol LACMOM, Constantine 25017, (Algeria); Boucekkine, A. [Univ Rennes 1, CNRS, UMR Sci Chim Rennes 6226, F-35042 Rennes, (France)

    2008-07-01

    Treatment Of [U(Cp*){sub 2}Cl{sub 2}] with KSBT in THF gave [U(Cp*){sub 2}(SBT){sub 2}], which exhibits the usual bent sandwich configuration in the solid state with the two SBT ligands adopting the bidentate ligation mode. The mono-cyclopentadienyl compound [U(Cp*)(SBT){sub 3}] was synthesized by reaction of [U(Cp*)(BH{sub 4}){sub 3}] with KSBT in THF, and its reduction with potassium amalgam in the presence of 18-crown-6 afforded the corresponding anionic complex [K(18-crown-6)(THF){sub 2}][U(Cp*)(SBT){sub 3}]. The lanthanide analogues [K(THF){sub 2}Ln(Cp*)(SBT){sub 3}] were obtained by treating [Ln(BH{sub 4}){sub 3}(THF){sub 3}] with KSBT and KCp*; isomorphous crystals of [K(15-crown-5){sub 2}] [Ln(Cp*)(SBT){sub 3}].THF [Ln = La, Ce, Nd] were formed upon addition of 15-crown-5. Comparison of the crystal structures of the pentagonal bipyramidal complexes [M(Cp*)(SBT){sub 3}]{sup -} reveals that the M-Nax distances are shorter than the M-Neq distances, whatever the metal, the phenomenon being enhanced in the U(III) compound versus the Ln(III) analogues. The structural data obtained by relativistic density functional theory (DFT) calculations reproduce experimental trends. Electronic population and molecular orbital analyses show that the structural differences in the series of [M(Cp*)(SBT){sub 3}]{sup -} anions are related to the uranium 5f orbital-ligand mixing, which is greater than the lanthanide 4f orbital-ligand mixing. Moreover, the consideration of the corresponding bond orders and the analysis of the bonding energy bring to light a strong and specific interaction between the uranium and apical nitrogen atoms. (authors)

  10. Structural Characterization of Am(III)- and Pu(III)-DOTA Complexes.

    Science.gov (United States)

    Audras, Matthieu; Berthon, Laurence; Berthon, Claude; Guillaumont, Dominique; Dumas, Thomas; Illy, Marie-Claire; Martin, Nicolas; Zilbermann, Israel; Moiseev, Yulia; Ben-Eliyahu, Yeshayahu; Bettelheim, Armand; Cammelli, Sebastiano; Hennig, Christoph; Moisy, Philippe

    2017-10-16

    The complexation of 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) ligand with two trivalent actinides (Am 3+ and Pu 3+ ) was investigated by UV-visible spectrophotometry, NMR spectroscopy, and extended X-ray absorption fine structure in conjunction with computational methods. The complexation process of these two cations is similar to what has been previously observed with lanthanides(III) of similar ionic radius. The complexation takes place in different steps and ends with the formation of a (1:1) complex [(An(III)DOTA)(H 2 O)] - , where the cation is bonded to the nitrogen atoms of the ring, the four carboxylate arms, and a water molecule to complete the coordination sphere. The formation of An(III)-DOTA complexes is faster than the Ln(III)-DOTA systems of equivalent ionic radius. Furthermore, it is found that An-N distances are slightly shorter than Ln-N distances. Theoretical calculations showed that the slightly higher affinity of DOTA toward Am over Nd is correlated with slightly enhanced ligand-to-metal charge donation arising from oxygen and nitrogen atoms.

  11. Actinide separative chemistry

    International Nuclear Information System (INIS)

    Boullis, B.

    2004-01-01

    Actinide separative chemistry has focused very heavy work during the last decades. The main was nuclear spent fuel reprocessing: solvent extraction processes appeared quickly a suitable, an efficient way to recover major actinides (uranium and plutonium), and an extensive research, concerning both process chemistry and chemical engineering technologies, allowed the industrial development in this field. We can observe for about half a century a succession of Purex plants which, if based on the same initial discovery (i.e. the outstanding properties of a molecule, the famous TBP), present huge improvements at each step, for a large part due to an increased mastery of the mechanisms involved. And actinide separation should still focus R and D in the near future: there is a real, an important need for this, even if reprocessing may appear as a mature industry. We can present three main reasons for this. First, actinide recycling appear as a key-issue for future nuclear fuel cycles, both for waste management optimization and for conservation of natural resource; and the need concerns not only major actinide but also so-called minor ones, thus enlarging the scope of the investigation. Second, extraction processes are not well mastered at microscopic scale: there is a real, great lack in fundamental knowledge, useful or even necessary for process optimization (for instance, how to design the best extracting molecule, taken into account the several notifications and constraints, from selectivity to radiolytic resistivity?); and such a need for a real optimization is to be more accurate with the search of always cheaper, cleaner processes. And then, there is room too for exploratory research, on new concepts-perhaps for processing quite new fuels- which could appear attractive and justify further developments to be properly assessed: pyro-processes first, but also others, like chemistry in 'extreme' or 'unusual' conditions (supercritical solvents, sono-chemistry, could be

  12. Nonlinear absorbing cationic iridium(III) complexes bearing benzothiazolylfluorene motif on the bipyridine (N∧N) ligand: synthesis, photophysics and reverse saturable absorption.

    Science.gov (United States)

    Li, Yuhao; Dandu, Naveen; Liu, Rui; Hu, Lei; Kilina, Svetlana; Sun, Wenfang

    2013-07-24

    Four new heteroleptic cationic Ir(III) complexes bearing benzothiazolylfluorene motif on the bipyridine (N∧N) (1 and 2) and phenylpyridine (C∧N) (3 and 4) ligands are synthesized and characterized. The influence of the position of the substituent and the extent of π-conjugation on the photophysics of these complexes is systematically investigated by spectroscopic methods and simulated by time-dependent density functional theory (TDDFT). The complexes exhibit ligand-centered (1)π,π* transitions with admixtures of (1)ILCT (π(benzothiazolylfluorene) → π*(bpy)) and (1)MLCT (metal-to-ligand charge transfer) characters below 475 nm, and very weak (1,3)MLCT and (1,3)LLCT (ligand-to-ligand charge transfer) transitions above 475 nm. The emission of these complexes at room temperature in CH2Cl2 solutions is ascribed to be predominantly from the (3)MLCT/(3)LLCT states for 1 and from the (3)π,π* state for 2, while the emitting state of 3 and 4 are assigned to be an admixture of (3)MLCT, (3)LLCT, and (3)π,π* characters. The variations of the photophysical properties of 1-4 are attributed to different degrees of π-conjugation in the bipyridine and phenylpyridine ligands induced by different positions of the benzothiazolylfluorenyl substituents on the bipyridine ligand and different extents of π-conjugation in the phenylpyridine ligands, which alters the energy and lifetime of the lowest singlet and triplet excited states. 1-4 all possess broadband transient absorption (TA) upon nanosecond laser excitation, which extends from the visible to the NIR region. Therefore, 1-4 all exhibit strong reverse saturable absorption (RSA) at 532 nm for ns laser pulses. However, the TA of complexes 1, 2, and 3 are much stronger than that of 4. This feature, combined with the difference in ground-state absorption and triplet excited-state quantum yield, result in the difference in RSA strength, which follows this trend: 1 ≈ 2 ≈ 3 > 4. Therefore, complexes 1-3 are strong

  13. Actinide oxide photodiode and nuclear battery

    Energy Technology Data Exchange (ETDEWEB)

    Sykora, Milan; Usov, Igor

    2017-12-05

    Photodiodes and nuclear batteries may utilize actinide oxides, such a uranium oxide. An actinide oxide photodiode may include a first actinide oxide layer and a second actinide oxide layer deposited on the first actinide oxide layer. The first actinide oxide layer may be n-doped or p-doped. The second actinide oxide layer may be p-doped when the first actinide oxide layer is n-doped, and the second actinide oxide layer may be n-doped when the first actinide oxide layer is p-doped. The first actinide oxide layer and the second actinide oxide layer may form a p/n junction therebetween. Photodiodes including actinide oxides are better light absorbers, can be used in thinner films, and are more thermally stable than silicon, germanium, and gallium arsenide.

  14. Innovative SANEX process for trivalent actinides separation from PUREX raffinate

    International Nuclear Information System (INIS)

    Sypula, Michal

    2013-01-01

    Recycling of nuclear spent fuel and reduction of its radiotoxicity by separation of long-lived radionuclides would definitely help to close the nuclear fuel cycle ensuring sustainability of the nuclear energy. Partitioning of the main radiotoxicity contributors followed by their conversion into short-lived radioisotopes is known as partitioning and transmutation strategy. To ensure efficient transmutation of the separated elements (minor actinides) the content of lanthanides in the irradiation targets has to be minimised. This objective can be attained by solvent extraction using highly selective ligands that are able to separate these two groups of elements from each other. The objective of this study was to develop a novel process allowing co-separation of minor actinides and lanthanides from a high active acidic feed solution with subsequent actinide recovery using just one cycle, so-called innovative SANEX process. The conditions of each step of the process were optimised to ensure high actinide separation efficiency. Additionally, screening tests of several novel lipophilic and hydrophilic ligands provided by University of Twente were performed. These tests were aiming in better understanding the influence of the extractant structural modifications onto An(III)/Ln(III) selectivity and complexation properties. Optimal conditions for minor actinides separation were found and a flow-sheet of a new innovative SANEX process was proposed. Tests using a single centrifugal contactor confirmed high Eu(III)/Am(III) separation factor of 15 while the lowest SF Ln/Am obtained was 6,5 (for neodymium). In addition, a new masking agent for zirconium was found as a substitution for oxalic acid. This new masking agent (CDTA) was also able to mask palladium without any negative influence on An(III)/Ln(III). Additional tests showed no influence of CDTA on plutonium present in the feed solution unlike oxalic acid which causes Pu precipitation. Therefore, CDTA was proposed as a Zr

  15. Innovative SANEX process for trivalent actinides separation from PUREX raffinate

    Energy Technology Data Exchange (ETDEWEB)

    Sypula, Michal

    2013-07-01

    Recycling of nuclear spent fuel and reduction of its radiotoxicity by separation of long-lived radionuclides would definitely help to close the nuclear fuel cycle ensuring sustainability of the nuclear energy. Partitioning of the main radiotoxicity contributors followed by their conversion into short-lived radioisotopes is known as partitioning and transmutation strategy. To ensure efficient transmutation of the separated elements (minor actinides) the content of lanthanides in the irradiation targets has to be minimised. This objective can be attained by solvent extraction using highly selective ligands that are able to separate these two groups of elements from each other. The objective of this study was to develop a novel process allowing co-separation of minor actinides and lanthanides from a high active acidic feed solution with subsequent actinide recovery using just one cycle, so-called innovative SANEX process. The conditions of each step of the process were optimised to ensure high actinide separation efficiency. Additionally, screening tests of several novel lipophilic and hydrophilic ligands provided by University of Twente were performed. These tests were aiming in better understanding the influence of the extractant structural modifications onto An(III)/Ln(III) selectivity and complexation properties. Optimal conditions for minor actinides separation were found and a flow-sheet of a new innovative SANEX process was proposed. Tests using a single centrifugal contactor confirmed high Eu(III)/Am(III) separation factor of 15 while the lowest SF{sub Ln/Am} obtained was 6,5 (for neodymium). In addition, a new masking agent for zirconium was found as a substitution for oxalic acid. This new masking agent (CDTA) was also able to mask palladium without any negative influence on An(III)/Ln(III). Additional tests showed no influence of CDTA on plutonium present in the feed solution unlike oxalic acid which causes Pu precipitation. Therefore, CDTA was proposed as

  16. Actinide recycling in reactors

    International Nuclear Information System (INIS)

    Kuesters, H.; Wiese, H.W.; Krieg, B.

    1995-01-01

    The objective is an assessment of the transmutation of long-lived actinides and fission products and the incineration of plutonium for reducing the risk potential of radioactive waste from reactors in comparison to direct waste disposal. The contribution gives an interim account on homogeneous and heterogeneous recycling of 'risk nuclides' in thermal and fast reactors. Important results: - A homogeneous 5 percent admixture of minor actinides (MA) from N4-PWRs to EFR fuel would allow a transmutation not only of the EFR MA, but in addition of the MA from 5 or 6 PWRs of equal power. However, the incineration is restricted by safety considerations. - LWR have only a very low MA incineration potential, due to their disadvantageous neutron capture/fission ratio. - In order to keep the Cm inventory at a low level, it is advantageous to concentrate the Am heterogeneously in particular fuel elements or rods. (orig./HP)

  17. Photochemistry of the actinides

    International Nuclear Information System (INIS)

    Toth, L.M.; Bell, J.T.; Friedman, H.A.

    1979-01-01

    It has been found that all three major actinides have a useful variety of photochemical reactions which could be used to achieve a separations process that requires fewer reagents. Several features merit enumerating: (1) Laser photochemistry is not now as uniquely important in fuel reprocessing as it is in isotopic enrichment. The photochemistry can be successfully accomplished with conventional light sources. (2) The easiest place to apply photo-reprocessing is on the three actinides U, Pu, and Np. The solutions are potentially cleaner and more amenable to photoreactions. (3) Organic-phase photoreactions are probably not worth much attention because of the troublesome solvent redox chemistry associated with the photochemical reaction. (4) Upstream process treatment on the raffinate (dissolver solution) may never be too attractive since the radiation intensity precludes the usage of many optical materials and the nature of the solution is such that light transmission into it might be totally impossible

  18. Analytical chemistry of actinides

    International Nuclear Information System (INIS)

    Chollet, H.; Marty, P.

    2001-01-01

    Different characterization methods specifically applied to the actinides are presented in this review such as ICP/OES (inductively coupled plasma-optical emission spectrometry), ICP/MS (inductively coupled plasma spectroscopy-mass spectrometry), TIMS (thermal ionization-mass spectrometry) and GD/OES (flow discharge optical emission). Molecular absorption spectrometry and capillary electrophoresis are also available to complete the excellent range of analytical tools at our disposal. (authors)

  19. Actinides: why are they important biologically

    International Nuclear Information System (INIS)

    Durbin, P.W.

    1978-01-01

    The following topics are discussed: actinide elements in energy systems; biological hazards of the actinides; radiation protection standards; and purposes of actinide biological research with regard to toxicity, metabolism, and therapeutic regimens

  20. Liquid-solid extraction of cationic metals by cationic amphiphiles

    International Nuclear Information System (INIS)

    Muller, W.

    2010-01-01

    In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl - , NO 3 - , C 2 O 4 2- ) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu 2+ , Zn 2+ , UO 2 2+ , Fe 3+ , Nd 3+ , Eu 3+ , Th 4+ ) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author) [fr

  1. Hexagonal perovskites with cationic vacancies. 16. Rhombohedral 12 L-stacking polytypes Ba/sub 3/Asup(III)M/sub 3/sup(V)vacantO/sub 12/ with Msup(V) = Nb, Ta

    Energy Technology Data Exchange (ETDEWEB)

    Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

    1980-02-01

    The white quaternary oxides Ba/sub 3/LaM/sub 3/sup(V)vacantO/sub 12/ with Msup(V) = Nb, Ta belong to the group of hexagonal perovskites with cationic vacancies. They crystallize in a rhombohedral 12 L-structure (sequence (hhcc)/sub 3/; space group R3m) with a = 5.75 A; c = 28.1 A (Msup(V) = Nb); a = 5.74 A; c = 28.2 A (Ta) and Z = 3. Signs for the formation of isotypic compounds with Asup(III) = Pr, Nd could be obtained as well.

  2. U(SMes*)n, (n=3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): Lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta(3) Ligation mode of the aryl-thiolate ligand, from X-ray diffraction and DFT analysis

    International Nuclear Information System (INIS)

    Roger, Mathieu; Barros, Noemi; Arliguie, Therese; Thuery, Pierre; Maron, Laurent; Ephritikhine, Michel

    2006-01-01

    Reaction of U(NEt 2 ) 4 with HS-2,4,6- t Bu 3 C 6 H 2 (HSMes*) gave U(SMes*) 3 (NEt 2 )(py) (1), whereas similar treatment of U[N(SiMe 3 )SiMe 2 CH 2 ][N(SiMe 3 ) 2 ] 2 afforded U(SMes*)[N(SiMe 3 ) 2 ] 3 (2) and U(SMes*) 3 [N(SiMe 3 ) 2 ]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes*) 4 (4), was isolated from the reaction of U(BH 4 ) 4 and KSMes*. The first homoleptic thiolate complex of uranium(III), U(SMes*) 3 (5), was synthesized by proton-lysis of U[N(SiMe 3 ) 2 ] 3 with HSMes* in cyclohexane. The crystal structure of 5 exhibits the novel η 3 ligation mode for the aryl-thiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes*) 3 (Ln) La, Ce, Pr, and Nd) indicates that the U-S, U-C ipso , and U-C ortho bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U center dot center dot center dot H-C ε agostic interaction of each thiolate ligand is shorter, by ∼ 0.05 angstrom, than that expected from a purely ionic bonding model. The lanthanide( III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M) U and ion-covalent (i.e. strongly ionic with low orbital interaction), for M) Ln. The strength of the U center dot center dot center dot H-C ε agostic interaction is proposed to be controlled by the maximization of the interaction between U + and S - under steric constraints. The η 3 ligation mode of the aryl-thiolate ligand is also obtained from DFT. (authors)

  3. U(SMes*)n, (n = 3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta3 ligation mode of the arylthiolate ligand, from X-ray diffraction and DFT analysis.

    Science.gov (United States)

    Roger, Mathieu; Barros, Noémi; Arliguie, Thérèse; Thuéry, Pierre; Maron, Laurent; Ephritikhine, Michel

    2006-07-12

    Reaction of U(NEt(2))(4) with HS-2,4,6-(t)Bu(3)C(6)H(2) (HSMes) gave U(SMes)(3)(NEt(2))(py) (1), whereas similar treatment of U[N(SiMe(3))SiMe(2)CH(2)][N(SiMe(3))(2)](2) afforded U(SMes)[N(SiMe(3))(2)](3) (2) and U(SMes)(3)[N(SiMe(3))(2)]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes)(4) (4), was isolated from the reaction of U(BH(4))(4) and KSMes. The first homoleptic thiolate complex of uranium(III), U(SMes)(3) (5), was synthesized by protonolysis of U[N(SiMe(3))(2)](3) with HSMes in cyclohexane. The crystal structure of 5 exhibits the novel eta(3) ligation mode for the arylthiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes)(3) (Ln = La, Ce, Pr, and Nd) indicates that the U-S, U-C(ipso)(), and U-C(ortho)() bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U...H-C epsilon agostic interaction of each thiolate ligand is shorter, by approximately 0.05 A, than that expected from a purely ionic bonding model. The lanthanide(III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M = U and iono-covalent (i.e. strongly ionic with low orbital interaction), for M = Ln. The strength of the U...H-C epsilon agostic interaction is proposed to be controlled by the maximization of the interaction between U(+) and S(-) under steric constraints. The eta(3) ligation mode of the arylthiolate ligand is also obtained from DFT.

  4. 'Americium(III)/trivalent lanthanides' separation using organothiophosphinic acids

    International Nuclear Information System (INIS)

    Hill, C.; Madic, C.; Baron, P.; Ozawa, Masaki; Tanaka, Yasumasa.

    1997-01-01

    The present paper describes the extraction of neodymium and other lanthanides by saponified Cyanex 301 acid. The saponification of commercial Cyanex 301 acid favoured the extraction of macro concentrations of neodymium from sodium nitrate aqueous solutions (pH eq ∼ 4). The amount of lanthanide extracted in the organic phase always reached the third of the initial concentration of saponified Cyanex 301 acid, which assumed a cation exchange mechanism to occur during the extraction. No nitrate anion took part in the complex formation. This paper also compares the abilities of purified Cyanex 301, Cyanex 302 and Cyanex 272 acids to extract and separate 241 Am(III) from 152 Eu(III). Very high separation factors S.F. Am/Eu were observed in the case of purified Cyanex 301 acid. Finally some studies are presented herein using tri-n-butylphosphate (TBP) as a synergistic extractant with Cyanex 301 acid to separate actinides from trivalent lanthanide. (author)

  5. On-line separation of Pu(III) and Am(III) using extraction and ion chromatography

    International Nuclear Information System (INIS)

    Jernstroem, J.; Lehto, J.; Betti, M.

    2007-01-01

    An on-line method developed for separating plutonium and americium was developed. The method is based on the use of HPLC pump with three analytical chromatographic columns. Plutonium is reduced throughout the procedure to trivalent oxidation state, and is recovered in the various separation steps together with americium. Light lanthanides and trivalent actinides are separated with TEVA resin in thiocyanate/formic acid media. Trivalent plutonium and americium are pre-concentrated in a TCC-II cation-exchange column, after which the separation is performed in CS5A ion chromatography column by using two different eluents. Pu(III) is eluted with a dipicolinic acid eluent, and Am(III) with oxalic acid eluent. Radiochemical and chemical purity of the eluted plutonium and americium fractions were ensured with alpha-spectrometry. (author)

  6. Complexes of actinides with naturally occuring organic substances - Literature survey

    International Nuclear Information System (INIS)

    Olofsson, U.; Allard, B.

    1983-02-01

    Properties of naturally occurring humic and fulvic acids and their formation of actinide complexes are reviewed. Actinides in all the oxdation states III, IV, V and VI would form complexes with many humic and fulvic acids, comparable in strength to the hydroxide and carbonate complexes. Preliminary experiments have shown, that the presence of predominantly humic acid complexes would significantly reduce the sorption of americium on geologic media. This does not, however, necessarily lead to a potentially enhanced mobility under environmental conditions, since humic and fulvic acids carrying trace metals also would be strongly bound to e.g. clayish material. (author)

  7. Complexation of biological ligands with lanthanides(III) for MRI: Structure, thermodynamic and methods; Complexation des cations lanthanides trivalents par des ligands d'origine biologique pour l'IRM: Structure, thermodynamique et methodes

    Energy Technology Data Exchange (ETDEWEB)

    Bonnet, C

    2006-07-15

    New cyclic ligands derived from sugars and amino-acids form a scaffold carrying a coordination sphere of oxygen atoms suitable to complex Ln(III) ions. In spite of their rather low molecular weights, the complexes display surprisingly high relaxivity values, especially at high field. The ACX and BCX ligands, which are acidic derivatives of modified and cyclo-dextrins, form mono and bimetallic complexes with Ln(III). The LnACX and LnBCX complexes show affinities towards Ln(III) similar to those of tri-acidic ligands. In the bimetallic Lu2ACX complex, the cations are deeply embedded in the cavity of the ligand, as shown by the X-ray structure. In aqueous solution, the number of water molecules coordinated to the cation in the LnACX complex depends on the nature and concentration of the alkali ions of the supporting electrolyte, as shown by luminescence and relaxometric measurements. There is only one water molecule coordinated in the LnBCX complex, which enables us to highlight an important second sphere contribution to relaxivity. The NMR study of the RAFT peptidic ligand shows the complexation of Ln(III), with an affinity similar to those of natural ligands derived from calmodulin. The relaxometric study also shows an important second sphere contribution to relaxivity. To better understand the intricate molecular factors affecting relaxivity, we developed new relaxometric methods based on probe solutes. These methods allow us to determine the charge of the complex, weak affinity constants, trans-metallation constants, and the electronic relaxation rate. (author)

  8. Complexation of biological ligands with lanthanides(III) for MRI: Structure, thermodynamic and methods; Complexation des cations lanthanides trivalents par des ligands d'origine biologique pour l'IRM: Structure, thermodynamique et methodes

    Energy Technology Data Exchange (ETDEWEB)

    Bonnet, C

    2006-07-15

    New cyclic ligands derived from sugars and amino-acids form a scaffold carrying a coordination sphere of oxygen atoms suitable to complex Ln(III) ions. In spite of their rather low molecular weights, the complexes display surprisingly high relaxivity values, especially at high field. The ACX and BCX ligands, which are acidic derivatives of modified and cyclo-dextrins, form mono and bimetallic complexes with Ln(III). The LnACX and LnBCX complexes show affinities towards Ln(III) similar to those of tri-acidic ligands. In the bimetallic Lu2ACX complex, the cations are deeply embedded in the cavity of the ligand, as shown by the X-ray structure. In aqueous solution, the number of water molecules coordinated to the cation in the LnACX complex depends on the nature and concentration of the alkali ions of the supporting electrolyte, as shown by luminescence and relaxometric measurements. There is only one water molecule coordinated in the LnBCX complex, which enables us to highlight an important second sphere contribution to relaxivity. The NMR study of the RAFT peptidic ligand shows the complexation of Ln(III), with an affinity similar to those of natural ligands derived from calmodulin. The relaxometric study also shows an important second sphere contribution to relaxivity. To better understand the intricate molecular factors affecting relaxivity, we developed new relaxometric methods based on probe solutes. These methods allow us to determine the charge of the complex, weak affinity constants, trans-metallation constants, and the electronic relaxation rate. (author)

  9. Uranyl and/or rare-earth mellitates in extended organic-inorganic networks: A unique case of hetero-metallic cation-cation interaction with U-VI=O-Ln(III) bonding (Ln = Ce, Nd)

    International Nuclear Information System (INIS)

    Volkringer, Christophe; Henry, Natacha; Grandjean, Stephane; Loiseau, Thierry

    2012-01-01

    A series of uranyl and lanthanide (trivalent Ce, Nd) mellitates (mel) has been hydrothermally synthesized in aqueous solvent. Mixtures of these 4f and 5f elements also revealed the formation of a rare case of lanthanide-uranyl coordination polymers. Their structures, determined by XRD single-crystal analysis, exhibit three distinct architectures. The pure lanthanide mellitate Ln 2 (H 2 O) 6 (mel) possesses a 3D framework built up from the connection of isolated LnO 6 (H 2 O) 3 polyhedra (tri-capped trigonal prism) through the mellitate ligand. The structure of the uranyl mellitate (UO 2 ) 3 (H 2 O) 6 - (mel).11.5H 2 O is lamellar and consists of 8-fold coordinated uranium atoms linked to each other through the organic ligand giving rise to the formation of a 2D 3 6 net. The third structural type, (UO 2 ) 2 Ln(OH)(H 2 O) 3 (mel).2.5H 2 O, involves direct oxygen bondings between the lanthanide and uranyl centers, with the isolation of a hetero-metallic dinuclear motif. The 9-fold coordinated Ln cation, LnO 5 (OH)(H 2 O) 3 , is linked to the 7-fold coordinated uranyl (UO 2 )O-4(OH) (pentagonal bipyramid) via one μ 2 -hydroxo group and one μ 2 -oxo group. The latter is shared between the uranyl bonding (U=O = 1.777(4)1.779(6) angstrom) and a long Ln-O bonding (Ce-O = 2.822(4) angstrom; Nd-O = 2.792(6) angstrom). This unusual linkage is a unique illustration of the so-called cation cation interaction associating 4f and 5f metals. The dinuclear motif is then further connected through the mellitate ligand, and this generates organic inorganic layers that are linked to each other via discrete uranyl (UO 2 )O 4 units (square bipyramid), which ensure the three-dimensional cohesion of the structure. The mixed U-Ln carboxylate is thermally decomposed from 260 to 280 degrees C and then transformed into the basic uranium oxide (U 3 O 8 ) together with U-Ln oxide with the fluorite structural type ('(Ln,U)O 2 '). At 1400 degrees C, only fluorite type '(Ln,U)O 2 ' is formed with

  10. The structure of actinide ions exchanged into native and modified zeolites and clays

    International Nuclear Information System (INIS)

    Wasserman, S. R.; Soderholm, L.; Giaquinta, D. M.

    2000-01-01

    X-ray absorption spectroscopy (XAS) has been used to investigate the structure and valence of thorium (Th 4+ ) and uranyl (UO 2 2+ ) cations exchanged into two classes of microporous aluminosilicate minerals: zeolites and smectite clays. XAS is also employed to examine the fate of the exchanged cations after modification of the mineral surface using self-assembled organic films and/or exposure to hydrothermal conditions. These treatments serve as models for the forces that ultimately determine the chemical fate of the actinide cations in the environment. The speciation of the cations depends on the pore size of the aluminosilicate, which is fixed for the zeolites and variable for the smectites

  11. Thermal neutron actinide data

    International Nuclear Information System (INIS)

    Tellier, H.

    1992-01-01

    During the 70's, the physicists involved in the cross section measurements for the low energy neutrons were almost exclusively interested in the resonance energy range. The thermal range was considered as sufficiently known. In the beginning of the 80's, reactor physicists had again to deal with the delicate problem of the power reactor temperature coefficient, essentially for the light water reactors. The measured value of the reactivity temperature coefficient does not agree with the computed one. The later is too negative. For obvious safety reasons, it is an important problem which must be solved. Several causes were suggested to explain this discrepancy. Among all these causes, the spectral shift in the thermal energy range seems to be very important. Sensibility calculations shown that this spectral shift is very sensitive to the shape of the neutron cross sections of the actinides for energies below one electron-volt. Consequently, reactor physicists require new and accurate measurements in the thermal and subthermal energy ranges. A part of these new measurement results were recently released and reviewed. The purpose of this study is to complete the preceding review with the new informations which are now available. In reactor physics the major actinides are the fertile nuclei, uranium 238, thorium 232 and plutonium 240 and the fissile nuclei, uranium 233, uranium 235 and plutonium 239. For the fertile nuclei the main datum is the capture cross section, for the fissile nuclei the data of interest are nu-bar, the fission and capture cross sections or a combination of these data such as η or α. In the following sections, we will review the neutron data of the major actinides for the energy below 1 eV

  12. Actinide Separation Demonstration Facility, Tarapur

    International Nuclear Information System (INIS)

    Vishwaraj, I.

    2017-01-01

    Partitioning of minor actinide from high level waste could have a substantial impact in lowering the radio toxicity associated with high level waste as well as it will reduce the burden on geological repository. In Indian context, the partitioned minor actinide could be routed into the fast breeder reactor systems scheduled for commissioning in the near period. The technological breakthrough in solvent development has catalyzed the partitioning programme in India, leading to the setting up and hot commissioning of the Actinide Separation Demonstration Facility (ASDF) at BARC, Tarapur. The engineering scale Actinide Separation Demonstration Facility (ASDF) has been retrofitted in an available radiological hot cell situated adjacent to the Advanced Vitrification Facility (AVS). This location advantage ensures an uninterrupted supply of high-level waste and facilitates the vitrification of the high-level waste after separation of minor actinides

  13. Synthesis and structural characterization of actinide oxalate compounds

    International Nuclear Information System (INIS)

    Tamain, C.

    2011-01-01

    Oxalic acid is a well-known reagent to recover actinides thanks to the very low solubility of An(IV) and An(III) oxalate compounds in acidic solution. Therefore, considering mixed-oxide fuel or considering minor actinides incorporation in ceramic fuel materials for transmutation, oxalic co-conversion is convenient to synthesize mixed oxalate compounds, precursors of oxide solid solutions. As the existing oxalate single crystal syntheses are not adaptable to the actinide-oxalate chemistry or to their manipulation constrains in gloves box, several original crystal growth methods were developed. They were first validate and optimized on lanthanides and uranium before the application to transuranium elements. The advanced investigations allow to better understand the syntheses and to define optimized chemical conditions to promote crystal growth. These new crystal growth methods were then applied to a large number of mixed An1(IV)-An2(III) or An1(IV)-An2(IV) systems and lead to the formation of the first original mixed An1(IV)-An2(III) and An1(IV)-An2(IV) oxalate single crystals. Finally thanks to the first thorough structural characterizations of these compounds, single crystal X-ray diffraction, EXAFS or micro-RAMAN, the particularly weak oxalate-actinide compounds structural database is enriched, which is essential for future studied nuclear fuel cycles. (author) [fr

  14. Partnew - New solvent extraction processes for minor actinides - final report

    International Nuclear Information System (INIS)

    Madic, C.; Testard, F.; Hudson, M.J.; Liljenzin, J.O.; Christiansen, B.; Ferrando, M.; Facchini, A.; Geist, A.; Modolo, G.; Gonzalez-Espartero, A.; Mendoza, J. de

    2004-01-01

    The objectives of the European project PARTNEW were to define solvent extraction processes for the partitioning of the minor actinides, Am and Cm, from the aqueous high active raffinate or high active concentrate issuing the reprocessing of nuclear spent fuels by the PUREX process. Eleven laboratories participated to the research: 1/ CEA-DEN (Marcoule), 2/ CEA-DSM (Saclay), 3/ UREAD (U.K.), 4/ CTU (Sweden), 5/ ITU (Germany), 6/ ENEA (Italy), 7/ PoliMi (Italy), 8/ FZK-INE (Germany), 9/ FZJ-ISR (Germany), 10/ CIEMAT (Spain) and 11/ UAM (Spain). The research was organised into eight work packages (WP): Basic and applied DIAMEX studies, using diamide extractants for the co-extraction of actinides(III) (An(III)) and lanthanides(III) (Ln(III)) nitrates (WP1 and WP2), Basic and applied SANEX studies based on the use of polydentate N-ligands for the An(III)/Ln(III) separation (WP3 and WP4), Basic and applied SANEX studies based on the use of synergistic mixtures made of bis-(chloro-phenyl)-di-thio-phosphinic acid + neutral O-bearing ligand, (WP5 and WP6), Basic SANEX studies for the An(III)/Ln(III) separation, based on the use of new S-bearing ligands, Basic and applied studies for the Am(III)/Cm(III) separation. The work done in the fundamental and applied domains was very fruitful. Several processes have been successfully tested with genuine high active raffinates and concentrate. (authors)

  15. Synthesis of New Blue Fluorescent Polymerizable 1,8-Naphthalimides and Their Copolymers with Styrene as Sensors for Fe(III Cations

    Directory of Open Access Journals (Sweden)

    Ivo Grabchev

    2014-01-01

    Full Text Available The synthesis, characterization, and functional properties of two new polymerizable 1,8-naphthalimides (MDs have been described. Their copolymers with styrene designed to act as a fluorescence PET chemosensor have been investigated. The study also reports the influence of different metal cations (Ag+, Mg2+, Cu2+, Sr2+, Co2+, Pb2+, and Fe3+ on the fluorescence intensity of both low and high molecular weight fluorophores.

  16. Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Schelter, Eric J.; Wu, Ruilian; Veauthier, Jacqueline M.; Bauer, Eric D.; Booth, Corwin H.; Thomson, Robert K.; Graves, Christopher R.; John, Kevin D.; Scott, Brian L.; Thompson, Joe D.; Morris, David E.; Kiplinger, Jaqueline L.

    2010-02-24

    A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are presented for (C{sub 5}Me{sub 5}){sub 2}An[-N=C(Bn)(tpy-M{l_brace}C{sub 5}Me4R{r_brace}{sub 2})]{sub 2} (where An = Th{sup IV}, U{sup IV}; Bn = CH{sub 2}C{sub 6}H{sub 5}; M = La{sup III}, Sm{sup III}, Yb{sup III}, U{sup III}; R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral 'M' site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb{sup III}-U{sup IV}-Yb{sup III}, Sm{sup III}-U{sup IV}-Sm{sup III}, and La{sup III}-U{sup IV}-La{sup III} complexes, [8]{sup -}, [9b]{sup -} and [10b]{sup -}, respectively, whose calculated comproportionation constant K{sub c} is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U{sup III}, U{sup IV}, and U{sup V} reveal small but detectable energy differences in the 'white-line' feature of the uranium L{sub III}-edges consistent with these variations in nominal oxidation state. The sum of this data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4{prime}-cyano-2,2{prime}:6{prime},2{double_prime}-terpyridine is also reported.

  17. Recovery actinide values

    International Nuclear Information System (INIS)

    Horwitz, E.P.; Delphin, W.H.; Mason, G.W.

    1979-01-01

    A process is described for partitioning and recovering actinide values from acidic waste solutions resulting from reprocessing of irradiated nuclear fuels by adding hydroxylammonium nitrate and hydrazine to the waste solution to adjust the valence of the neptunium and plutonium values in the solution to the +4 oxidation state, thus forming a feed solution and contacting the feed solution with an extractant of di-hexoxyethyl phosphoric acid in an organic diluent whereby the actinide values, most of the rare earth values and some fission product values are taken up by the extractant. Separation is achieved by contacting the loaded extractant with two aqueous strip solutions, a nitric acid solution to selectively strip the americium, curium and rare earth values and an oxalate solution of tetramethylammonium hydrogen oxalate and oxalic acid or trimethylammonium hydrogen oxalate to selectively strip the neptunium, plutonium and fission product values. Uranium values remain in the extractant and may be recovered with a phosphoric acid strip. The neptunium and plutonium values are recovered from the oxalate by adding sufficient nitric acid to destroy the complexing ability of the oxalate, forming a second feed, and contacting the second feed with a second extractant of tricaprylmethylammonium nitrate in an inert diluent whereby the neptunium and plutonium values are selectively extracted. The values are recovered from the extractant with formic acid. (author)

  18. Actinide AMS at DREAMS

    Energy Technology Data Exchange (ETDEWEB)

    Khojasteh, Nasrin B.; Merchel, Silke; Rugel, Georg; Scharf, Andreas; Ziegenruecker, Rene [HZDR, Dresden (Germany); Pavetich, Stefan [HZDR, Dresden (Germany); ANU, Canberra (Australia)

    2016-07-01

    Radionuclides such as {sup 236}U and {sup 239}Pu were introduced into the environment by atmospheric nuclear weapon tests, reactor accidents (Chernobyl, Fukushima), releases from nuclear reprocessing facilities (Sellafield, La Hague), radioactive waste disposal, and accidents with nuclear devices (Palomares, Thule) [1]. Accelerator Mass Spectrometry (AMS) is the most sensitive method to measure these actinides. The DREsden AMS (DREAMS) facility is located at a 6 MV accelerator, which is shared with ion beam analytics and implantation users, preventing major modifications of the accelerator and magnetic analyzers. DREAMS was originally designed for {sup 10}Be, {sup 26}Al, {sup 36}Cl, {sup 41}Ca, and {sup 129}I. To modify the system for actinide AMS, a Time-of-Flight (TOF) beamline at the high-energy side has been installed and performance tests are on-going. Ion beam and detector simulations are carried out to design a moveable ionization chamber. Especially, the detector window and anode dimensions have to be optimized. This ionization chamber will act as an energy detector of the system and its installation is planned as closely as possible to the stop detector of the TOF beamline for highest detection efficiency.

  19. Reversible optical sensor for the analysis of actinides in solution

    International Nuclear Information System (INIS)

    Lesage, B.; Picard, S.; Serein-Spirau, F.; Lereporte, J.P.

    2007-01-01

    In this work is presented a concept of reversible optical sensor for actinides. It is composed of a p doped conducing polymer support and of an anion complexing the actinides. The chosen conducing polymer is the thiophene-2,5-di-alkoxy-benzene whose solubility and conductivity are perfectly known. The actinides selective ligand is a lacunar poly-oxo-metallate such as P 2 W 17 O 61 10- or SiW 11 O 39 8- which are strong anionic complexing agents of actinides at the oxidation state (IV) even in a very acid medium. The sensor is prepared by spin coating of the composite mixture 'polymer + ligand' on a conducing glass electrode and then tested towards its optical and electrochemical answer in presence of uranium (IV). The absorption change due to the formation of cations complexes by poly-oxo-metallate reveals the presence of uranium (IV). After the measurement, the sensor is regenerated by anodic polarization of the support and oxidation of the uranium (IV) into uranium (VI) which weakly interacts with the poly-oxo-metallate and is then released in solution. (O.M.)

  20. Review of the sorption of actinides on natural minerals

    International Nuclear Information System (INIS)

    Beall, G.W.

    1981-01-01

    Over the past few years, a large body of data concerning sorption of actinides on geologic media has been built in connection with high-level-waste disposal. The primary aim of the work has been to allow predictions of the migration behavior of these radionuclides in the case of a breach of the repository that allowed groundwater flow through the repository. As a result of this work, some new backfill materials specifically tailored for the actinides have also been designed. Several major mechanisms of sorption that appear to dominate the sorption of actinides have emerged from these studies. These mechanisms can be divided into solution reactions dominated by hydrolysis, chemisorption reactions, and oxidation-reduction reactions. Each of these mechanisms will be discussed in detail, with experimental examples. Surprisingly, one mechanism, cation exchange, does not play an important role; why it fails to operate in any significant way in the environmental pH region will be discussed. The implications of the sorption mechanisms for waste forms and backfill materials will be discussed in detail. These discussions will center primarily around the valence state of the actinide in various waste forms and the effect of various anions on leachability from waste forms and backfill materials

  1. Liquid-solid extraction of metallic cations by cationic amphiphiles

    International Nuclear Information System (INIS)

    Mueller, Wolfram; Sievers, Torsten K.; Zemb, Thomas; Diat, Olivier; Sievers, Torsten K.; Dejugnat, Christophe

    2012-01-01

    In the field of selective metal ion separation, liquid-liquid extraction is usually conducted through an emulsion mixing of hydrophobic complexants dispersed in an organic phase and acidic water containing the ionic species. Recently, it has been shown that amphiphilic complexants could influence strongly extraction efficiency by enhancing the interfacial interaction between the metal ion in the aqueous and the complexant in the organic phase. Moreover, these amphiphiles can also substitute the organic phase if an appropriate aliphatic chain is chosen. The dispersion of such amphiphilic complexants in an aqueous solution of salt mixtures is not only attractive for studying specific interactions but also to better the understanding of complex formation in aqueous solution of multivalent metal ions, such as lanthanides and actinides. This understanding is of potential interest for a broad range of industries including purification of rare earth metals and pollute treatment e.g. of fission byproducts. This principle can also be applied to liquid-solid extraction, where the final state of the separation is a solid phase containing the selectively extracted ions. Indeed, a novel solid-liquid extraction method exploits the selective precipitation of metal ions from an aqueous salt mixture using a cationic surfactant, below its Krafft point (temperature below which the long aliphatic chains of surfactant crystallize). This technique has been proven to be highly efficient for the separation of actinides and heavy metal using long chain ammonium or pyridinium amphiphiles. The most important point in this process is the recognition of cationic metal ions by cationic surfactants. By computing the free energy of the polar head group per micelle as a function of the different counter-anions, we have demonstrated for the first time that different interactions exist between the micellar surface and the ions. These interactions depend on the nature of the cation but also on

  2. Thermodynamics of the extraction of scandium(III) by the liquid cation exchangers dinonylnaphthalenesulfonic acid and bis(2-ethylhexyl) phosphoric acid

    International Nuclear Information System (INIS)

    Raieh, M.A.; Zakareia, N.; Aly, H.F.

    1979-01-01

    The thermodynamic functions for the extraction of Sc 3+ by liquid cation exchangers HD and HDEHP are determined radiometrically by the temperature coefficient method. The role of the diluent dielectric constant on the extraction of Sc 3+ by HD is also studied. The thermodynamic parameters determined indicated that the free energy variation for the extraction of Sc 3+ by HD is mainly determined by the entropic terms arising from the hydration-dehydration process of the exchanged ions. In the case of HDEHP as extractant, the free energy variations are determined mainly by the entalpic terms of the system. (author)

  3. Concentration of actinides in the food chain

    International Nuclear Information System (INIS)

    Bulman, R.A.

    1976-06-01

    Considerable concern is now being expressed over the discharge of actinides into the environment. This report presents a brief review of the chemistry of the actinides and examines the evidence for interaction of the actinides with some naturally-occurring chelating agents and other factors which might stimulate actinide concentration in the food chain of man. This report also reviews the evidence for concentration of actinides in plants and for uptake through the gastrointestinal tract. (author)

  4. NMR and TRLFS studies of Ln(iii) and An(iii) C5-BPP complexes† †Electronic supplementary information (ESI) available: LIFDI-MS spectra and additional NMR spectra. See DOI: 10.1039/c4sc03103b

    Science.gov (United States)

    Beele, Björn B.; Geist, Andreas; Müllich, Udo; Kaden, Peter; Panak, Petra J.

    2015-01-01

    C5-BPP is a highly efficient N-donor ligand for the separation of trivalent actinides, An(iii), from trivalent lanthanides, Ln(iii). The molecular origin of the selectivity of C5-BPP and many other N-donor ligands of the BTP-type is still not entirely understood. We present here the first NMR studies on C5-BPP Ln(iii) and An(iii) complexes. C5-BPP is synthesized with 10% 15N labeling and characterized by NMR and LIFDI-MS methods. 15N NMR spectroscopy gives a detailed insight into the bonding of C5-BPP with lanthanides and Am(iii) as a representative for trivalent actinide cations, revealing significant differences in 15N chemical shift for coordinating nitrogen atoms compared to Ln(iii) complexes. The temperature dependence of NMR chemical shifts observed for the Am(iii) complex indicates a weak paramagnetism. This as well as the observed large chemical shift for coordinating nitrogen atoms show that metal–ligand bonding in Am(C5-BPP)3 has a larger share of covalence than in lanthanide complexes, confirming earlier studies. The Am(C5-BPP)3 NMR sample is furthermore spiked with Cm(iii) and characterized by time-resolved laser fluorescence spectroscopy (TRLFS), yielding important information on the speciation of trace amounts of minor complex species. PMID:29560242

  5. Lanthanide/Actinide Opacities

    Science.gov (United States)

    Hungerford, Aimee; Fontes, Christopher J.

    2018-06-01

    Gravitational wave observations benefit from accompanying electromagnetic signals in order to accurately determine the sky positions of the sources. The ejecta of neutron star mergers are expected to produce such electromagnetic transients, called macronovae (e.g. the recent and unprecedented observation of GW170817). Characteristics of the ejecta include large velocity gradients and the presence of heavy r-process elements, which pose significant challenges to the accurate calculation of radiative opacities and radiation transport. Opacities include a dense forest of bound-bound features arising from near-neutral lanthanide and actinide elements. Here we present an overview of current theoretical opacity determinations that are used by neutron star merger light curve modelers. We will touch on atomic physics and plasma modeling codes that are used to generate these opacities, as well as the limited body of laboratory experiments that may serve as points of validation for these complex atomic physics calculations.

  6. Relativistic studies in actinides

    International Nuclear Information System (INIS)

    Weinberger, P.; Gonis, A.

    1987-01-01

    In this review the theoretical background is given for a relativistic description for actinide systems. A short introduction is given of the density functional theory which forms the basis for a fully relativistic single-particle theory. A section on the Dirac Hamiltonian is followed by a brief summary on group theoretical concepts. Single site scattering is presented such that formal extensions to the case of the presence of an internal (external) magnetic field and/or anisotropic scattering are evident. Multiple scattering is discussed such that it can readily be applied also to the problem of dislocations. In connection with the problem of selfconsistency particular attention is drawn to the use of complex energies. Finally the various theoretical aspects discussed are illustrated through the results of numerical calculations. 101 refs.; 37 figs.; 5 tabs

  7. New insights into thorium and uranium oxo-arsenic (III/V) and oxo-phosphates (V) crystal chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Na

    2015-12-11

    The fundamental chemistry of actinides is of great interest owing to the diverse number of valence states and complex coordination chemistry of the actinides. The phases based on actinides and oxo-salt fragments have been under thorough investigation in the last decades. These compounds can be widely found in nature and they affect the migration process of actinides in nature. A better understanding of the fundamental coordination chemistry of actinide compounds with oxo-salts of group V elements is not only important for understanding the actinides behavior within the migration process but can also be used to understand actinide properties in phosphate ceramics. Concerning the radioactive issues, the less radioactive early actinides (i.e. U, Th) can be taken as modeling elements to study the crystal chemistry of the transuranic elements (Np, Pu) without the major handling problems. This can be done as Th(IV) has a very similar coordination chemistry with An(IV) and U(VI) can be chosen as a modeling element for transuranic elements in higher valence states. Therefore, a systematic research on the actinides (U, Th) bearing phases with tetrahedral oxo-anions such as phosphates and arsenates have been performed in this work. High temperature (HT) solid state reaction, High pressure high temperature (HP-HT) solid state reaction and the hydrothermal method were the methods of choice for synthesizing actinide bearing oxo-arsenic(III/V) and oxo- phosphorus(V) phases in the past three years. As a result, numerous novel compounds containing actinides were obtained. The structures of all compounds were determined using single crystal X-ray diffraction data. Raman spectroscopy, EDS, DSC and high temperature powder X-ray diffraction (HT-PXRD) measurements were implemented to characterize the chemical and physical properties of the obtained compounds. The core of this dissertation is a fundamental study of the crystal chemistry of actinides (Th, U) oxo-arsenic (III/V) and oxo

  8. New insights into thorium and uranium oxo-arsenic (III/V) and oxo-phosphates (V) crystal chemistry

    International Nuclear Information System (INIS)

    Yu, Na

    2015-01-01

    The fundamental chemistry of actinides is of great interest owing to the diverse number of valence states and complex coordination chemistry of the actinides. The phases based on actinides and oxo-salt fragments have been under thorough investigation in the last decades. These compounds can be widely found in nature and they affect the migration process of actinides in nature. A better understanding of the fundamental coordination chemistry of actinide compounds with oxo-salts of group V elements is not only important for understanding the actinides behavior within the migration process but can also be used to understand actinide properties in phosphate ceramics. Concerning the radioactive issues, the less radioactive early actinides (i.e. U, Th) can be taken as modeling elements to study the crystal chemistry of the transuranic elements (Np, Pu) without the major handling problems. This can be done as Th(IV) has a very similar coordination chemistry with An(IV) and U(VI) can be chosen as a modeling element for transuranic elements in higher valence states. Therefore, a systematic research on the actinides (U, Th) bearing phases with tetrahedral oxo-anions such as phosphates and arsenates have been performed in this work. High temperature (HT) solid state reaction, High pressure high temperature (HP-HT) solid state reaction and the hydrothermal method were the methods of choice for synthesizing actinide bearing oxo-arsenic(III/V) and oxo- phosphorus(V) phases in the past three years. As a result, numerous novel compounds containing actinides were obtained. The structures of all compounds were determined using single crystal X-ray diffraction data. Raman spectroscopy, EDS, DSC and high temperature powder X-ray diffraction (HT-PXRD) measurements were implemented to characterize the chemical and physical properties of the obtained compounds. The core of this dissertation is a fundamental study of the crystal chemistry of actinides (Th, U) oxo-arsenic (III/V) and oxo

  9. Projected benefits of actinide partitioning

    International Nuclear Information System (INIS)

    Braun, C.; Goldstein, M.

    1976-05-01

    Possible benefits that could accrue from actinide separation and transmutations are presented. The time frame for implementing these processes is discussed and the expected benefits are qualitatively described. These benefits are provisionally quantified in a sample computation

  10. Environmental research on actinide elements

    International Nuclear Information System (INIS)

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

    1987-08-01

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

  11. Properties of minor actinide nitrides

    International Nuclear Information System (INIS)

    Takano, Masahide; Itoh, Akinori; Akabori, Mitsuo; Arai, Yasuo; Minato, Kazuo

    2004-01-01

    The present status of the research on properties of minor actinide nitrides for the development of an advanced nuclear fuel cycle based on nitride fuel and pyrochemical reprocessing is described. Some thermal stabilities of Am-based nitrides such as AmN and (Am, Zr)N were mainly investigated. Stabilization effect of ZrN was cleary confirmed for the vaporization and hydrolytic behaviors. New experimental equipments for measuring thermal properties of minor actinide nitrides were also introduced. (author)

  12. Study of complexation process between 4'-nitrobenzo-15-crown-5 and yttrium(III) cation in binary mixed non-aqueous solvents using conductometric method

    Science.gov (United States)

    Habibi, N.; Rounaghi, G. H.; Mohajeri, M.

    2012-12-01

    The complexation reaction of macrocyclic ligand (4'-nitrobenzo-15C5) with Y3+ cation was studied in acetonitrile-methanol (AN-MeOH), acetonitrile-ethanol (AN-EtOH), acetonitrile-dimethylformamide (AN-DMF) and ethylacetate-methanol (EtOAc-MeOH) binary mixtures at different temperatures using conductometry method. The conductivity data show that in all solvent systems, the stoichiometry of the complex formed between 4'-nitrobenzo-15C5 and Y3+ cation is 1: 1 (ML). The stability order of (4'-nitrobenzo-15C5). Y3+ complex in pure non-aqueous solvents at 25°C was found to be: EtOAc > EtOH > AN ≈ DMF > MeOH, and in the case of most compositions of the binary mixed solvents at 25°C it was: AN≈MeOH ≈ AN-EtOH > AN-DMF > EtOAc-MeOH. But the results indicate that the sequence of the stability of the complex in the binary mixed solutions changes with temperature. A non-linear behavior was observed for changes of log K f of (4'-nitrobenzo-15C5 · Y3+) complex versus the composition of the binary mixed solvents, which was explained in terms of solvent-solvent interactions and also the hetero-selective solvation of the species involved in the complexation reaction. The values of thermodynamic parameters (Δ H {c/ℴ} and Δ S {c/ℴ}) for formation of the complex were obtained from temperature dependent of the stability constant using the van't Hoff plots. The results represent that in most cases, the complex is both enthalpy and entropy stabilized and the values and also the sign of thermodynamic parameters are influenced by the nature and composition of the mixed solvents.

  13. Structural and thermodynamic study of rare earth(III) complexation by poly-hydroxylated carboxylic acids: synthesis of new extractants and outlook for the extraction of these cations

    International Nuclear Information System (INIS)

    Aury, S.

    2002-12-01

    The aim of this work is: to improve the knowledge on the binding sites of the poly-hydroxylated carboxylic acids with the trivalent lanthanide(III) ions by comparing them to gluconic acid (previously studied) and to molecules with different configuration and with a variable number of OH functions (threonic acid, glyceric acid, 2-hydroxy-butanoic acid, 3-hydroxy-butanoic acid). To find the best complexing agent among different acids (aldonic acids, aldaric acids, di-hydroxybenzoic acids) (determination of the set of complexes and their stability constants by potentiometry, NMR and UV-Visible spectroscopy). To synthesize hydrophobic monoamides from one lactone form of saccharic acid, to study their complexing power and their capacity to extract the trivalent lanthanide(III) ions. (author)

  14. Actinide colloid generation in groundwater. Part 2

    International Nuclear Information System (INIS)

    Kim, J.I.

    1991-01-01

    The progress made in the investigation of actinide colloid generation in groundwater is summarized and discussed with particular examples relevant to an understanding of the migration behaviour of actinides in natural aquifer systems. The first part deals with the characterization of colloids: groundwater colloids, actinide real-colloids and actinide pseudocolloids. The second part concentrates on the generation processes and migration behaviour of actinide pseudo colloids, which are discussed with some notable experimental examples. Importance is stressed more on the chemical aspects of the actinide colloid generation in groundwater. This work is a contribution to the CEC Mirage II project, in particular the complexation and colloids research area

  15. Research in actinide chemistry. Progress report, March 1, 1980-February 28, 1981

    International Nuclear Information System (INIS)

    1981-01-01

    The primary purpose of this research is to study the behavior of actinide cations in aqueous solution. The interaction of trivalent actinides with a wide variety of both inorganic and organic ligands has been investigated with emphasis on the thermodynamics and kinetics of complexation at tracer concentrations using radiochemical techniques. In order to expand the scope of the experimental techniques, thereby obtaining additional understanding of the fundamental processes involved, non-radioactive experiments with the trivalent lanthanides have been conducted. Visible spectroscopy, nmr ( 1 1 H, 6 13 C, 57 139 La) spectroscopy, potentiometry, solvent extraction and calorimetry are examples of techniques for these lanthanide studies which have allowed much more thorough interpretation of the actinide tracer data due to the close chemical similarity of the lanthanide and actinide families of trivalent cations. The following were investigated: nmr shifts of 139 La for both halate and chloroacetate complexes; interaction of Pu(VI) with carbonates and bicarbonates; Ca +2 , UO 2 +2 , and Th +4 reactions with halate and chloroacetate anions; complexation of the lanthanides by benzoic acid; thermodynamic formation constants for trivalent lanthanide ions with succinic, glutaric, and adipic acids; complexation of benzene polycarboxylates with lanthanides; complexation of lanthanide ions by AMP (adenosine monophosphate), ADP (adenosine diphosphate) and ATP (adenosine triphosphate); interaction of the actinides ions with humic acid; measurements of water and benzoic acid concentrations in several organic solvents by potentiometric and spectral methods; and plutonium and neptunium redox behavior in the presence of organic complexing agents

  16. Actinides and heavy fermions

    International Nuclear Information System (INIS)

    Smith, J.L.; Fisk, Z.; Ott, H.R.

    1987-01-01

    The actinide series of elements begins with f-shell electrons forming energy bands, contributing to the bonding, and possessing no magnetic moments. At americium the series switches over to localized f electrons with magnetic moments. In metallic compounds this crossover of behavior can be modified and studied. In this continuum of behavior a few compounds on the very edge of localized f-electron behavior exhibit enormous electronic heat capacities at low temperatures. This is associated with an enhanced thermal mass of the conduction electrons, which is well over a hundred times the free electron mass, and is what led to the label heavy fermion for such compounds. A few of these become superconducting at even lower temperatures. The excitement in this field comes from attempting to understand how this heaviness arises and from the likelihood that the superconductivity is different from that of previously known superconductors. The effects of thorium impurities in UBe 13 were studied as a representative system for studying the nature of the superconductivity

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

    Energy Technology Data Exchange (ETDEWEB)

    Raymond, K.N.; White, D.J.; Xu, Jide; Mohs, T.R. [Univ. of California, Berkeley, CA (United States)

    1997-10-01

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

  18. Determination of actinides using ICP-SFMS

    International Nuclear Information System (INIS)

    Nygren, Ulrika

    2006-01-01

    Interest in the determination of the actinides using ICP-MS has steadily increased with the development of systems capable of more sensitive and precise measurements. However, the analysis of less abundant actinides such as Pu and Am is not straightforward due to the need for chemical separation of these elements prior to determination. In many applications of mass-spectrometric actinide analysis, isotope ratio measurements are important, either for the analysis of the isotopic composition of, e.g., U or Pu in the sample, or for quantitative determinations using isotope dilution mass spectrometry. In order to achieve high precision and accuracy in an isotope ratio measurement, corrections for instrumentally induced systematic errors, e.g., due to dead-time and mass bias, need to be considered. In this thesis, different aspects of actinide analysis using ICP-SFMS have been addressed. In Papers I and III, separation procedures based on solid phase extraction for Pu, Am and U were developed and evaluated with respect to chemical yield and separation from elements causing spectral interferences. Applications of the analytical procedures developed comprised measurement of the 240 Pu/ 2 3 9Pu ratio in environmental reference materials, and age determination of Pu based on the 241 Pu/ 241 Am and 240 Pu/ 236 U ratios. In the application of different separation procedures for Pu, previously unidentified spectral interferences were discovered. In Paper II, these interferences were identified as lanthanide phosphate ions and the composition and formation of these species with respect to different instrumental parameters were further examined. Due to the importance of precise and accurate isotope ratio determination, a thorough investigation of the instrumental dead time of an ICP-SFMS system was performed. The dead time was evaluated via both isotope ratio and electronic measurements of the output from the detector amplifier. It was found that the overall uncertainty in ratio

  19. Mechanistic Study of the Oxidative Coupling of Styrene with 2-Phenylpyridine Derivatives Catalyzed by Cationic Rhodium( III) via C–H Activation

    Science.gov (United States)

    Brasse, Mikaël; Cámpora, Juan; Ellman, Jonathan A.; Bergman, Robert G.

    2013-01-01

    The Rh(III) catalyzed oxidative coupling of alkenes with arenes provides a greener alternative to the classical Heck reaction for the synthesis of arene-functionalized alkenes. The present mechanistic study gives insights for the rational development of this key transformation. The catalyst resting states and the rate law of the reaction have been identified. The reaction rate is solely dependent on catalyst and alkene concentrations and the rate determining step is the migratory insertion of alkene into a Rh–C(aryl) bond. PMID:23590843

  20. Lanthanides and actinides extraction by calixarenes containing CMPO groups

    International Nuclear Information System (INIS)

    Garcia Carrera, A.

    2001-01-01

    In the framework of the French program SPIN concerning the radioactive waste management, researches are performed to develop processes allowing the separation of long-lived radioisotopes in order to their transmutation or their specific conditioning. These studies deal with the extraction and the separation of trivalent lanthanides and actinides in acid solution. Many systems ''calixarene-diluent-aqueous phase'' are examined by extraction liquid-liquid and membrane transport. The extraction efficiency and the selectivity of the synthesized calixarene-CMPO and of the CMPO are compared with these cations, as the nitric acid extraction by these molecules. (A.L.B.)

  1. Actinide burning and waste disposal

    Energy Technology Data Exchange (ETDEWEB)

    Pigford, T H [University of California, Berkeley, CA (United States)

    1990-07-01

    Here we review technical and economic features of a new proposal for a synergistic waste-management system involving reprocessing the spent fuel otherwise destined for a U.S. high-level waste repository and transmuting the recovered actinides in a fast reactor. The proposal would require a U.S. fuel reprocessing plant, capable of recovering and recycling all actinides, including neptunium americium, and curium, from LWR spent fuel, at recoveries of 99.9% to 99.999%. The recovered transuranics would fuel the annual introduction of 14 GWe of actinide-burning liquid-metal fast reactors (ALMRs), beginning in the period 2005 to 2012. The new ALMRs would be accompanied by pyrochemical reprocessing facilities to recover and recycle all actinides from discharged ALMR fuel. By the year 2045 all of the LWR spent fuel now destined f a geologic repository would be reprocessed. Costs of constructing and operating these new reprocessing and reactor facilities would be borne by U.S. industry, from the sale of electrical energy produced. The ALMR program expects that ALMRs that burn actinides from LWR spent fuel will be more economical power producers than LWRs as early as 2005 to 2012, so that they can be prudently selected by electric utility companies for new construction of nuclear power plants in that era. Some leaders of DOE and its contractors argue that recovering actinides from spent fuel waste and burning them in fast reactors would reduce the life of the remaining waste to about 200-300 years, instead of 00,000 years. The waste could then be stored above ground until it dies out. Some argue that no geologic repositories would be needed. The current view expressed within the ALMR program is that actinide recycle technology would not replace the need for a geologic repository, but that removing actinides from the waste for even the first repository would simplify design and licensing of that repository. A second geologic repository would not be needed. Waste now planned

  2. Actinide burning and waste disposal

    International Nuclear Information System (INIS)

    Pigford, T.H.

    1990-01-01

    Here we review technical and economic features of a new proposal for a synergistic waste-management system involving reprocessing the spent fuel otherwise destined for a U.S. high-level waste repository and transmuting the recovered actinides in a fast reactor. The proposal would require a U.S. fuel reprocessing plant, capable of recovering and recycling all actinides, including neptunium americium, and curium, from LWR spent fuel, at recoveries of 99.9% to 99.999%. The recovered transuranics would fuel the annual introduction of 14 GWe of actinide-burning liquid-metal fast reactors (ALMRs), beginning in the period 2005 to 2012. The new ALMRs would be accompanied by pyrochemical reprocessing facilities to recover and recycle all actinides from discharged ALMR fuel. By the year 2045 all of the LWR spent fuel now destined f a geologic repository would be reprocessed. Costs of constructing and operating these new reprocessing and reactor facilities would be borne by U.S. industry, from the sale of electrical energy produced. The ALMR program expects that ALMRs that burn actinides from LWR spent fuel will be more economical power producers than LWRs as early as 2005 to 2012, so that they can be prudently selected by electric utility companies for new construction of nuclear power plants in that era. Some leaders of DOE and its contractors argue that recovering actinides from spent fuel waste and burning them in fast reactors would reduce the life of the remaining waste to about 200-300 years, instead of 00,000 years. The waste could then be stored above ground until it dies out. Some argue that no geologic repositories would be needed. The current view expressed within the ALMR program is that actinide recycle technology would not replace the need for a geologic repository, but that removing actinides from the waste for even the first repository would simplify design and licensing of that repository. A second geologic repository would not be needed. Waste now planned

  3. 33rd Actinide Separations Conference

    Energy Technology Data Exchange (ETDEWEB)

    McDonald, L M; Wilk, P A

    2009-05-04

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

  4. 33rd Actinide Separations Conference

    International Nuclear Information System (INIS)

    McDonald, L.M.; Wilk, P.A.

    2009-01-01

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

  5. Thermal-hydraulics of actinide burner reactors

    International Nuclear Information System (INIS)

    Takizuka, Takakazu; Mukaiyama, Takehiko; Takano, Hideki; Ogawa, Toru; Osakabe, Masahiro.

    1989-07-01

    As a part of conceptual study of actinide burner reactors, core thermal-hydraulic analyses were conducted for two types of reactor concepts, namely (1) sodium-cooled actinide alloy fuel reactor, and (2) helium-cooled particle-bed reactor, to examine the feasibility of high power-density cores for efficient transmutation of actinides within the maximum allowable temperature limits of fuel and cladding. In addition, calculations were made on cooling of actinide fuel assembly. (author)

  6. Cation Recognition: Novel Potentiometric PVC-Membrane Sensor based on Meso-octamethylcalix[4]pyrrole for the Determination of Trace Amounts of Titanium (III) Ions

    International Nuclear Information System (INIS)

    Saeid Ahmadzadeh; Anuar Kassim Majid Rezayi

    2011-01-01

    The present work deals with developing a novel high selective membrane electrode based on meso-octamethylcalix[4]pyrrole for accurate determination of trace amount of titanium (III) ions in real sample solutions. The amounts of ionophore (4 mg), PVC (33 mg), dioctyl phthalate (DOP) as plasticizer (62.8 mg) and sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (NaTFPB) as an ionic additive (0.2 mg) were optimized in the preparation of the membrane. The electrode exhibited a linear response with a near Nernstian slope of 29.49±0.16 (mV per decade of activity) over the pH range from 1 to 3 with a satisfactory concentration range of 1.0 x 10 -6 to 1.0 x x10 -2 M. The developed sensor exhibited good reproducibility over a period of about 3 months with a fast response time of 15 seconds. (author)

  7. Solvation and complexation study by fluorescence spectroscopy of Eu(III) and Cm(III) ions in octanol solution and at the interface with water

    International Nuclear Information System (INIS)

    Vu, T.H.

    2008-01-01

    Polydentate N-donors ligands like bis-triazine-pyridine (BTP) and bis-triazine-bis-pyridine (BTBP) can selectively extract minor actinides (III) from lanthanides (III) ions and therefore have been studied in the field of nuclear waste reprocessing. The aim of the researches carried out during this thesis is a better description of this family in biphasic systems: speciation in the organic phase and around the interfacial area. After an exhaustive description of the solvation of europium(III) cation in mixed solutions n-octanol water with TRLIF spectrometry, the complexation with nitrogen ligands iPr-BTP, C5-BTBP and CyMe4-BTBP has been studied by TRLIF and ESI-MS techniques. For each compound, the inner sphere of europium has been described and the conditional stability constants determined. The composition of the organic medium, and particularly the hydration degree of n-octanol, has an impact on the nature and the ratio of species 'cation - counter ion - ligand - water'. With high water content (representative of extraction systems), the complexes observed with Cm(III) and Eu(III) have the same stoichiometry but the affinity towards the curium cation is higher and consistent to separation factors measured with biphasic systems. The method TIRF (total internal reflection fluorescence) was retained to study the behaviour of europium(III) inside the interfacial area. Fluorescence spectra of europium have been obtained but side signals and the high depth resolution of detection lead to difficulty in obtaining the signal of interfacial europium alone. The selected technique remains promising but some improvements need to be implemented for forthcoming measurement at liquid/liquid interface. (author) [fr

  8. Fusion barrier characteristics of actinides

    Science.gov (United States)

    Manjunatha, H. C.; Sridhar, K. N.

    2018-03-01

    We have studied fusion barrier characteristics of actinide compound nuclei with atomic number range 89 ≤ Z ≤ 103 for all projectile target combinations. After the calculation of fusion barrier heights and positions, we have searched for their parameterization. We have achieved the empirical formula for fusion barrier heights (VB), positions (RB), curvature of the inverted parabola (ħω) of actinide compound nuclei with atomic number range 89 ≤ Z ≤ 103 for all projectile target combinations (6 projectile target combinations. The values produced by the present formula are also compared with experiments. The present pocket formula produces fusion barrier characteristics of actinides with the simple inputs of mass number (A) and atomic number (Z) of projectile-targets.

  9. ALMR potential for actinide consumption

    International Nuclear Information System (INIS)

    Cockey, C.L.; Thompson, M.L.

    1992-01-01

    The Advanced Liquid Metal Reactor (ALMR) is a US Department of Energy (DOE) sponsored fast reactor design based on the Power Reactor, Innovative Small Module (PRISM) concept originated by General Electric. This reactor combines a high degree of passive safety characteristics with a high level of modularity and factory fabrication to achieve attractive economics. The current reference design is a 471 MWt modular reactor fueled with ternary metal fuel. This paper discusses actinide transmutation core designs that fit the design envelope of the ALMR and utilize spent LWR fuel as startup material and for makeup. Actinide transmutation may be accomplished in the ALMR core by using either a breeding or burning configuration. Lifetime actinide mass consumption is calculated as well as changes in consumption behavior throughout the lifetime of the reactor. Impacts on system operational and safety performance are evaluated in a preliminary fashion. Waste disposal impacts are discussed. (author)

  10. Thin layers in actinide research

    International Nuclear Information System (INIS)

    Gouder, T.

    1998-01-01

    Surface science research at the ITU is focused on the synthesis and surface spectroscopy studies of thin films of actinides and actinide compounds. The surface spectroscopies used are X-ray and ultra violet photoelectron spectroscopy (XPS and UPS, respectively), and Auger electron spectroscopy (AES). Thin films of actinide elements and compounds are prepared by sputter deposition from elemental targets. Alloy films are deposited from corresponding alloy targets and could be used, in principle, as replicates of these targets. However, there are deviations between alloy film and target composition, which depend on the deposition conditions, such as pressure and target voltage. Mastering of these effects may allow us to study stoichiometric film replicates instead of thick bulk compounds. As an example, we discuss the composition of U-Ni films prepared from a UNi 5 target. (orig.)

  11. Nuclear waste forms for actinides

    Science.gov (United States)

    Ewing, Rodney C.

    1999-01-01

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

  12. Extraction chromatogrpahy of actinides, ch. 7

    International Nuclear Information System (INIS)

    Mueller, W.

    1975-01-01

    This review on extraction chromatography of actinides emphasizes the important usage of neutral (Tributylphosphate), basic (substituted ammonium salts), and acidic (HDEHP) extractants, and their application to separations of actinides in the di-to hexavalent oxidation state. Furthermore, the actinide extraction by ketones, ethers, alcohols and β-diketones is discussed

  13. Actinides integral measurements on FCA assemblies

    International Nuclear Information System (INIS)

    Mukaiyama, Takehiko; Okajima, Shigeaki

    1984-01-01

    Actinide integral measurements were performed on eight assemblies of FCA where neutron energy spectra were shifted systematically from soft to hard in order to evaluate and modify the nuclear cross section data of major actinides. Experimental values on actinide fission rates and sample reactivity worths are compared with the calculated values using JENDL-2 and ENDF/B-V (or IV) data sets. (author)

  14. Moessbauer effect studies with actinides

    International Nuclear Information System (INIS)

    Stone, J.A.

    1966-01-01

    Moessbauer resonance studies in the actinide elements offer a new technique for measuring solid-state properties to a region of the periodic chart where such information is relatively sparse. It is well known that the actinides, the elements with atomic numbers from 90 to 103, form a transition series due to filling of the 5f electron shell, analogous to the rare-earth series in which the 4f shell is filled. Like the rare earths, the actinide metals and compounds are expected to exhibit a variety of interesting magnetic properties, but, unlike the rare earths, there have been few studies of the magnetic behaviour of actinides, and these properties are largely unknown. The chemical properties of the actinides have been studied somewhat more extensively, and, in contrast to the rare earths, form a multiplicity of stable valence states, especially in the lighter members of the series. It is just these properties, magnetic and chemical, for which the Moessbauer effect is a valuable probe, sensitive to the magnetic and electric environment of an atom. The rare-earth series has been a particularly fruitful region in terms of the number of elements which have been shown to exhibit the Moessbauer effect, and for this reason the exploitation of the Moessbauer effect to yield new solid-state and chemical information on the rare earths is a highly active field of research today. There is every reason to believe that the actinides can be similarly studied by the Moessbauer effect. 43 refs, 6 figs, 4 tabs

  15. Preliminary considerations concerning actinide solubilities

    International Nuclear Information System (INIS)

    Newton, T.W.; Bayhurst, B.P.; Daniels, W.R.; Erdal, B.R.; Ogard, A.E.

    1980-01-01

    Work at the Los Alamos Scientific Laboratory on the fundamental solution chemistry of the actinides has thus far been confined to preliminary considerations of the problems involved in developing an understanding of the precipitation and dissolution behavior of actinide compounds under environmental conditions. Attempts have been made to calculate solubility as a function of Eh and pH using the appropriate thermodynamic data; results have been presented in terms of contour maps showing lines of constant solubility as a function of Eh and pH. Possible methods of control of the redox potential of rock-groundwater systems by the use of Eh buffers (redox couples) is presented

  16. Orbital effects in actinide systems

    International Nuclear Information System (INIS)

    Lander, G.H.

    1983-01-01

    Actinide magnetism presents a number of important challenges; in particular, the proximity of 5f band to the Fermi energy gives rise to strong interaction with both d and s like conduction electrons, and the extended nature of the 5f electrons means that they can interact with electron orbitals from neighboring atoms. Theory has recently addressed these problems. Often neglected, however, is the overwhelming evidence for large orbital contributions to the magnetic properties of actinides. Some experimental evidence for these effects are presented briefly in this paper. They point, clearly incorrectly, to a very localized picture for the 5f electrons. This dichotomy only enhances the nature of the challenge

  17. Safe actinide disposition in molten salt reactors

    International Nuclear Information System (INIS)

    Gat, U.

    1997-01-01

    Safe molten salt reactors (MSR) can readily accommodate the burning of all fissile actinides. Only minor compromises associated with plutonium are required. The MSRs can dispose safely of actinides and long lived isotopes to result in safer and simpler waste. Disposing of actinides in MSRs does increase the source term of a safety optimized MSR. It is concluded that the burning and transmutation of actinides in MSRs can be done in a safe manner. Development is needed for the processing to handle and separate the actinides. Calculations are needed to establish the neutron economy and the fuel management. 9 refs

  18. Burning actinides in very hard spectrum reactors

    International Nuclear Information System (INIS)

    Robinson, A.H.; Shirley, G.W.; Prichard, A.W.; Trapp, T.J.

    1978-01-01

    The major unresolved problem in the nuclear industry is the ultimate disposition of the waste products of light water reactors. The study demonstrates the feasibility of designing a very hard spectrum actinide burner reactor (ABR). A 1100 MW/sub t/ ABR design fueled entirely with actinides reprocessed from light water reactor (LWR) wastes is proposed as both an ultimate disposal mechanism for actinides and a means of concurrently producing usable power. Actinides from discharged ABR fuel are recycled to the ABR while fission products are routed to a permanent repository. As an integral part of a large energy park, each such ABR would dispose of the waste actinides from 2 LWRs

  19. Actinides and environmental interfaces: striving for molecular-level understanding

    International Nuclear Information System (INIS)

    Heino Nitsche

    2005-01-01

    enhanced second harmonic generation can probe the electronic (UV-vis region) structure of metal species adsorbed at a surface or interface. Infrared-visible sum frequency generation spectroscopy probes the infrared vibrational spectrum of molecules adsorbed at the interface. SHG/SFG studies will greatly assist with understanding reactivity at interfaces of oxides and soil organic matter with heavy metals and radionuclides/actinides. Time-resolved Laser-fluorescence spectroscopy (TRLFS) is a highly sensitive tool for actinides that absorb light and de-excite by fluorescence emission, e.g., U(VI) and Cm(III), to probe changes in actinide speciation and coordination environment in solution. This method can also be used to differentiate whether adsorbed species form surface complexes or surface precipitates. Recently, it was shown that the intense synchrotron radiation can change the oxidation states of redox-sensitive actinide samples which may cause erroneous results, and low temperature measurements are now used to alleviate this shortcoming. X-ray Absorption Fine Structure (XAFS) Spectroscopy is composed of two component spectroscopies, X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) which provide element specific oxidation state and local structure information, respectively. EXAFS (Extended X-ray Absorption Fine Structure Spectroscopy) provides information on the chemical environment of particular actinide, in particular bond lengths and the number of neighboring atoms. Combining both methods, detailed knowledge of the different processes resulting from the interaction of the selected actinides with environmental interfaces can be gained. XANES and EXAFS measurements and TRLFS studies to obtain molecular-level mechanistic details of actinide interaction with common environmental solutions and interfaces will be presented together with first SHG/SFG characterization results of model systems for environmental interfaces

  20. The complex formation of selected actinides (U, Np, Cm) with microbial ligands

    International Nuclear Information System (INIS)

    Glorius, Maja

    2009-01-01

    One of the urgent tasks in the field of nuclear technology is the final storage of radioactive substances. As a part of the safety requirements the protection of humans and the environment from the danger of radioactive substances in case of the release from the final storage is essential. For performing long-term safety calculations the detailed understanding of the physico-chemical effects and influences which cause the mobilisation and transport of actinides are necessary. The presented work was a discrete part of a project, which was focused on the clarification of the influence of microorganisms on the migration of actinides in case of the release of actinides from a final storage. The influence of microbial produced substances on the mobilisation of selected actinides was studied thereby. The microbial produced substances studied in this project were synthesized by bacteria from the Pseudomonas genus under special conditions. Fluorescent Pseudomonads secrete bacterial pyoverdin-type siderophores with a high potential to complex and transport metals, especially iron(III). The aim of the project was to determine how and under which conditions the bioligands are able to complex also radioactive substances and therefore to transport them. For this work the alpha-emitting actinides uranium, curium and neptunium were chosen because their long-life cycle and their radiotoxicity are a matter of particular interest. This work dealed with the interaction of the actinides U(VI), Np(V) and Cm(III) with model ligands simulating the functionality of the pyoverdins. So, such bioligands can essentially influence the behaviour of actinides in the environment. The results of this work contribute to a better understanding and assessment of the influence of the microbial ligands to the mobilisation and migration of the radionuclides. The outcomes could be used to quantify the actinide-mobilising effect of the bioligands, which are released, for example, in the vicinity of a

  1. Sol-gel chemistry applied to the synthesis of polymetallic oxides including actinides reactivity and structure from solution to solid state; Synthese par voie douce d'oxydes polymetalliques incluant des actinides: reactivite et structure de la solution au solide

    Energy Technology Data Exchange (ETDEWEB)

    Lemonnier, St

    2006-02-15

    Minor actinides transmutation is studied at present in order to reduce the radiotoxicity of nuclear waste and the assessment of its technical feasibility requires specific designed materials. When considering americium, yttria stabilized zirconia (Am{sup III} YII Zriv)Or{sub x} is among the ceramic phases that one which presents the required physico-chemical properties. An innovative synthesis of this mixed oxide by sol-gel process is reported in this manuscript. The main aim of this work is to adjust the reactivity of the different metallic cations in aqueous media using complexing agent, in order to initiate a favourable interaction for a homogeneous elements repartition in the forming solid phase. The originality of the settled synthesis lies on an in-situ formation of a stable and monodisperse nano-particles dispersion in the presence of acetylacetone. The main reaction mechanisms have been identified: the sol stabilisation results from an original interaction between the three compounds (Zrly, trivalent cations and acetylacetone). The sol corresponds to a structured system at the nanometer scale for which zirconium and trivalent cations are homogeneously dispersed, preliminary to the sol-gel transition. Furthermore, preliminary studies were carried out with a view to developing materials. They have demonstrated that numerous innovative and potential applications can be developed by taking advantage of the direct and controlled formation of the sol and by adapting the sol-gel transition. The most illustrating result is the preparation of a sintered pellet with the composition Am0,13Zro,73Yo,0901,89 using this approach. (author)

  2. Research on the chemical speciation of actinides

    International Nuclear Information System (INIS)

    Jung, Euo Chang; Park, K. K.; Cho, H. R.

    2010-04-01

    A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using advanced laser-based highly sensitive spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been performed for the chemical speciation of actinide in an aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. (1) Development of TRLFS technology for chemical speciation of actinides, (2) Development of LIBD technology for measuring solubility of actinides, (3) Chemical speciation of plutonium complexes by using a LWCC system, (4) Development of LIBS technology for the quantitative analysis of actinides, (5) Development of technology for the chemical speciation of actinides by CE, (6) Evaluation on the chemical reactions between actinides and humic substances, (7) Chemical speciation of actinides adsorbed on metal oxides surfaces, (8) Determination of actinide source terms of spent nuclear fuel

  3. A literature review of actinide-carbonate mineral interactions

    International Nuclear Information System (INIS)

    Stout, D.L.

    1993-10-01

    Chemical retardation of actinides in groundwater systems is a potentially important mechanism for assessing the performance of the Waste Isolation Pilot Plant (WIPP), a facility intended to demonstrate safe disposal of transuranic waste. Rigorous estimation of chemical retardation during transport through the Culebra Dolomite, a water-bearing unit overlying the WIPP, requires a mechanistic understanding of chemical reactions between dissolved elements and mineral surfaces. This report represents a first step toward this goal by examining the literature for pertinent experimental studies of actinide-carbonate interactions. A summary of existing models is given, along with the types of experiments on which these models are based. Articles pertaining to research into actinide interactions with carbonate minerals are summarized. Select articles involving trace element-carbonate mineral interactions are also reviewed and may serve as templates for future research. A bibliography of related articles is included. Americium(III), and its nonradioactive analog neodymium(III), partition strongly from aqueous solutions into carbonate minerals. Recent thermodynamic, kinetic, and surface studies show that Nd is preferentially removed from solution, forming a Nd-Ca carbonate solid solution. Neptunium(V) is rapidly removed from solution by carbonates. Plutonium incorporation into carbonates is complicated by multiple oxidation states. Little research has been done on the radium(H) and thorium(IV) carbonate systems. Removal of uranyl ion from solution by calcite is limited to monolayer surface coverage

  4. ENDF/B-V actinides

    International Nuclear Information System (INIS)

    Kocherov, N.; Lemmel, H.D.

    1981-01-01

    This document summarizes the contents of the actinides part of the ENDF/B-V nuclear data library released by the US National Nuclear Data Center. This library or selective retrievals of it, are available from the IAEA Nuclear Data Section. (author)

  5. Environmental research on actinide elements

    Energy Technology Data Exchange (ETDEWEB)

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

    1987-08-01

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

  6. Actinide solubility in deep groundwaters - estimates for upper limits based on chemical equilibrium calculations

    International Nuclear Information System (INIS)

    Schweingruber, M.

    1983-12-01

    A chemical equilibrium model is used to estimate maximum upper concentration limits for some actinides (Th, U, Np, Pu, Am) in groundwaters. Eh/pH diagrams for solubility isopleths, dominant dissolved species and limiting solids are constructed for fixed parameter sets including temperature, thermodynamic database, ionic strength and total concentrations of most important inorganic ligands (carbonate, fluoride, phosphate, sulphate, chloride). In order to assess conservative conditions, a reference water is defined with high ligand content and ionic strength, but without competing cations. In addition, actinide oxides and hydroxides are the only solid phases considered. Recommendations for 'safe' upper actinide solubility limits for deep groundwaters are derived from such diagrams, based on the predicted Eh/pH domain. The model results are validated as far as the scarce experimental data permit. (Auth.)

  7. Effects of humic substances on the migration of radionuclides: Complexation of actinides with humic substances. 3. Progress report

    International Nuclear Information System (INIS)

    Kim, J.I.; Rhee, D.S.; Buckau, G.; Moulin, V.; Tits, J.; Decambox, P.; Franz, C.; Herrmann, G.; Trautmann, N.; Dierckx, A.; Vancluysen, J.; Maes, A.

    1993-03-01

    The aim of the present research programme is to study the complexation behaviour of actinide ions with humic substances in natural aquifer systems and hence to quantify the effect of humic substances on the actinide migration. Aquatic humic substances commonly found in all groundwaters in different concentrations have a strong tendency towards complexation with actinide ions. This is one of the major geochemical reactions but hitherto least quantified. Therefore, the effect of humic substances on the actinide migration is poorly understood. In the present research programme the complexation of actinide ions with humic substances will be described thermodynamically. This description will be based on a model being as simple as possible to allow an easy introduction of the resulting reaction constants into geochemical modelling of the actinide migration. This programme is a continuation of the activities of the COCO group in the second phase of the CEC-MIRAGE project. The programme consists of the following three main tasks: Task 1: Complexation reactions of actinide ions with well characterized reference and site-specific humic and fulvic acids; Task 2: Competition reactions with major cations in natural groundwaters; Task 3: Validation of the complexation data in natural aquatic systems by comparison of calculation with spectroscopic experiment. (orig./EF)

  8. Use of Electro-spray Ionization Mass Spectrometry (ESI-MS) for the characterization of complexes 'ligand - metallic cations' in solution

    Energy Technology Data Exchange (ETDEWEB)

    Berthon, Laurence; Zorz, Nicole; Lagrave, Stephanie; Gannaz, Benoit; Hill, Clement [CEA-Marcoule DEN-DRCP-SCPS-LCSE, BP 17171, 30207 Bagnols sur Ceze cedex (France)

    2008-07-01

    In the framework of nuclear waste reprocessing, separation processes of minor actinides from fission products are developed by Cea. In order to understand the mechanisms involved in the extraction processes, the 'ligand/metallic cation' complexes, formed in the organic phases are characterized by electro-spray-mass-spectrometry (ESI-MS). This paper deals with the extraction of lanthanides (III) and americium (III) cations by an organic phase composed of a malonamide or / and a dialkyl phosphoric acid, diluted in an aliphatic diluent. For the dialkyl phosphoric acid, Ln(DEHP){sub 3}(HDEHP){sub 3} complexes are observed and in the presence of a large excess of Ln(NO{sub 3}){sub 3}, dinuclear species are also observed. For the malonamide extractant, it appears that the complexes formed in the organic phase are of the Nd(NO{sub 3}){sub 3}D{sub x} type, with 2 {<=} x {<=} 4: their distributions depend on the ratio [Ln]/[DMDOHEMA]. When the two extractants are present in the organic phase, mixed 'Ln-malonamide-dialkyl phosphoric acid' species are observed. The influence of several parameters, such as extractant concentration, solute concentration, aqueous acidity and the nature of the cations (lanthanides or americium) are studied. (authors)

  9. Lanthanide and actinide ion phytoextraction: investigations of biosorption chemistry

    International Nuclear Information System (INIS)

    Rayson, Gary D.; Serna, Debbie D.; Moore, Jessica L.

    2009-01-01

    Investigations of the chemical interactions responsible for passive biosorption of a lanthanide (Eu (III)) and an actinide (U (VI)) metal ion is described. Spectroscopic methods for the elucidation of chemical functionalities on cultured anther cell walls from the plant Datura innoxia include metal ion luminescence measurements. These have revealed the presence of distinctly different binding environments involving one, two, and three carboxylate moieties for Eu (III) and UO 2 2+ binding and sulfonates (or sulfates) and phosphates for sequestration of Eu (III) on the uranyl ion, respectively. Additional investigations of the apparent affinities of these metals to this material have revealed the presence of both low and high affinity sites for the binding of Eu (III) with weak electrostatic attractions proposed for binding at high metal concentrations (i.e., low affinities) and surface coordination interactions responsible for higher affinities. Conversely, total uranyl ion binding revealed only a single distribution of interactions based on apparent affinities. (author)

  10. Synthesis and Evaluation of new Polyfunctional Molecules for Group Actinide Extraction

    International Nuclear Information System (INIS)

    Marie, C.

    2009-10-01

    The aim of this project is to design new extracting molecules for spent nuclear fuel reprocessing. In order to minimize the long-term residual radiotoxicity of the waste, the GANEX process is an option based on homogeneous recycling of actinides. All actinides (U, Np, Pu, Am, Cm), present in a highly acidic aqueous solution, would be extracted together and separated from fission products (especially from lanthanides) using liquid-liquid extraction. In this context, twenty new bi-topic ligands constituted of a nitrogen poly-aromatic unit functionalized by amide groups were synthesized. Liquid-liquid extraction tests with these ligands dissolved alone in the organic phase show that N, N, N', N'-tetra-alkyl-6, 6''(2, 2':6', 2''-terpyridine)-diamides are able to selectively extract actinides at different oxidation states (Np(V et VI), U(VI), Pu(IV), Am(III), Cm(III)) from an aqueous solution 3M HNO 3 . Nevertheless, actinides(III) are poorly extracted. According to crystallographic structures of complexes with Nd(III) and U(VI) determined by X-rays diffraction, these ligands are penta-dentate. In solution (methanol), complexes stoichiometries (1:1) of Nd(III), U(VI) and Pu(IV) were determined by electro-spray ionization mass spectrometry. Stability constants, evaluated by UV-visible spectrophotometry in MeOH/H 2 O solutions, confirm the selectivity of ligands toward actinides(III) with respect to lanthanides(III). Associate to nuclear magnetic resonance experiments and DFT calculations (Density Functional Theory), a better knowledge of their coordination mode was achieved. (author)

  11. Recent development in computational actinide chemistry

    International Nuclear Information System (INIS)

    Li Jun

    2008-01-01

    Ever since the Manhattan project in World War II, actinide chemistry has been essential for nuclear science and technology. Yet scientists still seek the ability to interpret and predict chemical and physical properties of actinide compounds and materials using first-principle theory and computational modeling. Actinide compounds are challenging to computational chemistry because of their complicated electron correlation effects and relativistic effects, including spin-orbit coupling effects. There have been significant developments in theoretical studies on actinide compounds in the past several years. The theoretical capabilities coupled with new experimental characterization techniques now offer a powerful combination for unraveling the complexities of actinide chemistry. In this talk, we will provide an overview of our own research in this field, with particular emphasis on applications of relativistic density functional and ab initio quantum chemical methods to the geometries, electronic structures, spectroscopy and excited-state properties of small actinide molecules such as CUO and UO 2 and some large actinide compounds relevant to separation and environment science. The performance of various density functional approaches and wavefunction theory-based electron correlation methods will be compared. The results of computational modeling on the vibrational, electronic, and NMR spectra of actinide compounds will be briefly discussed as well [1-4]. We will show that progress in relativistic quantum chemistry, computer hardware and computational chemistry software has enabled computational actinide chemistry to emerge as a powerful and predictive tool for research in actinide chemistry. (authors)

  12. Simulations of the Thermodynamic and Diffusion Properties of Actinide Oxide Fuel Materials

    International Nuclear Information System (INIS)

    Becker, Udo

    2013-01-01

    Spent nuclear fuel from commercial reactors is comprised of 95-99 percent UO 2 and 1-5 percent fission products and transuranic elements. Certain actinides and fission products are of particular interest in terms of fuel stability, which affects reprocessing and waste materials. The transuranics found in spent nuclear fuels are Np, Pu, Am, and Cm, some of which have long half- lives (e.g., 2.1 million years for 237 Np). These actinides can be separated and recycled into new fuel matrices, thereby reducing the nuclear waste inventory. Oxides of these actinides are isostructural with UO 2 , and are expected to form solid solutions. This project will use computational techniques to conduct a comprehensive study on thermodynamic properties of actinide-oxide solid solutions. The goals of this project are to: Determine the temperature-dependent mixing properties of actinide-oxide fuels; Validate computational methods by comparing results with experimental results; Expand research scope to complex (ternary and quaternary) mixed actinide oxide fuels. After deriving phase diagrams and the stability of solid solutions as a function of temperature and pressure, the project team will determine whether potential phase separations or ordered phases can actually occur by studying diffusion of cations and the kinetics of potential phase separations or ordered phases. In addition, the team will investigate the diffusion of fission product gases that can also have a significant influence on fuel stability. Once the system has been established for binary solid solutions of Th, U, Np, and Pu oxides, the methodology can be quickly applied to new compositions that apply to ternaries and quaternaries, higher actinides (Am, Cm), burnable poisons (B, Gd, Hf), and fission products (Cs, Sr, Tc) to improve reactivity

  13. The reprocessing-recycling of spent nuclear fuel. Actinides separation - Application to wastes management

    International Nuclear Information System (INIS)

    2008-01-01

    After its use in the reactor, the spent fuel still contains lot of recoverable material for an energetic use (uranium, plutonium), but also fission products and minor actinides which represent the residues of nuclear reactions. The reprocessing-recycling of the spent fuel, as it is performed in France, implies the chemical separation of these materials. The development and the industrial implementation of this separation process represent a major contribution of the French science and technology. The reprocessing-recycling allows a good management of nuclear wastes and a significant saving of fissile materials. With the recent spectacular rise of uranium prices, this process will become indispensable with the development of the next generation of fast neutron reactors. This book takes stock of the present and future variants of the chemical process used for the reprocessing of spent fuels. It describes the researches in progress and presents the stakes and recent results obtained by the CEA. content: the separation of actinides, a key factor for a sustainable nuclear energy; the actinides, a discovery of the 20. century; the radionuclides in nuclear fuels; the aquo ions of actinides; some redox properties of actinides; some complexing properties of actinide cations; general considerations about treatment processes; some characteristics of nuclear fuels in relation with their reprocessing; technical goals and specific constraints of the PUREX process; front-end operations of the PUREX process; separation and purification operations of the PUREX process; elaboration of finite products in the framework of the PUREX process; management and treatment of liquid effluents; solid wastes of the PUREX process; towards a joint management of uranium and plutonium: the COEX TM process; technical options of treatment and recycling techniques; the fuels of generation IV reactors; front-end treatment processes of advanced fuels; hydrometallurgical processes for future fuel cycles

  14. Partnew - New solvent extraction processes for minor actinides - final report; Partnew - Nouveaux procedes d'extraction par solvant pour les actinides mineurs - rapport final

    Energy Technology Data Exchange (ETDEWEB)

    Madic, C.; Testard, F.; Hudson, M.J.; Liljenzin, J.O.; Christiansen, B.; Ferrando, M.; Facchini, A.; Geist, A.; Modolo, G.; Gonzalez-Espartero, A.; Mendoza, J. de

    2004-07-01

    The objectives of the European project PARTNEW were to define solvent extraction processes for the partitioning of the minor actinides, Am and Cm, from the aqueous high active raffinate or high active concentrate issuing the reprocessing of nuclear spent fuels by the PUREX process. Eleven laboratories participated to the research: 1/ CEA-DEN (Marcoule), 2/ CEA-DSM (Saclay), 3/ UREAD (U.K.), 4/ CTU (Sweden), 5/ ITU (Germany), 6/ ENEA (Italy), 7/ PoliMi (Italy), 8/ FZK-INE (Germany), 9/ FZJ-ISR (Germany), 10/ CIEMAT (Spain) and 11/ UAM (Spain). The research was organised into eight work packages (WP): Basic and applied DIAMEX studies, using diamide extractants for the co-extraction of actinides(III) (An(III)) and lanthanides(III) (Ln(III)) nitrates (WP1 and WP2), Basic and applied SANEX studies based on the use of polydentate N-ligands for the An(III)/Ln(III) separation (WP3 and WP4), Basic and applied SANEX studies based on the use of synergistic mixtures made of bis-(chloro-phenyl)-di-thio-phosphinic acid + neutral O-bearing ligand, (WP5 and WP6), Basic SANEX studies for the An(III)/Ln(III) separation, based on the use of new S-bearing ligands, Basic and applied studies for the Am(III)/Cm(III) separation. The work done in the fundamental and applied domains was very fruitful. Several processes have been successfully tested with genuine high active raffinates and concentrate. (authors)

  15. MICROBIAL IMPACTS ON THE MIGRATION OF ACTINIDES -EFFECTS OF EXUDATES ON ADSORPTION-

    International Nuclear Information System (INIS)

    OHNUKI, T.; OZAKI, T.; YOSHIDA, T.; NANKAWA, T.; KOZAI, N.; SAKAMOTO, F.; SUZUKI, Y.; FRANCIS, A.J.

    2006-01-01

    The interaction of actinides with microorganisms has been extensively studied to elucidate migration behavior of actinides in the environments. However, the mechanisms of interaction of microorganisms and actinides are poorly understood. They have been conducting basic science on microbial accumulation of actinides in order to elucidate the environmental behavior of actinides under relevant conditions. The effect of exudates from bacteria cells on the sorption of Eu(III) and Cm(III) by Chlorella vulgaris was studied by a batch method. The pH dependence of log K d of Eu(III) and Cm(III) for cellulose, major component of C. vulgaris cell, differed from that for C. vulgaris. On the contrary, log K d of Eu(III) and Cm(III) for cellulose in the solution containing exudates from C. vulgaris cells in a 0.5% NaCl solution showed a similar pH dependence to that by C. vulgaris. These results strongly suggested that exudates affect on the sorption of Eu(III) and Cm(III) on C. vulgaris. Effect of desferrioxamine B (DFO), one of exudates to chelate the insoluble Fe(III), on the sorption of Pu(IV), Th(IV) and Eu(III) by Pseudomonas fluorescens was studied. In the presence of DFO the sorption of Pu(IV), Th(IV) and Eu(III) on the cells increased with a decrease in pH from 7 to 4. In contrast, without DFO most of Pu(IV), Th(IV) and Eu(III) were precipitated from solution. Adsorption of DFO on the cells was negligible in the solution with and without metals. Adsorption of Pu(IV), Th(IV) and Eu(III) on P. fluorescens cells decreased in the order Eu(III) > Th(IV) > Pu(IV), which corresponds to increasing stability constant of the DFO complexes. These results indicate that Th(IV), Pu(IV) and Eu(III) dissociate when in contact with cells, after which the metals are adsorbed

  16. Microbial impacts on the migration of actinides. Effects of exudates on adsorption

    International Nuclear Information System (INIS)

    Ohnuki, Toshihiko; Ozaki, Takuo; Nakawa, Takuya; Kozai, Naofumi; Sakamoto, Fuminori; Suzuki, Yosinori; Yoshida, Takahiro; Francis, Arokiasamy J.

    2007-01-01

    The interaction of actinides with microorganisms has been extensively studied to elucidate migration behavior of actinides in the environments. However, the mechanisms of interaction of microorganisms and actinides are poorly understood. We have been conducting basic science on microbial accumulation of actinides in order to elucidate the environmental behavior of actinides under relevant conditions. The effect of exudates from bacteria cells on the sorption of Eu(III) and Cm(III) by Chlorella vulgaris was studied by a batch method. The pH dependence of log K d of Eu(III) and Cm(III) for cellulose, major component of C. vulgaris cell, differed from that for C. vulgaris. On the contrary, log K d of Eu(III) and Cm(III) for cellulose in the solution containing exudates from C. vulgaris cells in a 0.5% NaCl solution showed a similar pH dependence to that by C. vulgaris. These results strongly suggested that exudates affect on the sorption of Eu(III) and Cm(III) on C. vulgaris. Effect of desferrioxamine B (DFO), one of exudates to chelate with insoluble Fe(III), on the sorption of Pu(IV), Th(IV) and Eu(III) by Pseudomonas fluorescens was studied. In the presence of DFO the sorption of Pu(IV), Th(IV) and Eu(III) on the cells increased with a decrease in pH from 7 to 4. In contrast, without DFO most of Pu(IV), Th(IV) and Eu(III) were precipitated from solution. Adsorption of DFO on the cells was negligible in the solution with and without metals. Adsorption of Pu(IV), Th(IV) and Eu(III) on P. fluorescens cells decreased in the order Eu(III) > Th(IV) > Pu(IV), which corresponds to increasing stability constant of the DFO complexes. These results indicate that Th(IV), Pu(IV) and Eu(III) dissociate when in contact with cells, after which the metals are adsorbed. (author)

  17. Structural and thermodynamic study of rare earth(III) complexation by poly-hydroxylated carboxylic acids: synthesis of new extractants and outlook for the extraction of these cations; Etude structurale et thermodynamique de la complexation de lanthanides (III) par des acides carboxyliques polyhydroxyles: synthese de nouveaux extractants et perspectives pour l'extraction de ces cations

    Energy Technology Data Exchange (ETDEWEB)

    Aury, S

    2002-12-15

    The aim of this work is: to improve the knowledge on the binding sites of the poly-hydroxylated carboxylic acids with the trivalent lanthanide(III) ions by comparing them to gluconic acid (previously studied) and to molecules with different configuration and with a variable number of OH functions (threonic acid, glyceric acid, 2-hydroxy-butanoic acid, 3-hydroxy-butanoic acid). To find the best complexing agent among different acids (aldonic acids, aldaric acids, di-hydroxybenzoic acids) (determination of the set of complexes and their stability constants by potentiometry, NMR and UV-Visible spectroscopy). To synthesize hydrophobic monoamides from one lactone form of saccharic acid, to study their complexing power and their capacity to extract the trivalent lanthanide(III) ions. (author)

  18. Actinide recovery techniques utilizing electromechanical processes

    International Nuclear Information System (INIS)

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

    1994-01-01

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

  19. Actinide recovery techniques utilizing electromechanical processes

    International Nuclear Information System (INIS)

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

    1994-01-01

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

  20. Curso de análisis cualitativo inorgánico. Sistemática de identificación de cationes en disolución. Ejercicio interactivo III.

    OpenAIRE

    Milla González, Miguel

    2016-01-01

    Se muestra en este ejercicio de análisis cualitativo los pasos necesarios para identificar los cationes Ca, Ba y Pb(II) en disolución. De estos tres cationes, solo Pb(II) da un sulfuro negro lo que hace fácil su detección. Para analizar los cationes alcalinotérreos es necesario primero eliminar el plomo del precipitado de sulfatos. Ca se extrae de este precipitado con agua fría. Para llevar a cabo el ensayo del bario, es importante eliminar los dos cationes anteriores y disolver el sulfato de...

  1. Analytical evaluation of actinide sensitivities

    International Nuclear Information System (INIS)

    Sola, A.

    1977-01-01

    The analytical evaluation of the sensitivities of actinides to various parameters such as cross sections, decay constants, flux and time is presented. The formulae are applied to isotopes of the Uranium, Neptunium, Plutonium and Americium series. The agreement between analytically obtained and computer evaluated sensitivities being always good, it is throught that the formulation includes all the important parameters entering in the evaluation of sensitivities. A study of the published data is made

  2. Interface reactions of actinides on muscovite; Grenzflaechenreaktionen von Actiniden an Muskovit

    Energy Technology Data Exchange (ETDEWEB)

    Hellebrandt, Stefan

    2017-11-06

    adsorbed U was detected at the muscovite interface according to all methods applied, despite the larger concentration of the adsorbate. This difference in the sorption behavior can be explained by the different redox behavior of U and Pu. U will stay mainly in its predominant oxidation state VI, due to its higher stability compared to Pu, while Pu will be present as Pu(VI), but also in a greater extent in its reduced oxidation states. Due to this difference Pu is able to form nanoparticles, whereas this is not the case for U. The third part compares the sorption of trivalent actinides Am(III) and Cm(III) and their homolog Eu(III) on alumino-silicates muscovite (phyllosilicate) and orthoclase (framework silicate). Under acidic conditions all elements adsorb as outer-sphere complexes, while the relative amount of inner-sphere sorption increases with increasing pH. At higher pH a transition from adsorbed aquoions to adsorbed hydrolysis-species and eventually a ternary sorption complex is observed. While TRLFS itself is a strong tool to investigate the speciation of metals in solution or in contact with a mineral surface the complementary use of SXS techniques is able to improve these findings. The results of this work, achieved by using modern methods such as X-ray scattering techniques (CTR/RAXR) and TRLFS, have afforded new insights into the surface reactivity of a wide range of actinides (Th, U, Pu, Am, and Cm) in contact with muscovite and orthoclase. New influence factors could be identified in the influence of the background electrolyte on the sorption behavior, where both cation and anion affect the actinide's retention. The different redox behavior of redox-active actinides like U and Pu also influenced the sorption behavior tremendously, even in contact with the redox-inactive mineral muscovite. The complementary use of surface X-ray diffraction and laser spectroscopic methods was instrumental to enable us to investigate the distribution, occupancy, and

  3. Solid-state actinide acid phosphites from phosphorous acid melts

    International Nuclear Information System (INIS)

    Oh, George N.; Burns, Peter C.

    2014-01-01

    The reaction of UO 3 and H 3 PO 3 at 100 °C and subsequent reaction with dimethylformamide (DMF) produces crystals of the compound (NH 2 (CH 3 ) 2 )[UO 2 (HPO 2 OH)(HPO 3 )]. This compound crystallizes in space group P2 1 /n and consists of layers of uranyl pentagonal bipyramids that share equatorial vertices with phosphite units, separated by dimethylammonium. In contrast, the reaction of phosphorous acid and actinide oxides at 210 °C produces a viscous syrup. Subsequent dilution in solvents and use of standard solution-state methods results in the crystallization of two polymorphs of the actinide acid phosphites An(HPO 2 OH) 4 (An=U, Th) and of the mixed acid phosphite–phosphite U(HPO 3 )(HPO 2 OH) 2 (H 2 O)·2(H 2 O). α- and β-An(HPO 2 OH) 4 crystallize in space groups C2/c and P2 1 /n, respectively, and comprise a three-dimensional network of An 4+ cations in square antiprismatic coordination corner-sharing with protonated phosphite units, whereas U(HPO 3 )(HPO 2 OH) 2 (H 2 O) 2 ·(H 2 O) crystallizes in a layered structure in space group Pbca that is composed of An 4+ cations in square antiprismatic coordination corner-sharing with protonated phosphites and water ligands. We discuss our findings in using solid inorganic reagents to produce a solution-workable precursor from which solid-state compounds can be crystallized. - Graphical abstract: Reaction of UO 3 and H 3 PO 3 at 100 °C and subsequent reaction with DMF produces crystals of (NH 2 (CH 3 ) 2 )[UO 2 (HPO 2 OH)(HPO 3 )] with a layered structure. Reaction of phosphorous acid and actinide oxides at 210 °C produces a viscous syrup and further solution-state reactions result in the crystallization of the actinide acid phosphites An(HPO 2 OH) 4 (An=U, Th), with a three-dimensional network structure, and the mixed acid phosphite–phosphite U(HPO 3 )(HPO 2 OH) 2 (H 2 O) 2 ·(H 2 O) with a layered structure. - Highlights: • U(VI), U(IV) and Th(IV) phosphites were synthesized by solution

  4. Coordination chemistry of several radius-sensitive complexones and applications to lanthanide-actinide separations

    Energy Technology Data Exchange (ETDEWEB)

    Potter, M.W.

    1981-10-01

    The relationships between the lanthanide complex formation equilibria and the lanthanide-actinide separation application of three radius sensitive ligands have been studied. The consecutive stepwise formation constants of the 1:1, 2:1, and 3:1 chelate species formed by the interaction of DHDMB and the tripositive lanthanides and yttrium were determined potentiometrically at 0.1 M ionic strength and 25/sup 0/C. Results indicate that three different coordination modes, one tridentate and two bidentate are in evidence. Tracer level /sup 241/Am - /sup 155/Eu cation-exchange experiments utilizing DHDMB eluents indicate that this dihydroxycarboxylate does not form a sufficiently strong americium complex to elute that actinide ahead of europium. The overall stability of the americium 3:1 complex appears intermediate between samarium and europium. Cation-exchange elutions of /sup 241/Am, /sup 155/Eu, and /sup 160/Tb mixtures with EEDTA solutions prove that the EEDTA ligand is capable of eluting americium ahead of all of the tripositive lanthanide cations. The minimum separation occurs with terbium, where the Am-Tb separation factor is 1.71. 1,5-diaminopentane-N,N,N',N'-tetraacetic acid (PMDTA) was synthesized using cation exchange. A mathematical method was developed for the formation constants of the protonated and unprotonated lanthanide-PMDTA complexes from potentiometry. Cation-exchange elutions of tracer quantities of Am, Eu, and Tb revealed that terbium is eluted ahead of both americium and europium.

  5. Speciation of actinides in aqueous solution by time-resolved laser-induced fluorescence spectroscopy (TRLFS)

    International Nuclear Information System (INIS)

    Kimura, Takaumi; Kato, Yoshiharu; Meinrath, G.; Yoshida, Zenko; Choppin, G.R.

    1995-01-01

    Time-resolved laser-induced fluorescence spectroscopy (TRLFS) as a sensitive and selective method has been applied to the speciation of actinides in aqueous solution. Studies on hydrolysis and carbonate complexation of U(VI) and on determination of hydration number of Cm(III) are reported. (author)

  6. Research on the chemical speciation of actinides

    International Nuclear Information System (INIS)

    Jung, Euo Chang; Park, K. K.; Cho, H. R.

    2012-04-01

    A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using highly sensitive and advanced laser-based spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been applied for the chemical speciation of actinide in aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. Development of TRLFS technology for the chemical speciation of actinides, Development of laser-induced photo-acoustic spectroscopy (LPAS) system, Application of LIBD technology to investigate dynamic behaviors of actinides dissolution reactions, Development of nanoparticle analysis technology in groundwater using LIBD, Chemical speciation of plutonium complexes by using a LWCC system, Development of LIBS technology for the quantitative analysis of actinides, Evaluation on the chemical reactions between actinides and humic substances, Spectroscopic speciation of uranium-ligand complexes in aqueous solution, Chemical speciation of actinides adsorbed on metal oxides surfaces

  7. Chemistry of actinides and fission products

    International Nuclear Information System (INIS)

    Pruett, D.J.; Sherrow, S.A.; Toth, L.M.

    1988-01-01

    This task is concerned primarily with the fundamental chemistry of the actinide and fission product elements. Special efforts are made to develop research programs in collaboration with researchers at universities and in industry who have need of national laboratory facilities. Specific areas currently under investigation include: (1) spectroscopy and photochemistry of actinides in low-temperature matrices; (2) small-angle scattering studies of hydrous actinide and fission product polymers in aqueous and nonaqueous solvents; (3) kinetic and thermodynamic studies of complexation reactions in aqueous and nonaqueous solutions; and (4) the development of inorganic ion exchange materials for actinide and lanthanide separations. Recent results from work in these areas are summarized here

  8. Chemical interaction of tetravalent actinides simulators and the engineering barrier

    International Nuclear Information System (INIS)

    Chain, Pablo; Alba, Maria D.; Castro, Miguel A.; Pavon, Esperanza; Mar Orta, M.

    2010-01-01

    Document available in extended abstract form only. The Deep Geological Repository (DGR) is the most internationally accepted option for the storage of high radioactive wastes. This confinement is based on the Multi-barrier Concept where the engineered barrier is a crucial safety wise. Nowadays, bentonite is accepted as the best argillaceous material in the engineered barrier of DGR. Additionally to its well-known physical role, a chemical interaction between lutetium, as actinide simulator, and the smectite has been demonstrated. The existence of a reaction mechanism, which was not previously described, based on the chemical interaction between the lanthanide cations and the orthosilicate anions of the lamellar structure has been identified. This finding has aroused the interest of the scientific community because lanthanides are used as simulators of high activity radionuclide (HAR) in agreement with the guidelines established in the bibliography. It has been observed that in conditions of moderate temperature and pressure a chemical interaction exists between smectites and rare earth elements (RE) and phases of insoluble di-silicate, RE 2 Si 2 O 7 , which would immobilize RE, are generated. It is remarkable that the reaction extends to all the set of the smectites, although they do not display the same reactivity, the saponite being the most reactive. The main isotopes present in the HLW belong to the actinide elements Np, Pu, Am and Cm, in addition to uranium generated by neutron capture during the fuel combustion process. The study of the mobilization of actinide (IV) thorough the bentonite barrier is limited because of their radioactivity. However, U(IV), Np(IV), Pu(IV) and Th(IV) can be simulated by the stable isotopes of the Zr(IV) and Hf(IV), because they exhibit ionic radius and physicochemical properties very similar to those of the actinide elements. It is the main objective of this research to investigate the chemical interaction of Zr(IV) as actinide

  9. Synthesis and evaluation structure/extracting and complexing properties of new bi-topic ligands for group actinides extraction

    International Nuclear Information System (INIS)

    Bisson, J.

    2011-01-01

    The aim of this project is to design and study new extractants for spent nuclear fuel reprocessing. To decrease the long-term radiotoxicity of the waste, the GANEX process is an option to homogeneously recycle actinides. All actinides (U, Np, Pu, Am, Cm) would be extracted together from a highly acidic media and separated from fission products (especially from lanthanides). In this context, fourteen new bi-topic ligands constituted of a nitrogen poly-aromatic unit from the dipyridyl-phenanthroline and dipyridyl-1,3,5-triazine families and functionalized by amid groups were synthesized. Extraction studies performed with some of these ligands confirmed their interest to selectively separate actinides at different oxidation states from an aqueous solution 3M HNO 3 . To determine the influence of ligands structure on cation complexation, a study in a homogenous media (MeOH/H 2 O) has been carried out. Electro-spray ionization mass spectrometry have been used to characterize the complexes stoichiometries formed with several cations (Eu 3+ , Nd 3+ , Am 3+ , Pu 4+ and NpO 2 + ). Stability constants, evaluated by UV-Visible spectrophotometry, confirm the selectivity of these ligands toward actinides. Lanthanides and actinides complexes have also been characterized in the solid state by infra-red spectroscopy and X-Ray diffraction. Associated to nuclear magnetic resonance experiments and DFT calculations (Density Functional Theory), a better knowledge of their coordination mode was achieved. (author) [fr

  10. Minor Actinide Separations Using Ion Exchangers Or Ionic Liquids

    International Nuclear Information System (INIS)

    Hobbs, D.; Visser, A.; Bridges, N.

    2011-01-01

    This project seeks to determine if (1) inorganic-based ion exchange materials or (2) electrochemical methods in ionic liquids can be exploited to provide effective Am and Cm separations. Specifically, we seek to understand the fundamental structural and chemical factors responsible for the selectivity of inorganic-based ion-exchange materials for actinide and lanthanide ions. Furthermore, we seek to determine whether ionic liquids can serve as the electrolyte that would enable formation of higher oxidation states of Am and other actinides. Experiments indicated that pH, presence of complexants and Am oxidation state exhibit significant influence on the uptake of actinides and lanthanides by layered sodium titanate and hybrid zirconium and tin phosphonate ion exchangers. The affinity of the ion exchangers increased with increasing pH. Greater selectivity among Ln(III) ions with sodium titanate materials occurs at a pH close to the isoelectric potential of the ion exchanger. The addition of DTPA decreased uptake of Am and Ln, whereas the addition of TPEN generally increases uptake of Am and Ln ions by sodium titanate. Testing confirmed two different methods for producing Am(IV) by oxidation of Am(III) in ionic liquids (ILs). Experimental results suggest that the unique coordination environment of ionic liquids inhibits the direct electrochemical oxidation of Am(III). The non-coordinating environment increases the oxidation potential to a higher value, while making it difficult to remove the inner coordination of water. Both confirmed cases of Am(IV) were from the in-situ formation of strong chemical oxidizers.

  11. EUROPART: an European integrated project on actinide partitioning

    International Nuclear Information System (INIS)

    Madic, C.; Baron, P.; Hudson, M.J.

    2006-01-01

    Full text of publication follows: The EUROPART project is a scientific integrated project between 24 European partners, from 10 countries, mostly funded by the European Community within the FP6, together with CRIEPI from Japan and ANSTO from Australia. EUROPART aims at developing chemical partitioning processes for the so-called minor actinides (MA) contained in nuclear wastes, i.e. from Am to Cf. In the case of the treatment of dedicated spent fuels or targets, the actinides to be separated also include U, Pu and Np. The techniques considered for the separation of these radionuclides belong to the fields of hydrometallurgy and pyrometallurgy, as in the previous European FP5 programs named PARTNEW, CALIXPART and PYROREP, respectively. The two main axes of research within EUROPART are: 1/ the partitioning of MA (from Am to Cf) from wastes issuing from the reprocessing of high burn-up UOX fuels and multi-recycled MOX fuels, 2/ the partitioning of the whole actinide family of elements for recycling, as an option for advanced dedicated fuel cycles (this work will be connected to the studies to be performed within the EUROTRANS European integrated project). In hydrometallurgy, the research is organized in five Work Packages (WP). Four are dedicated to the study of partitioning methods mainly based on the use of solvent extraction methods and of solid extractants, one WP is dedicated to the development of actinide co-conversion methods for fuel or target preparations. The research in pyrometallurgy is organized into four WPs, listed hereafter: (i) study of the basic chemistry of transuranium elements and of some fission products in molten salts (chlorides, fluorides), (ii) development of actinide partitioning methods, (iii) study of the conditioning of the salt wastes, (iv) system studies. Moreover, a strong management team is concerned not only with the technical and financial issues arising from EUROPART, but also with information, communication and benefits for Europe

  12. Analysis of large soil samples for actinides

    Science.gov (United States)

    Maxwell, III; Sherrod, L [Aiken, SC

    2009-03-24

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

  13. Burn of actinides in MOX fuel cells

    International Nuclear Information System (INIS)

    Martinez C, E.; Ramirez S, J. R.; Alonso V, G.

    2017-09-01

    The spent fuel from nuclear reactors is stored temporarily in dry repositories in many countries of the world. However, the main problem of spent fuel, which is its high radio-toxicity in the long term, is not solved. A new strategy is required to close the nuclear fuel cycle and for the sustain ability of nuclear power generation, this strategy could be the recycling of plutonium to obtain more energy and recycle the actinides generated during the irradiation of the fuel to transmute them in less radioactive radionuclides. In this work we evaluate the quantities of actinides generated in different fuels and the quantities of actinides that are generated after their recycling in a thermal reactor. First, we make a reference calculation with a regular enriched uranium fuel, and then is changed to a MOX fuel, varying the plutonium concentrations and determining the quantities of actinides generated. Finally, different amounts of actinides are introduced into a new fuel and the amount of actinides generated at the end of the fuel burn is calculated, in order to determine the reduction of minor actinides obtained. The results show that if the concentration of plutonium in the fuel is high, then the production of minor actinides is also high. The calculations were made using the cell code CASMO-4 and the results obtained are shown in section 6 of this work. (Author)

  14. Environmental chemistry of the actinide elements

    International Nuclear Information System (INIS)

    Rao Linfeng

    1986-01-01

    The environmental chemistry of the actinide elements is a new branch of science developing with the application of nuclear energy on a larger and larger scale. Various aspects of the environmental chemistry of the actinide elements are briefly reviewed in this paper, such as its significance in the nuclear waste disposal, its coverage of research fields and possible directions for future study

  15. Calculated Atomic Volumes of the Actinide Metals

    DEFF Research Database (Denmark)

    Skriver, H.; Andersen, O. K.; Johansson, B.

    1979-01-01

    The equilibrium atomic volume is calculated for the actinide metals. It is possible to account for the localization of the 5f electrons taking place in americium.......The equilibrium atomic volume is calculated for the actinide metals. It is possible to account for the localization of the 5f electrons taking place in americium....

  16. Minor Actinides Recycling in PWRs

    International Nuclear Information System (INIS)

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

    2006-01-01

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

  17. PIE analysis for minor actinide

    International Nuclear Information System (INIS)

    Suyama, Kenya

    2005-01-01

    Minor actinide (MA) is generated in nuclear fuel during the operation of power reactor. For fuel design, reactivity decrease due to it should be considered. Out of reactors, MA plays key role to define the property of spent fuel (SF) such as α-radioactivity, neutron emission rate, and criticality of SF. In order to evaluate the calculation codes and libraries for predicting the amount of MA, comparison between calculation results and experimentally obtained data has been conducted. In this report, we will present the status of PIE data of MA taken by post irradiation examinations (PIE) and several calculation results. (author)

  18. Review of actinide decorporation with chelating agents

    Energy Technology Data Exchange (ETDEWEB)

    Ansoborlo, E. [CEA Valrho, Dir. de l' Energie Nucleaire (DEN/DRCP/CETAMA), 30 - Marcoule (France); Amekraz, B.; Moulin, Ch. [CEA Saclay, Dept. de Physico-Chimie (DEN/DPC/SECR), 91 - Gif sur Yvette (France); Moulin, V. [CEA Saclay, Dir. du Developpement et de l' Innovation Nucleares (DEN/DDIN/MR), 91 - Gif Sur Yvette (France); Taran, F. [CEA Saclay (DSV/DBJC/SMMCB), 91 - Gif-sur-Yvette (France); Bailly, Th.; Burgada, R. [Centre National de la Recherche Scientifique (CNRS/LCSB/UMR 7033), 93 - Bobigny (France); Henge-Napoli, M.H. [CEA Valrho, Site de Marcoule (INSTN), 30 (France); Jeanson, A.; Den Auwer, Ch.; Bonin, L.; Moisy, Ph. [CEA Valrho, Dir. de l' Energie Nucleaire (DEN/DRCP/SCPS), 30 - Marcoule (France)

    2007-10-15

    In case of accidental release of radionuclides in a nuclear facility or in the environment, internal contamination (inhalation, ingestion or wound) with actinides represents a severe health risk to human beings. It is therefore important to provide effective chelation therapy or decorporation to reduce acute radiation damage, chemical toxicity, and late radiation effects. Speciation governs bioavailability and toxicity of elements and it is a prerequisite tool for the design and success of new ligands or chelating agents. The purpose of this review is to present the state-of-the-art of actinide decorporation within biological media, to recall briefly actinide metabolism, to list the basic constraints of actinide-ligand for development, to describe main tools developed and used for decorporation studies, to review mainly the chelating agents tested for actinides, and finally to conclude on the future trends in this field. (authors)

  19. Catalytic Organic Transformations Mediated by Actinide Complexes

    Directory of Open Access Journals (Sweden)

    Isabell S. R. Karmel

    2015-10-01

    Full Text Available This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.

  20. Ammonium diphosphitoindate(III

    Directory of Open Access Journals (Sweden)

    Farida Hamchaoui

    2013-04-01

    Full Text Available The crystal structure of the title compound, NH4[In(HPO32], is built up from InIII cations (site symmetry 3m. adopting an octahedral environment and two different phosphite anions (each with site symmetry 3m. exhibiting a triangular–pyramidal geometry. Each InO6 octahedron shares its six apices with hydrogen phosphite groups. Reciprocally, each HPO3 group shares all its O atoms with three different metal cations, leading to [In(HPO32]− layers which propagate in the ab plane. The ammonium cation likewise has site symmetry 3m.. In the structure, the cations are located between the [In(HPO32]− layers of the host framework. The sheets are held together by hydrogen bonds formed between the NH4+ cations and the O atoms of the framework.

  1. Preparation of minor actinides targets or blankets by the means of Ionic Exchange Resin

    Energy Technology Data Exchange (ETDEWEB)

    Picart, S.; Mokhtari, H.; Ramiere, I.; Jobelin, I. [CEA, Nuclear Energy Division, RadioChemistry and Process Department, Actinides Chemistry Laboratory, BP17171, Bagnols-sur-Ceze, 30207 (France)

    2009-06-15

    The objective of our R and D work is the elaboration by the use of ionic exchange resin of minor actinide precursors for target or blanket dedicated to their transmutation in sodium fast reactor. From the beginning, the resin process called WAR (acronym of Weak Acid Resin) was developed in the 70's at the ORNL for the making of uranium carbide kernels for the high temperature gas reactor [1] [2]. By now, our aim is to extend this concept to the manufacturing of minor actinides oxide mixed with uranium oxides [3]. More precisely, this process can be divided in two major steps: the loading of the resin and the thermal treatment of the fully loaded resin driving either to oxide or carbide phases depending on the gas atmosphere. The difficulty stems from the preparation of the loading solutions which must fulfill precise conditions of pH in presence of actinides cations prone to hydrolysis. Furthermore, the proportions of uranium and minor actinides in solutions must be adjusted to fit the right ratio in the solid. The study presented here will then focus on the experiments and tests which enable us to optimize the fixing of minor actinides on ionic exchange resin and their carbonization in oxide. [1] G. W. Weber, R. L. Beatty et V. J. Tennery, Nuclear Technology, 35, 217-226, (1977), 'Processing and composition control of weak-acid-resin derived fuel microspheres'. [2] K. J. Notz, P. A. Haas, J. H. Shaffer, Radiochimica Acta, 25, 153-160, (1978). 'The preparation of HTGR Fissile Fuel Kernels by Uranium Loading of Ion Exchange Resin'. [3] S. Picart, H. Mokhtari, I. Ramiere, 'Plutonium Futures, The Science 2008', 7-11 july 2008, Dijon, France. 'Modelling of the ionic Exchange between a weak acid resin in its ammonium form and a minor actinide'. (authors)

  2. Phosphonates as alternative to tributyl phosphate for the separation of actinides from fission products

    International Nuclear Information System (INIS)

    Vyas, Chirag K.; Joshirao, Pranav M.; Manchanda, Vijay K.; Rao, C.V.S. Brahmmananda; Jayalakshmi, S.

    2015-01-01

    The present work investigates the role of increase in the basicity of organophosphorus extractant (dialkylalkyl phosphonates) on the uptake of actinides and fission products vis-a-vis tributyl phosphate (TBP), currently employed as a universal extractant. Two dialkylalkyl phosphonates viz. dibutylpropyl phosphonate (DBPrP) and dibutylpentyl phosphonate (DBPeP) were synthesized, characterized and evaluated for their solvent extraction behavior towards U(VI), Th(IV), Eu(III) and Tc(VII) in nitric acid medium ranging from 0.01-6 M. It was observed that increasing the basicity of the phosphoryl oxygen enhanced the uptake of the actinides and the distribution coefficient values were significantly larger as compared to TBP. The limiting organic concentration (LOC) value was estimated for Th(IV) for these extractants and compared with the TBP system. The separation factors of actinides with phosphonates over Tc(VII) are distinctly better than that with TBP.

  3. Subtle interactions and electron transfer between UIII, NpIII, or PuIII and uranyl mediated by the oxo group

    International Nuclear Information System (INIS)

    Arnold, Polly L.; Zegke, Markus; Hollis, Emmalina; Pecharman, Anne-Frederique; Love, Jason B.; Dutkiewicz, Michal S.; Walter, Olaf; Apostolidis, Christos; Magnani, Nicola; Griveau, Jean-Christophe; Colineau, Eric; Caciuffo, Roberto; Zhang, Xiaobin; Schreckenbach, Georg

    2016-01-01

    A dramatic difference in the ability of the reducing An III center in AnCp 3 (An=U, Np, Pu; Cp=C 5 H 5 ) to oxo-bind and reduce the uranyl(VI) dication in the complex [(UO 2 )(THF)(H 2 L)] (L=''Pacman'' Schiff-base polypyrrolic macrocycle), is found and explained. These are the first selective functionalizations of the uranyl oxo by another actinide cation. At-first contradictory electronic structural data are explained by combining theory and experiment. Complete one-electron transfer from Cp 3 U forms the U IV -uranyl(V) compound that behaves as a U V -localized single molecule magnet below 4 K. The extent of reduction by the Cp 3 Np group upon oxo-coordination is much less, with a Np III -uranyl(VI) dative bond assigned. Solution NMR and NIR spectroscopy suggest Np IV U V but single-crystal X-ray diffraction and SQUID magnetometry suggest a Np III -U VI assignment. DFT-calculated Hirshfeld charge and spin density analyses suggest half an electron has transferred, and these explain the strongly shifted NMR spectra by spin density contributions at the hydrogen nuclei. The Pu III -U VI interaction is too weak to be observed in THF solvent, in agreement with calculated predictions. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Molecular and supramolecular speciations of solvent extraction systems based on malonamide and/or dialkyl-phosphoric acids for An(III)/Ln(III); Speciations moleculaire et supramoleculaire de systemes d'extraction liquide-liquide a base de malonamide et/ou d'acides dialkylphosphoriques pour la separation An(III)/Ln(III)

    Energy Technology Data Exchange (ETDEWEB)

    Gannaz, B

    2006-06-15

    The solvent extraction system used in the DIAMEX-SANEX process, developed for the actinide(III)/lanthanide(III) separation, is based on the use of mixtures of the malonamide DMDOHEMA and a dialkyl-phosphoric acid (HDEHP or HDHP), in hydrogenated tetra-propylene. The complexity of these systems urges on a novel approach to improve the conventional methods (thermodynamics, solvent extraction) which hardly explain the macroscopic behaviors observed (3. phase, over-stoichiometry). This approach combines studies on both supramolecular (VPO, SANS, SAXS) and molecular (liquid-liquid extraction, ESI-MS, IR, EXAFS) speciations of single extractant systems (DMDOHEMA or HDHP in in n-dodecane) and their mixture. In spite of safety constraints due to the handling of radio-material, they were used in the studies as much as possible, like for SAXS measurements on americium-containing samples, a worldwide first-time. In each of the investigated systems, actinides(III) and lanthanides(III) are extracted to the organic phase in polar cores of reversed micelles, the inner and outer-sphere compositions of which are proposed. Thus, the 4f and 5f cations are extracted by reversed micelles such as [(DMDOHEMA){sub 2}M(NO{sub 3}){sub 3}]{sub inn} (DMDOHEMA){sub x}(HNO{sub 3}){sub z}(H{sub 2}O){sub w}]{sub out} and M(DHP){sub 3}(HDHP){sub y-3}(H{sub 2}O){sub w} with y = 3 to 6, for the single extractant systems. In the case of the two extractants system, the less concentrated one acts like a co-surfactant regarding the mixed aggregate formation [(DMDOHEMA){sub 2}M(NO{sub 3}){sub 3-v}(DHP){sub v}]{sub inn} [(DMDOFIEMA){sub x}(HDHP){sub y}(HNO{sub 3})z(H{sub 2}O){sub w}]{sub out}. (author)

  5. Trivalent lanthanide/actinide separation in the spent nuclear fuel wastes' reprocessing

    International Nuclear Information System (INIS)

    Narbutt, J.; Krejzler, J.

    2006-01-01

    Separation of trivalent actinides, in particular americium and curium, from lanthanides is an important step in an advanced partitioning process for future reprocessing of spent nuclear fuels. Since the trivalent actinides and lanthanides have similar chemistries, it is rather difficult to separate them from each other. The aim of presented work was to study solvent extraction of Am(III) and Eu(III) in a system containing diethylhemi-BTP (6-(5,6-diethyl-1,2,4-triazin-3-yl)-2,2'-bipyridine) and COSAN (protonated bis(chlorodicarbollido)cobalt(III)). The system was chosen by several groups working in the integrated EC research Project EUROPART. Several physicochemical properties of the extraction system were analyzed and discussed

  6. Modelling thermodynamic properties of lanthanide (LnL)3+ and actinide (AnL)3+ complexes with tridentate planar nitrogen ligands (L)

    International Nuclear Information System (INIS)

    Ionova, G.; Rabbe, C.; Charbonnel, M.C.; Hill, C.; Guillaumont, D.; Guillaumont, R.; Ionov, S.; Madic, C.

    2004-01-01

    We report here the results obtained from a systematic theoretical study on the thermodynamic properties of trivalent lanthanide (Ln) and actinide (An) complexes with chelating nitrogen tridentate ligands. The mechanism of chelation has been investigated and the role of cation dissolution is investigated through a comparison of the thermodynamic properties of solvated cations and complexes. The difference in thermodynamic properties of LnL and AnL complexes is analyzed. (authors)

  7. Partitioning technologies and actinide science: towards pilot facilities in Europe (ACSEPT project)

    International Nuclear Information System (INIS)

    Bourg, S.; Hill, C.; Ouvrier, N.

    2010-01-01

    ACSEPT is an essential contribution to the demonstration, in the long term, of the potential benefits of actinide recycling to minimize the burden on the geological repositories. To succeed, ACSEPT is organized into three technical domains: (i) Considering technically mature aqueous separation processes, ACSEPT works to optimize and select the most promising ones dedicated either to actinide partitioning or to grouped actinide separation. A substantial review was undertaken either to be sure that the right molecule families are being studied, or, on the contrary, to identify new candidates. Results of the first hot tests allowed the validation of some process options. (ii) Concerning pyrochemical separation processes, ACSEPT is focused on the enhancement of the two reference cores of process selected within EUROPART with specific attention to the exhaustive electrolysis in molten chloride (quantitative recovery of the actinides with the lowest amount of fission products) and to actinide back-extraction from an An-Al alloy. R and D efforts are also brought to key scientific and technical issues compulsory for building a complete separation process (head-end steps, salt treatment for recycling and waste management). (iii) By integrating all the experimental results within engineering and systems studies, both in hydro and pyro domains, ACSEPT will deliver relevant flowsheets and recommendations to prepare for future demonstration at a pilot level, in relation with strategies developed through the SNE-TP. In addition, a training and education programme is implemented to share the knowledge among the partitioning community and the future generations of researchers

  8. Swedish-German actinide migration experiment at ÄSPÖ hard rock laboratory

    Science.gov (United States)

    Kienzler, B.; Vejmelka, P.; Römer, J.; Fanghänel, E.; Jansson, M.; Eriksen, T. E.; Wikberg, P.

    2003-03-01

    Within the scope of a bilateral cooperation between Svensk Kärnbränslehantering (SKB) and Forschungszentrum Karlsruhe, Institut für Nukleare Entsorgung (FZK-INE), an actinide migration experiment is currently being performed at the Äspö Hard Rock Laboratory (HRL) in Sweden. This paper covers laboratory and in situ investigations on actinide migration in single-fractured granite core samples. For the in situ experiment, the CHEMLAB 2 probe developed by SKB was used. The experimental setup as well as the breakthrough of inert tracers and of the actinides Am, Np and Pu are presented. The breakthrough curves of inert tracers were analyzed to determine hydraulic properties of the fractured samples. Postmortem analyses of the solid samples were performed to characterize the flow path and the sorbed actinides. After cutting the cores, the abraded material was analyzed with respect to sorbed actinides. The slices were scanned optically to visualize the flow path. Effective volumes and inner surface areas were measured. In the experiments, only breakthrough of Np(V) was observed. In each experiment, the recovery of Np(V) was ≤40%. Breakthrough of Am(III) and Pu(IV) as well as of Np(IV) was not observed.

  9. Ordered perovskites with cationic vacancies. 10. Compounds of type A/sub 2/sup(II)Bsub(1/4)sup(II)Bsub(1/2)sup(III)vacantsub(1/4)Msup(VI)O/sub 6/ equal to A/sub 8/sup(II)Bsup(II)B/sub 2/sup(III)vacantM/sub 4/sup(VI)O/sub 24/ with Asup(II), Bsup(II) = Ba, Sr, Ca and Msup(VI) = U, W

    Energy Technology Data Exchange (ETDEWEB)

    Betz, B; Schittenhelm, H J; Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

    1982-01-01

    Perovskites of type Ba/sub 8/Bsup(II)B/sub 2/sup(III)vacantU/sub 4/sup(VI)O/sub 24/ show polymorphic phase transformations of order disorder type. An 1:1 ordered orthorhombic HT form is transformed into a higher ordered LT modification with a fourfold cell content (four formula units Ba/sub 8/Bsup(II)B/sub 2/sup(III)vacantU/sub 4/O/sub 24/), compared to cubic 1:1 ordered perovskites A/sub 2/BMO/sub 6/. In the series Ba/sub 8/BaB/sub 2/sup(III)vacantW/sub 4/O/sub 24/ and Sr/sub 8/SrB/sub 2/sup(III)vacantW/sub 4/O/sub 24/ different ordering phenomena are observed. In comparison with 1:1 ordered cubic perovskites A/sub 2/BMO/sub 6/, the cell contains eight formula units A/sub 8/sup(II)Bsup(II) B/sub 2/sup(III)vacantW/sub 4/O/sub 2/4. The higher ordered cells with Usup(VI) and Wsup(VI) are face centered, which has its origin in an ordering of cationic vacancies.

  10. Minor actinide transmutation - a waste management option

    International Nuclear Information System (INIS)

    Koch, L.

    1986-01-01

    The incentive to recycle minor actinides results from the reduction of the long-term α-radiological risk rather than from a better utilization of the uranium resources. Nevertheless, the gain in generated electricity by minor actinide transmutation in a fast breeder reactor can compensate for the costs of their recovery and make-up into fuel elements. Different recycling options of minor actinides are discussed: transmutation in liquid metal fast breeder reactors (LMFBRs) is possible as long as plutonium is not recycled in light water reactors (LWRs). In this case a minor actinide burner with fuel of different composition has to be introduced. The development of appropriate minor actinide fuels and their properties are described. The irradiation experiments underway or planned are summarized. A review of minor actinide partitioning from the PUREX waste stream is given. From the present constraints of LMFBR technology a reduction of the long-term α-radiological risk by a factor of 200 is deduced relative to that from the direct storage of spent LWR fuel. Though the present accumulation of minor actinides is low, nuclear transmutation may be needed when nuclear energy production has grown. (orig.)

  11. Criteria for achieving actinide reduction goals

    International Nuclear Information System (INIS)

    Liljenzin, J.O.

    1996-01-01

    In order to discuss various criteria for achieving actinide reduction goals, the goals for actinide reduction must be defined themselves. In this context the term actinides is interpreted to mean plutonium and the so called ''minor actinides'' neptunium, americium and curium, but also protactinium. Some possible goals and the reasons behind these will be presented. On the basis of the suggested goals it is possible to analyze various types of devices for production of nuclear energy from uranium or thorium, such as thermal or fast reactors and accelerator driven system, with their associated fuel cycles with regard to their ability to reach the actinide reduction goals. The relation between necessary single cycle burn-up values, fuel cycle processing losses and losses to waste will be defined and discussed. Finally, an attempt is made to arrange the possible systems on order of performance with regard to their potential to reduce the actinide inventory and the actinide losses to wastes. (author). 3 refs, 3 figs, 2 tabs

  12. Actinides burnup in a sodium fast reactor

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez S, J. R.; Pineda A, R.; Martinez C, E.; Alonso, G., E-mail: ramon.ramirez@inin.gob.mx [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2017-09-15

    The burnup of actinides in a nuclear reactor is been proposed as part of an advanced nuclear fuel cycle, this process would close the fuel cycle recycling some of the radioactive material produced in the open nuclear fuel cycle. These actinides are found in the spent nuclear fuel from nuclear power reactors at the end of their burnup in the reactor. Previous studies of actinides recycling in thermal reactors show that would be possible reduce the amounts of actinides at least in 50% of the recycled amounts. in this work, the amounts of actinides that can be burned in a fast reactor is calculated, very interesting results surge from the calculations, first, the amounts of actinides generated by the fuel is higher than for thermal fuel and the composition of the actinides vector is different as in fuel for thermal reactor the main isotope is the {sup 237}Np in the fuel for fast reactor the main isotope is the {sup 241}Am, finally it is concluded that the fast reactor, also generates important amounts of waste. (Author)

  13. Phase Behavior and Equations of State of the Actinide Oxides

    Science.gov (United States)

    Chidester, B.; Pardo, O. S.; Panero, W. R.; Fischer, R. A.; Thompson, E. C.; Heinz, D. L.; Prescher, C.; Prakapenka, V. B.; Campbell, A.

    2017-12-01

    The distribution of the long-lived heat-producing actinide elements U and Th in the deep Earth has important implications for the dynamics of the mantle and possibly the energy budget of Earth's core. The low shear velocities of the Large Low-Shear Velocity Provinces (LLSVPs) on the core-mantle boundary suggests that these regions are at least partially molten and may contain concentrated amounts of the radioactive elements, as well as other large cations such as the rare Earth elements. As such, by exploring the phase behavior of actinide-bearing minerals at extreme conditions, some insight into the mineralogy, formation, and geochemical and geodynamical effects of these regions can be gained. We have performed in situ high-pressure, high-temperature synchrotron X-ray diffraction experiments and calculations on two actinide oxide materials, UO2 and ThO2, to determine their phase behavior at the extreme conditions of the lower mantle. Experiments on ThO2 reached 60 GPa and 2500 K, and experiments on UO2 reached 95 GPa and 2500 K. We find that ThO2 exists in the fluorite-type structure to 20 GPa at high temperatures, at which point it transforms to the high-pressure cotunnite-type structure and remains thus up to 60 GPa. At room temperature, an anomalous expansion of the fluorite structure is observed prior to the transition, and may signal anion sub-lattice disorder. Similarly, UO2 exists in the fluorite-type structure at ambient conditions and up to 28 GPa at high temperatures. Above these pressures, we have observed a previously unidentified phase of UO2 with a tetragonal structure as the lower-temperature phase and the cotunnite-type phase at higher temperatures. Above 78 GPa, UO2 undergoes another transition or possible dissociation into two separate oxide phases. These phase diagrams suggest that the actinides could exist as oxides in solid solution with other analogous phases (e.g. ZrO2) in the cotunnite-type structure throughout much of Earth's lower mantle.

  14. Specific sequestering agents for iron and the actinides

    Energy Technology Data Exchange (ETDEWEB)

    Raymond, K.N.

    1983-06-01

    The transuranium actinide ions represent one unique environmental hazard associated with the waste of the nuclear power industry. A major component associated with that waste and a potential hazard is plutonium. The synthesis of metal-ion-specific complexing agents for ions such as Pu(IV) potentially represents a powerful new approach to many of the problems posed by waste treatment. This document is a progress report of a rational approach to the synthesis of such chelating agents based on the similarities of Pu(IV) and Fe(III), the structures of naturally-occurring complexing agents which are highly specific for Fe(III), and the incorporation of the same kinds of ligating groups present in the iron complexes to make octadentate complexes highly specific for plutonium. Both thermodynamic and animal test results indicate that a relatively high degree of success has already been achieved in this aim.

  15. Investigation of actinides speciation within the presence of ligands of interest for decorporation

    International Nuclear Information System (INIS)

    Bonin, L.

    2008-01-01

    Data about the behaviour of actinides in biological media are required in order to investigate their decorporation. Those data are obtained through in vivo experiments and the study of chemical speciation of actinides within the presence of biological constituents. A part of this work consists in the development of a method leading to the determination of the speciation of actinides at the oxidation state +IV within the presence of a complexing species, as well as its structure. The method was applied to two types of ligands: 1) a constituent of blood plasma: the citrate anion. The various complexes formed were investigated and their formation constants were quantified. The coordination mode of the ligand was then clarified through a structural study of the complexes, underlining the role of only one carboxylic site and of the alcohol function. 2) chelating agents used for decorporation. The formation constants of complexes of An(IV) with NTA and DTPA were determined. The coordination number of the metallic cation in those complexes as well as the role of the nitrogen atom were proved. Lastly, the behaviour of Pu(IV) within the presence of LIHOPO was investigated. This chelating agent, more efficient than DTPA in the case of in vivo decorporation of Np, forms very stable complexes with the metallic cation. One of those complexes can be assumed to present a stoichiometry 2:3. (author)

  16. Sol-gel chemistry applied to the synthesis of polymetallic oxides including actinides reactivity and structure from solution to solid state

    International Nuclear Information System (INIS)

    Lemonnier, St.

    2006-02-01

    Minor actinides transmutation is studied at present in order to reduce the radiotoxicity of nuclear waste and the assessment of its technical feasibility requires specific designed materials. When considering americium, yttria stabilized zirconia (Am III YII Zriv)Or x is among the ceramic phases that one which presents the required physico-chemical properties. An innovative synthesis of this mixed oxide by sol-gel process is reported in this manuscript. The main aim of this work is to adjust the reactivity of the different metallic cations in aqueous media using complexing agent, in order to initiate a favourable interaction for a homogeneous elements repartition in the forming solid phase. The originality of the settled synthesis lies on an in-situ formation of a stable and monodisperse nano-particles dispersion in the presence of acetylacetone. The main reaction mechanisms have been identified: the sol stabilisation results from an original interaction between the three compounds (Zrly, trivalent cations and acetylacetone). The sol corresponds to a structured system at the nanometer scale for which zirconium and trivalent cations are homogeneously dispersed, preliminary to the sol-gel transition. Furthermore, preliminary studies were carried out with a view to developing materials. They have demonstrated that numerous innovative and potential applications can be developed by taking advantage of the direct and controlled formation of the sol and by adapting the sol-gel transition. The most illustrating result is the preparation of a sintered pellet with the composition Am0,13Zro,73Yo,0901,89 using this approach. (author)

  17. Experimental studies of actinides in molten salts

    International Nuclear Information System (INIS)

    Reavis, J.G.

    1985-06-01

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

  18. Experimental studies of actinides in molten salts

    Energy Technology Data Exchange (ETDEWEB)

    Reavis, J.G.

    1985-06-01

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

  19. Neutron nuclear data evaluation for actinide nucleic

    International Nuclear Information System (INIS)

    Chen Guochang; Yu Baosheng; Duan Junfeng; Ge Zhigang; Cao Wentian; Tang Guoyou; Shi Zhaomin; Zou Yubin

    2010-01-01

    The nuclear data with high accuracy for minor actinides are playing an important role in nuclear technology applications, including reactor design and operation, fuel cycle concepts, estimation of the amount of minor actinides in high burn-up reactors and the minor actinides transmutation. Through describe the class of nuclear data and nuclear date library, and introduce the procedure of neutron nuclear data evaluation. 234 U(n, f) and 237 Np(n, 2n) reaction experimental data evaluation was evaluated. The fission nuclear data are updated and improved. (authors)

  20. Actinide chemistry in the far field

    International Nuclear Information System (INIS)

    Livens, F.R.; Morris, K.; Parkman, R.; Moyes, L.

    1996-01-01

    The environmental chemistry of the actinides is complicated due both to the extensive redox and coordination chemistry of the elements and also to the complexity of the reactive phases encountered in natural environments. In the far field, interactions with reactive surfaces, coatings and colloidal particles will play a crucial role in controlling actinide mobility. By virtue of both their abundance and reactivity; clays and other layer aluminosilicate minerals, hydrous oxides and organic matter (humic substances) are all identified as having the potential to react with actinide ions and some possible modes of interaction are described, together with experimental evidence for their occurrence. (author)

  1. Spin and orbital moments in actinide compounds

    DEFF Research Database (Denmark)

    Lebech, B.; Wulff, M.; Lander, G.H.

    1991-01-01

    The extended spatial distribution of both the transition-metal 3d electrons and the actinide 5f electrons results in a strong interaction between these electron states when the relevant elements are alloyed. A particular interesting feature of this hybridization, which is predicted by single...... experiments designed to determine the magnetic moments at the actinide and transition-metal sublattice sites in compounds such as UFe2, NpCo2, and PuFe2 and to separate the spin and orbital components at the actinide sites. The results show, indeed, that the ratio of the orbital to spin moment is reduced...

  2. Leaching of irradiated polymers: solution characterization and actinides complexation

    International Nuclear Information System (INIS)

    Fromentin, Elodie

    2017-01-01

    The first aim of this work is to study the degradation of an industrial poly-esterurethane (PURm) by radio-oxidation and then by leaching in an alkaline aqueous solution. The second aim is to measure the complexing power of hydro-soluble degradation products (HDP) with actinides. To reach these goals, PURm was first characterized and then radio-oxidized at room temperature with γ rays up to 10 MGy. Second, it was leached at pH 13.3 at different temperature values. Numerous analytical techniques were employed in order to characterize the HDP which were obtained. Europium(III) was used as an analogue of actinides(III) and the behavior of HDP with europium(III) was analyzed by time-resolved luminescence spectroscopy (TRLS). Whatever the dose received by PURm, adipic acid and butane-1,4-diol are the two main HDP in leachates. The leaching data acquired at 40 and 60 C, on the 1 MGy radio-oxidized PURm, correlate with the model given by Yoon et al. (1997). However, the data at room temperature (22 C in average) are not in agreement with the model. Nevertheless, it seems that the plateau which was reached at long-term leaching is the same whatever the temperature used in this study. The results allow to conclude that the predominant mechanism occurring during the leaching of unirradiated and radio-oxidized PURm in an alkaline medium is the hydrolysis of the soft segments ester groups. The complexation of europium(III) by HDP in alkaline medium was demonstrated. The measurement of the complexing power and the identification of ligands was achieved under certain conditions. (author) [fr

  3. Sorption of actinides in granitic rock

    International Nuclear Information System (INIS)

    Allard, B

    1982-11-01

    The sorption of americium (III), neptunium(V) and plutonium on geologic media under oxic conditions has been measured by a batch technique. The aqueous phase was a synthetic groundwater or 4M NaCl solution. The solid phase was a pure mineral, representative of igneous rocks, or granite. Altogether 40 different minerals and rocks were used. The effects of pH and the ionic strength of the aqueous phase as well as of the cation exchange capacity and the surface/mass ratio of the solid sorbent are discussed. Empirical equations giving the distribution coefficient as a function of pH in the environmental pH-range 7-9 are suggested. Some observations and conclusions concerning sorption mechanisms are given. (author)

  4. Lanthanides and actinides extraction by calixarenes containing CMPO groups; Extraction des lanthanides et des actinides au moyen de calixarenes portant des groupements CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Garcia Carrera, A

    2001-07-01

    In the framework of the French program SPIN concerning the radioactive waste management, researches are performed to develop processes allowing the separation of long-lived radioisotopes in order to their transmutation or their specific conditioning. These studies deal with the extraction and the separation of trivalent lanthanides and actinides in acid solution. Many systems ''calixarene-diluent-aqueous phase'' are examined by extraction liquid-liquid and membrane transport. The extraction efficiency and the selectivity of the synthesized calixarene-CMPO and of the CMPO are compared with these cations, as the nitric acid extraction by these molecules. (A.L.B.)

  5. Actinide recovery from pyrochemical residues

    International Nuclear Information System (INIS)

    Avens, L.R.; Clifton, D.G.; Vigil, A.R.

    1984-01-01

    A new process for recovery of plutonium and americium from pyrochemical waste has been demonstrated. It is based on chloride solution anion exchange at low acidity, which eliminates corrosive HCl fumes. Developmental experiments of the process flowsheet concentrated on molten salt extraction (MSE) residues and gave >95% plutonium and >90% americium recovery. The recovered plutonium contained 6 = from high chloride-low acid solution. Americium and other metals are washed from the ion exchange column with 1N HNO 3 -4.8M NaCl. The plutonium is recovered, after elution, via hydroxide precipitation, while the americium is recovered via NaHCO 3 precipitation. All filtrates from the process are discardable as low-level contaminated waste. Production-scale experiments are now in progress for MSE residues. Flow sheets for actinide recovery from electrorefining and direct oxide reduction residues are presented and discussed

  6. Actinide recovery from pyrochemical residues

    International Nuclear Information System (INIS)

    Avens, L.R.; Clifton, D.G.; Vigil, A.R.

    1985-05-01

    We demonstrated a new process for recovering plutonium and americium from pyrochemical waste. The method is based on chloride solution anion exchange at low acidity, or acidity that eliminates corrosive HCl fumes. Developmental experiments of the process flow chart concentrated on molten salt extraction (MSE) residues and gave >95% plutonium and >90% americium recovery. The recovered plutonium contained 6 2- from high-chloride low-acid solution. Americium and other metals are washed from the ion exchange column with lN HNO 3 -4.8M NaCl. After elution, plutonium is recovered by hydroxide precipitation, and americium is recovered by NaHCO 3 precipitation. All filtrates from the process can be discardable as low-level contaminated waste. Production-scale experiments are in progress for MSE residues. Flow charts for actinide recovery from electro-refining and direct oxide reduction residues are presented and discussed

  7. Subsurface interactions of actinide species and microorganisms. Implications for the bioremediation of actinide-organic mixtures

    International Nuclear Information System (INIS)

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

    1999-01-01

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

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

    International Nuclear Information System (INIS)

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

    1999-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-02-12

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

  10. Ordered perovskites with cationic vacancies. 4. Compounds of type Ba/sub 6/B/sub 2/sup(III)vacantTe/sub 3/sup(VI)O/sub 18/

    Energy Technology Data Exchange (ETDEWEB)

    Schittenhelm, H J; Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

    1979-07-01

    Compounds of the composition Ba/sub 6/B(III)/sub 2/vacantTe(VI)/sub 3/O/sub 18/ equivalent to Ba/sub 2/Ba(III)sub(2/3)vacantsub(1/3)Te(VI)O/sub 6/, with B(III) = Pr, Nd, Sm-Lu, Y crystallize with a cubic perovskite lattice. The cell parameters diminish as the size of B(III) falls (B(III) = Pr: a = 8.52 A; Lu: a = 8.33 A). In contrast to the corresponding perovskites with U(VI) and W(VI) no polymorphism is observed.

  11. Sorption Speciation of Lanthanides/Actinides on Minerals by TRLFS, EXAFS and DFT Studies: A Review

    Directory of Open Access Journals (Sweden)

    Xiaoli Tan

    2010-11-01

    Full Text Available Lanthanides/actinides sorption speciation on minerals and oxides by means of time resolved laser fluorescence spectroscopy (TRLFS, extended X-ray absorption fine structure spectroscopy (EXAFS and density functional theory (DFT is reviewed in the field of nuclear disposal safety research. The theoretical aspects of the methods are concisely presented. Examples of recent research results of lanthanide/actinide speciation and local atomic structures using TRLFS, EXAFS and DFT are discussed. The interaction of lanthanides/actinides with oxides and minerals as well as their uptake are also of common interest in radionuclide chemistry. Especially the sorption and inclusion of radionuclides into several minerals lead to an improvement in knowledge of minor components in solids. In the solid-liquid interface, the speciation and local atomic structures of Eu(III, Cm(III, U(VI, and Np(IV/VI in several natural and synthetic minerals and oxides are also reviewed and discussed. The review is important to understand the physicochemical behavior of lanthanides/actinides at a molecular level in the natural environment.

  12. Subtle interactions and electron transfer between U{sup III}, Np{sup III}, or Pu{sup III} and uranyl mediated by the oxo group

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, Polly L.; Zegke, Markus; Hollis, Emmalina; Pecharman, Anne-Frederique; Love, Jason B. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom); Dutkiewicz, Michal S. [EaStCHEM School of Chemistry, University of Edinburgh (United Kingdom); European Commission, Directorate for Nuclear Safety and Security, Joint Research Centre, Karlsruhe (Germany); Walter, Olaf; Apostolidis, Christos; Magnani, Nicola; Griveau, Jean-Christophe; Colineau, Eric; Caciuffo, Roberto [European Commission, Directorate for Nuclear Safety and Security, Joint Research Centre, Karlsruhe (Germany); Zhang, Xiaobin; Schreckenbach, Georg [Department of Chemistry, University of Manitoba, Winnipeg, MB (Canada)

    2016-10-04

    A dramatic difference in the ability of the reducing An{sup III} center in AnCp{sub 3} (An=U, Np, Pu; Cp=C{sub 5}H{sub 5}) to oxo-bind and reduce the uranyl(VI) dication in the complex [(UO{sub 2})(THF)(H{sub 2}L)] (L=''Pacman'' Schiff-base polypyrrolic macrocycle), is found and explained. These are the first selective functionalizations of the uranyl oxo by another actinide cation. At-first contradictory electronic structural data are explained by combining theory and experiment. Complete one-electron transfer from Cp{sub 3}U forms the U{sup IV}-uranyl(V) compound that behaves as a U{sup V}-localized single molecule magnet below 4 K. The extent of reduction by the Cp{sub 3}Np group upon oxo-coordination is much less, with a Np{sup III}-uranyl(VI) dative bond assigned. Solution NMR and NIR spectroscopy suggest Np{sup IV}U{sup V} but single-crystal X-ray diffraction and SQUID magnetometry suggest a Np{sup III}-U{sup VI} assignment. DFT-calculated Hirshfeld charge and spin density analyses suggest half an electron has transferred, and these explain the strongly shifted NMR spectra by spin density contributions at the hydrogen nuclei. The Pu{sup III}-U{sup VI} interaction is too weak to be observed in THF solvent, in agreement with calculated predictions. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. The reprocessing-recycling of spent nuclear fuel. Actinides separation - Application to wastes management; Le traitement-recyclage du combustible nucleaire use. La separation des actinides - Application a la gestion des dechets

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2008-07-01

    After its use in the reactor, the spent fuel still contains lot of recoverable material for an energetic use (uranium, plutonium), but also fission products and minor actinides which represent the residues of nuclear reactions. The reprocessing-recycling of the spent fuel, as it is performed in France, implies the chemical separation of these materials. The development and the industrial implementation of this separation process represent a major contribution of the French science and technology. The reprocessing-recycling allows a good management of nuclear wastes and a significant saving of fissile materials. With the recent spectacular rise of uranium prices, this process will become indispensable with the development of the next generation of fast neutron reactors. This book takes stock of the present and future variants of the chemical process used for the reprocessing of spent fuels. It describes the researches in progress and presents the stakes and recent results obtained by the CEA. content: the separation of actinides, a key factor for a sustainable nuclear energy; the actinides, a discovery of the 20. century; the radionuclides in nuclear fuels; the aquo ions of actinides; some redox properties of actinides; some complexing properties of actinide cations; general considerations about treatment processes; some characteristics of nuclear fuels in relation with their reprocessing; technical goals and specific constraints of the PUREX process; front-end operations of the PUREX process; separation and purification operations of the PUREX process; elaboration of finite products in the framework of the PUREX process; management and treatment of liquid effluents; solid wastes of the PUREX process; towards a joint management of uranium and plutonium: the COEX{sup TM} process; technical options of treatment and recycling techniques; the fuels of generation IV reactors; front-end treatment processes of advanced fuels; hydrometallurgical processes for future fuel

  14. Advanced Aqueous Separation Systems for Actinide Partitioning

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-03-21

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

  15. Electronic structure and correlation effects in actinides

    International Nuclear Information System (INIS)

    Albers, R.C.

    1998-01-01

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

  16. BWR Assembly Optimization for Minor Actinide Recycling

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-03-22

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

  17. Actinide isotopes in the marine environment

    International Nuclear Information System (INIS)

    Holm, E.; Fukai, R.

    1986-01-01

    Studies of actinide isotopes in the environment are important not only from the viewpoint of their radiological effects on human life, but also from the fact that they act as excellent biochemical and geochemical tracers especially in the marine environment. For several of the actinide isotopes there is still a lack of basic data on concentration levels and further investigations on their chemical and physical speciation are required to understand their behaviour in the marine environment. The measured and estimated activity concentration levels of artificial actinides are at present in general a few orders of magnitude lower than those of the natural ones and their concentration factors in biota are relatively low, except in a few species of macroalgae and phytoplankton. The contribution from seafood to total ingestion of actinides by the world population is a few per cent and, therefore, the dose to man from these long-lived radionuclides caused by seafood ingestion is usually low. (orig.)

  18. Robust membrane systems for actinide separations

    International Nuclear Information System (INIS)

    Jarvinen, Gordon D.; McCleskey, T. Mark; Bluhm, Elizabeth A.; Abney, Kent D.; Ehler, Deborah S.; Bauer, Eve; Le, Quyen T.; Young, Jennifer S.; Ford, Doris K.; Pesiri, David R.; Dye, Robert C.; Robison, Thomas W.; Jorgensen, Betty S.; Redondo, Antonio; Pratt, Lawrence R.; Rempe, Susan L.

    2000-01-01

    Our objective in this project is to develop very stable thin membrane structures containing ionic recognition sites that facilitate the selective transport of target metal ions, especially the actinides

  19. Impact of Eu(III) on mammalian cells as a function of its speciation

    Energy Technology Data Exchange (ETDEWEB)

    Sachs, Susanne; Heller, Anne; Geipel, Gerhard; Bernhard, Gert [Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, Bautzner Landstr. 400, 01328 Dresden (Germany)

    2014-07-01

    In the case of the accidental release of long-lived radionuclides, e.g., actinides, into the environment, knowledge of their behavior in bio-systems is necessary to asses and to prevent radiological and chemical induced adverse health effects. This includes knowledge of the bioavailability and chemo-/radio-toxicity of these elements for/onto cells, which are governed to a large extent by their speciation [1,2]. In order to gain a better process understanding, we study the interaction of trivalent actinides/lanthanides with mammalian cells on a cellular level combining biochemical and analytical methods. Results of these studies can contribute to the estimation of low dose effects and the development of new decontamination strategies. The cellular tolerance of FaDu cells (human squamous cell carcinoma cell line) toward Eu(III) as an analog for trivalent actinides as well as its uptake into the cells has been studied as a function of the Eu(III) concentration and nutrient composition. To differentiate between chemo-toxic and radio-toxic effects of Eu(III), {sup 152}Eu (β{sup -}, ε) was applied as radioactive tracer besides europium with natural isotope composition. The Eu(III) speciation in the cell culture media has been investigated by time-resolved laser-induced fluorescence spectroscopy as well as by solubility studies in combination with ultrafiltration, ultracentrifugation, cation and anion analysis. These results are used to correlate cytotoxicity and uptake of Eu(III) on/into the cells with its chemical speciation in the nutrient. Presently, we are studying the interaction of Eu(III) with NRK-52E cells (rat kidney epithelial-like cells). The results of these studies will be discussed and compared to those obtained with FaDu cells. From the studies with FaDu cells it was concluded that the Eu(III) cytotoxicity onto these cells depends on the Eu(III) concentration and is influenced by its chemical speciation. This was also reported, for instance, for the

  20. Local structure near actinides and nucleating elements in borosilicate glass for nuclear industry: Results of X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Petit-Maire, D.

    1988-01-01

    Possibilities and limits of X-ray absorption spectroscopy for cation site description in silicate glasses and possible applications for complex glasses, like glass for fission product containment, are examined. In borosilicate glasses two types of sites are evidenced for actinides at the valence 4: Coordinance 6 sites with a narrow radial distribution for the distance An-0; higher coordination (7, 8 or more) with a wider and asymmetrical radial distribution. Proportion of low coordinance sites increases when cation size decreases (Th > Np). U and Np VI and V are characterized as actinyles with a chain 0-An-0 practically linear, coordinance in a plane perpendicular to this complex is probably 5. X-ray absorption spectroscopy allows an accurate description of actinide sites in fission product glasses [fr

  1. Possible existence of backbending in actinide nuclei

    International Nuclear Information System (INIS)

    Dudek, J.; Nazarewicz, W.; Szymanski, Z.

    1982-01-01

    The possibilities for the backbending effect to occur in actinide nuclei are studied using the pairing-self-consistent independent quasiparticle method. The Hamiltonian used is that of the deformed Woods-Saxon potential plus monopole pairing term. The results of the calculations explain why there is no backbending in most actinide nuclei and simultaneously suggest that in some light neutron deficient nuclei around Th and 22 Ra a backbending effect may occur

  2. Lattice effects in the light actinides

    International Nuclear Information System (INIS)

    Lawson, A.C.; Cort, B.; Roberts, J.A.; Bennett, B.I.; Brun, T.O.; Dreele, R.B. von; Richardson, J.W. Jr.

    1998-01-01

    The light actinides show a variety of lattice effects that do not normally appear in other regions of the periodic table. The article will cover the crystal structures of the light actinides, their atomic volumes, their thermal expansion behavior, and their elastic behavior as reflected in recent thermal vibration measurements made by neutron diffraction. A discussion of the melting points will be given in terms of the thermal vibration measurements. Pressure effects will be only briefly indicated

  3. Transmutation of actinides in power reactors.

    Science.gov (United States)

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

    2005-01-01

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

  4. Predictive Modeling in Actinide Chemistry and Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-05-16

    These are slides from a presentation on predictive modeling in actinide chemistry and catalysis. The following topics are covered in these slides: Structures, bonding, and reactivity (bonding can be quantified by optical probes and theory, and electronic structures and reaction mechanisms of actinide complexes); Magnetic resonance properties (transition metal catalysts with multi-nuclear centers, and NMR/EPR parameters); Moving to more complex systems (surface chemistry of nanomaterials, and interactions of ligands with nanoparticles); Path forward and conclusions.

  5. Subcritical limits for special fissile actinides

    International Nuclear Information System (INIS)

    Clark, H.K.

    1980-01-01

    Critical masses and subcritical mass limits in oxide-water mixtures were calculated for actinide nuclides other than /sup 233/U, /sup 235/U, and /sup 239/Pu that have an odd number of neutrons in the nucleus; S/sub n/ transport theory was used together with cross sections, drawn from the GLASS multigroup library, developed to provide accurate forecasts of actinide production at Savannah River

  6. Proposal for experiments with actinide elements

    International Nuclear Information System (INIS)

    Sanchez, R.G.

    1994-01-01

    An analytical study was conducted in which critical masses for some actinide isotopes were calculated with the Monte Carlo Neutron Photon (MCNP) Transport computer code. Different spherical computer models were used for even- and odd-neutron nuclides. Critical masses obtained are tabulated for Np-237, Pu-242, Am-241, Am-243, Pu-241, and Am-242m, together with indirect experimental data. Experimental data are needed for actinides with odd number of neutrons

  7. Interaction between actinides and protein: the calmodulin

    International Nuclear Information System (INIS)

    Brulfert, Florian

    2016-01-01

    Considering the environmental impact of the Fukushima nuclear accident, it is fundamental to study the mechanisms governing the effects of the released radionuclides on the biosphere and thus identify the molecular processes generating the transport and deposition of actinides, such as neptunium and uranium. However, the information about the microscopic aspect of the interaction between actinides and biological molecules (peptides, proteins...) is scarce. The data being mostly reported from a physiological point of view, the structure of the coordination sites remains largely unknown. These microscopic data are indeed essential for the understanding of the interdependency between structural aspect, function and affinity.The Calmodulin (CaM) (abbreviation for Calcium-Modulated protein), also known for its affinity towards actinides, acts as a metabolic regulator of calcium. This protein is a Ca carrier, which is present ubiquitously in the human body, may also bind other metals such as actinides. Thus, in case of a contamination, actinides that bind to CaM could avoid the protein to perform properly and lead to repercussions on a large range of vital functions.The complexation of Np and U was studied by EXAFS spectroscopy which showed that actinides were incorporated in a calcium coordination site. Once the thermodynamical and structural aspects studied, the impact of the coordination site distortion on the biological efficiency was analyzed. In order to evaluate these consequences, a calorimetric method based on enzyme kinetics was developed. This experiment, which was conducted with both uranium (50 - 500 nM) and neptunium (30 - 250 nM) showed a decrease of the heat produced by the enzymatic reaction with an increasing concentration of actinides in the medium. Our findings showed that the Calmodulin actinide complex works as an enzymatic inhibitor. Furthermore, at higher neptunium (250 nM) and uranium (500 nM) concentration the metals seem to have a poison

  8. Positron Spectroscopy of Hydrothermally Grown Actinide Oxides

    Science.gov (United States)

    2014-03-27

    actinide oxides . The work described here is an attempt to characterize the quality of crystals using positron annihilation spectroscopy (PALS). The...Upadhyaya, R. V. Muraleedharan, B. D. Sharma and K. G. Prasad, " Positron lifetime studies on thorium oxide powders," Philosohical Magazine A, vol. 45... crystals . A strong foundation for actinide PALS studies was laid, but further work is required to build a more effective system. Positron Spectroscopy

  9. Separation of actinides and their transmutation

    International Nuclear Information System (INIS)

    Bouchard, M.; Bathelier, M.; Cousin, M.

    1978-08-01

    Neutron irradiation of long-half-life actinides for transmutation into elements with shorter half-life is investigated as a means to reduce the long-term hazards of these actinides. The effectiveness of the method is analysed by applying it to fission product solutions from the first extraction cycle of fuel reprocessing plants. Basic principles, separation techniques and transmutation efficiencies are studied and discussed in detail

  10. The removal of actinide metals from solution

    International Nuclear Information System (INIS)

    Hancock, R.D.; Howell, I.V.

    1980-01-01

    A process is specified for removing actinide metals (e.g. uranium) from solutions. The solution is contacted with a substrate comprising the product obtained by reacting an inorganic solid containing surface hydroxyl groups (e.g. silica gel) with a compound containing a silane grouping, a nitrogen-containing group (e.g. an amine) and other specified radicals. After treatment, the actinide metal is recovered from the substrate. (U.K.)

  11. PREPARATION OF ACTINIDE-ALUMINUM ALLOYS

    Science.gov (United States)

    Moore, R.H.

    1962-09-01

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

  12. Evaluation of actinide partitioning and transmutation

    International Nuclear Information System (INIS)

    1982-01-01

    After a few centuries of radioactive decay the long-lived actinides, the elements of atomic numbers 89-103, may constitute the main potential radiological health hazard in nuclear wastes. This is because all but a very few fission products (principally technetium-99 and iodine-129) have by then undergone radioactive decay to insignificant levels, leaving the actinides as the principal radionuclides remaining. It was therefore at first sight an attractive concept to recycle the actinides to nuclear reactors, so as to eliminate them by nuclear fission. Thus, investigations of the feasibility and potential benefits and hazards of the concept of 'actinide partitioning and transmutation' were started in numerous countries in the mid-1970s. This final report summarizes the results and conclusions of technical studies performed in connection with a four-year IAEA Co-ordinated Research Programme, started in 1976, on the ''Environmental Evaluation and Hazard Assessment of the Separation of Actinides from Nuclear Wastes followed by either Transmutation or Separate Disposal''. Although many related studies are still continuing, e.g. on waste disposal, long-term safety assessments, and waste actinide management (particularly for low and intermediate-level wastes), some firm conclusions on the overall concept were drawn by the programme participants, which are reflected in this report

  13. Advances in computational actinide chemistry in China

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Dongqi; Wu, Jingyi; Chai, Zhifang [Chinese Academy of Sciences, Beijing (China). Multidisciplinary Initiative Center; Su, Jing [Chinese Academy of Sciences, Shanghai (China). Div. of Nuclear Materials Science and Engineering; Li, Jun [Tsinghua Univ., Beijing (China). Dept. of Chemistry and Laboratory of Organic Optoelectronics and Molecular Engineering

    2014-04-01

    The advances in computational actinide chemistry made in China are reviewed. Several areas relevant to chemistry of actinides in gas, liquid, and solid phases have been explored. However, we limit the scope to selected contributions in the chemistry of molecular actinide systems in gas and liquid phases. These studies may be classified into two categories: treatment of relativistic effects, which cover the development of two- and four-component Hamiltonians and the optimization of relativistic pseudopotentials, and the applications of theoretical methods in actinide chemistry. The applications include (1) the electronic structures of actinocene, noble gas complexes, An-C multiple bonding compounds, uranyl and its isoelectronic species, fluorides and oxides, molecular systems with metal-metal bonding in their isolated forms (U{sub 2}, Pu{sub 2}) and in fullerene (U{sub 2} rate at C{sub 60}), and the excited states of actinide complexes; (2) chemical reactions, including oxidation, hydrolysis of UF{sub 6}, ligand exchange, reactivities of thorium oxo and sulfido metallocenes, CO{sub 2}/CS{sub 2} functionalization promoted by trivalent uranium complex; and (3) migration of actinides in the environment. A future outlook is discussed. (orig.)

  14. Rapid determination of actinides in seawater samples

    International Nuclear Information System (INIS)

    Maxwell, S.L.; Culligan, B.K.; Hutchison, J.B.; Utsey, R.C.; McAlister, D.R.

    2014-01-01

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

  15. Recovery of Actinides from Actinide-Aluminium Alloys: Chlorination Route

    International Nuclear Information System (INIS)

    Mendes, E.; Malmbeck, R.; Soucek, P.; Jardin, R.; Glatz, J.P.; Cassayre, L.

    2008-01-01

    A method for recovery of actinides (An) from An-Al alloys formed by electrochemical separation of metallic spent nuclear fuel on solid aluminium electrodes in molten chloride salts is described. The proposed route consists of three main steps: -) vacuum distillation of salt adhered on the electrodes, -) chlorination of An-Al alloy by pure chlorine gas and -) sublimation of formed AlCl 3 . A thermochemical study of the route was performed to determine important chemical reactions and to find optimum experimental conditions for all process steps. Vacuum distillation of the electrode is efficient for complete removal of remaining salt and most fission products, full chlorination of the An-Al alloys is possible at any working temperature and evaporation of AlCl 3 is achieved by heating under argon. Experiments have been carried out using U-Al alloy in order to define parameters providing full alloy chlorination without formation of volatile UCl 5 and UCl 6 . It was shown that full chlorination of An-Al alloys without An losses should be possible at a temperature approx. 150 deg. C. (authors)

  16. Recovery of Actinides from Actinide-Aluminium Alloys: Chlorination Route

    Energy Technology Data Exchange (ETDEWEB)

    Mendes, E.; Malmbeck, R.; Soucek, P.; Jardin, R.; Glatz, J.P. [European Commission, JRC, Institute for Transuranium Elements, Postfach 2340, 76125 Karlsruhe (Germany); Cassayre, L. [Laboratoire de Genie Chimique (LGC), Universite Paul Sabatier, UMR CNRS 5503, 118 route de Narbonne, 31062 Toulouse Cedex 04 (France)

    2008-07-01

    A method for recovery of actinides (An) from An-Al alloys formed by electrochemical separation of metallic spent nuclear fuel on solid aluminium electrodes in molten chloride salts is described. The proposed route consists of three main steps: -) vacuum distillation of salt adhered on the electrodes, -) chlorination of An-Al alloy by pure chlorine gas and -) sublimation of formed AlCl{sub 3}. A thermochemical study of the route was performed to determine important chemical reactions and to find optimum experimental conditions for all process steps. Vacuum distillation of the electrode is efficient for complete removal of remaining salt and most fission products, full chlorination of the An-Al alloys is possible at any working temperature and evaporation of AlCl{sub 3} is achieved by heating under argon. Experiments have been carried out using U-Al alloy in order to define parameters providing full alloy chlorination without formation of volatile UCl{sub 5} and UCl{sub 6}. It was shown that full chlorination of An-Al alloys without An losses should be possible at a temperature approx. 150 deg. C. (authors)

  17. Sol-gel chemistry applied to the synthesis of polymetallic oxides including actinides reactivity and structure from solution to solid state; Synthese par voie douce d'oxydes polymetalliques incluant des actinides: reactivite et structure de la solution au solide

    Energy Technology Data Exchange (ETDEWEB)

    Lemonnier, St

    2006-02-15

    Minor actinides transmutation is studied at present in order to reduce the radiotoxicity of nuclear waste and the assessment of its technical feasibility requires specific designed materials. When considering americium, yttria stabilized zirconia (Am{sup III} YII Zriv)Or{sub x} is among the ceramic phases that one which presents the required physico-chemical properties. An innovative synthesis of this mixed oxide by sol-gel process is reported in this manuscript. The main aim of this work is to adjust the reactivity of the different metallic cations in aqueous media using complexing agent, in order to initiate a favourable interaction for a homogeneous elements repartition in the forming solid phase. The originality of the settled synthesis lies on an in-situ formation of a stable and monodisperse nano-particles dispersion in the presence of acetylacetone. The main reaction mechanisms have been identified: the sol stabilisation results from an original interaction between the three compounds (Zrly, trivalent cations and acetylacetone). The sol corresponds to a structured system at the nanometer scale for which zirconium and trivalent cations are homogeneously dispersed, preliminary to the sol-gel transition. Furthermore, preliminary studies were carried out with a view to developing materials. They have demonstrated that numerous innovative and potential applications can be developed by taking advantage of the direct and controlled formation of the sol and by adapting the sol-gel transition. The most illustrating result is the preparation of a sintered pellet with the composition Am0,13Zro,73Yo,0901,89 using this approach. (author)

  18. Reactor physics aspects of burning actinides in a nuclear reactor

    International Nuclear Information System (INIS)

    Hage, W.; Schmidt, E.

    1978-01-01

    A short review of the different recycling strategies of actinides other than fuel treated in the literature, is given along with nuclear data requirements for actinide build-up and transmutation studies. The effects of recycling actinides in a nuclear reactor on the flux distribution, the infinite neutron multiplication factor, the reactivity control system, the reactivity coefficients and the delayed neutron fraction are discussed considering a notional LWR or LMFBR as an Actinide Trasmutaton Reactor. Some operational problems of Actinide Transmutation reactors are mentioned, which are caused by the α-decay heat and the neutron sources of Actinide Target Elements

  19. New strategies in actinide separation - water-soluble complexing agents for the innovative SANEX process

    International Nuclear Information System (INIS)

    Ruff, Christian M.; Muelllich, Udo; Geist, Andreas; Panak, Petra J.

    2012-01-01

    Reduction of the radiotoxicity and thermal output of radioactive wastes prior to their permanent disposal is a topic of extreme interest for the issue of final nuclear waste disposal. One possibility to this end is a process referred to as actinide separation. This process can be optimised by means of a newly developed water-soluble molecule, as has been shown in studies on the molecule's complex chemistry using ultra-modern laser-based spectroscopy methods under process-relevant reaction conditions. Through the use of curium (III) and europium (III), which as members of the trivalent actinides and lanthanides family have excellent spectroscopic properties, it has been possible to generate spectroscopic and thermodynamic data which will facilitate our understanding of the complex chemistry and extraction chemistry of this molecule family.

  20. A review of the demonstration of innovative solvent extraction processes for the recovery of trivalent minor actinides from PUREX raffinate

    International Nuclear Information System (INIS)

    Modolo, G.; Wilden, A.; Geist, A.; Magnusson, D.; Malmbeck, R.

    2012-01-01

    The selective partitioning (P) of long-lived minor actinides from highly active waste solutions and their transmutation (T) to short-lived or stable isotopes by nuclear reactions will reduce the long-term hazard of the high-level waste and significantly shorten the time needed to ensure their safe confinement in a repository. The present paper summarizes the on-going research activities at Forschungszentrum Juelich (FZJ), Karlsruher Institut fuer Technologie (KIT) and Institute for Transuranium Elements (ITU) in the field of actinide partitioning using innovative solvent extraction processes. European research over the last few decades, i.e. in the NEWPART, PARTNEW and EUROPART programmes, has resulted in the development of multi-cycle processes for minor actinide partitioning. These multi-cycle processes are based on the co-separation of trivalent actinides and lanthanides (e.g. by the DIAMEX process), followed by the subsequent actinide(III)/lanthanide(III) group separation in the SANEX process. The current direction of research for the development of innovative processes within the recent European ACSEPT project is discussed additionally. This paper is focused on the development of flow-sheets for recovery of americium and curium from highly active waste solutions. The flow-sheets are verified by demonstration processes, in centrifugal contactors, using synthetic or genuine fuel solutions. The feasibility of the processes is also discussed. (orig.)

  1. Thermodynamic data for predicting concentrations of Pu(III), Am(III), and Cm(III) in geologic environments

    Energy Technology Data Exchange (ETDEWEB)

    Rai, Dhanpat; Rao, Linfeng; Weger, H.T.; Felmy, A.R. [Pacific Northwest National Laboratory, WA (United States); Choppin, G.R. [Florida State University, Florida (United States); Yui, Mikazu [Japan Nuclear Cycle Development Inst., Tokai Works, Tokai, Ibaraki (Japan)

    1999-01-01

    This report provides thermodynamic data for predicting concentrations of Pu(III), Am(III), and Cm(III) in geologic environments, and contributes to an integration of the JNC chemical thermodynamic database, JNC-TDB (previously PNC-TDB), for the performance analysis of geological isolation system for high-level radioactive wastes. Thermodynamic data for the formation of complexes or compounds with hydroxide, chloride, fluoride, carbonate, nitrate, sulfate and phosphate are discussed in this report. Where data for specific actinide(III) species are lacking, the data were selected based on chemical analogy to other trivalent actinides. In this study, the Pitzer ion-interaction model is mainly used to extrapolate thermodynamic constants to zero ionic strength at 25degC. (author)

  2. Stabilization of actinides and lanthanides in unusually high oxidation states

    International Nuclear Information System (INIS)

    Eller, P.G.; Penneman, R.A.

    1986-01-01

    Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO 3 or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF 5 /HF solution or Pu(VII) in Li 5 PuO 6 ). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs

  3. Actinide transmutation in nuclear reactors

    International Nuclear Information System (INIS)

    Bultman, J.H.

    1995-01-01

    An optimization method is developed to maximize the burning capability of the ALMR while complying with all constraints imposed on the design for reliability and safety. This method leads to a maximal transuranics enrichment, which is being limited by constraints on reactivity. The enrichment can be raised by using the neutrons less efficiently by increasing leakage from the fuel. With the developed optimization method, a metallic and an oxide fueled ALMR were optimized. Both reactors perform equally well considering the burning of transuranics. However, metallic fuel has a much higher heat conductivity coefficient, which in general leads to better safety characteristics. In search of a more effective waste transmuter, a modified Molten Salt Reactor was designed. A MSR operates on a liquid fuel salt which makes continuous refueling possible, eliminating the issue of the burnup reactivity loss. Also, a prompt negative reactivity feedback is possible for an overmoderated reactor design, even when the Doppler coefficient is positive, due to the fuel expansion with fuel temperature increase. Furthermore, the molten salt fuel can be reprocessed based on a reduction process which is not sensitive to the short-lived spontaneously fissioning actinides. (orig./HP)

  4. Actinide/crown ether chemistry

    International Nuclear Information System (INIS)

    Benning, M.M.

    1988-01-01

    A structural survey of actinide/crown ether compounds was conducted in order to investigate the solid state chemistry of these complexes. Several parameters - the metal size, crown type, counterion, solvent systems and reaction and crystallization conditions - were varied to correlate their importance in complexation. Under atmospheric conditions, two types of complexes were isolated, those containing only hydrogen-bonded crown interactions and instances where the crown interacts directly with the metal center. In both cases, water seems to play a very important role. When coordinated to the metal, water molecules exhibit the necessary donor properties required for the formation of hydrogen-bonded contacts. The water molecules also provide fierce competition with the crown ethers for metal-binding sites and in most cases prohibit the formation of complexes in which direct metal-ligand association exists. The results of this study indicate that direct interaction between the metal atoms and the crown ethers, in the presence of water, can only occur with polyether conformations which limit the steric replusions within the metal coordination sphere

  5. Actinide transmutation in nuclear reactors

    Energy Technology Data Exchange (ETDEWEB)

    Bultman, J H

    1995-01-17

    An optimization method is developed to maximize the burning capability of the ALMR while complying with all constraints imposed on the design for reliability and safety. This method leads to a maximal transuranics enrichment, which is being limited by constraints on reactivity. The enrichment can be raised by using the neutrons less efficiently by increasing leakage from the fuel. With the developed optimization method, a metallic and an oxide fueled ALMR were optimized. Both reactors perform equally well considering the burning of transuranics. However, metallic fuel has a much higher heat conductivity coefficient, which in general leads to better safety characteristics. In search of a more effective waste transmuter, a modified Molten Salt Reactor was designed. A MSR operates on a liquid fuel salt which makes continuous refueling possible, eliminating the issue of the burnup reactivity loss. Also, a prompt negative reactivity feedback is possible for an overmoderated reactor design, even when the Doppler coefficient is positive, due to the fuel expansion with fuel temperature increase. Furthermore, the molten salt fuel can be reprocessed based on a reduction process which is not sensitive to the short-lived spontaneously fissioning actinides. (orig./HP).

  6. Lithium actinide recycle process demonstration

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, G.K.; Pierce, R.D.; McPheeters, C.C. [Argonne National Laboratory, IL (United States)

    1995-10-01

    Several pyrochemical processes have been developed in the Chemical Technology Division of Argonne Laboratory for recovery of actinide elements from LWR spent fuel. The lithium process was selected as the reference process from among the options. In this process the LWR oxide spent fuel is reduced by lithium at 650{degrees}C in the presence of molten LiCl. The Li{sub 2}O formed during the reduction process is soluble in the salt. The spent salt and lithium are recycled after the Li{sub 2}O is electrochemically reduced. The oxygen is liberated as CO{sub 2} at a carbon anode or oxygen at an inert anode. The reduced metal components of the LWR spent fuel are separated from the LiCL salt phase and introduced into an electrorefiner. The electrorefining step separates the uranium and transuranium (TRU) elements into two product streams. The uranium product, which comprises about 96% of the LWR spent fuel mass, may be enriched for recycle into the LWR fuel cycle, stored for future use in breeder reactors, or converted to a suitable form for disposal as waste. The TRU product can be recycled as fast reactor fuel or can be alloyed with constituents of the LWR cladding material to produce a stable waste form.

  7. Atomistic modeling of the solid-state chemistry of actinide materials

    Science.gov (United States)

    Shuller, Lindsay C.

    Materials that incorporate actinides are critical to the nuclear fuel cycle, either as nuclear fuels or nuclear waste forms. In this thesis, I examine four materials: i) ThO2-UO2 solid solutions, ii) binary ThO2-CeO2-ZrO2 solid solutions, iii) Np-doped studtite, iv) Np-doped boltwoodite. Computational methods, particularly density functional theory (DFT) calculations and Monte-Carlo (MC) simulations, are used to determine the energetics and structures of these actinide-bearing materials. The solid-solution behavior of nuclear fuels and nuclear waste forms indicate the thermodynamic stability of the material, which is important for understanding the in-reactor fuel properties and long-term stability of used fuel. The ThxU1-xO2 and ThxCe 1-xO2 binaries are almost completely miscible; however, DeltaGmix reveals a small tendency for the systems to exsolve (e.g., DeltaEexsoln(Th xU1-xO2) = 0.13 kJ/(mol cations) at 750 K). Kinetic hindrances (e.g., interfacial energy) may inhibit exsolution, especially at the low temperatures necessary to stabilize the nanoscale exsolution lamellae observed in the ThxU1-xO2 and Ce xZr1-xO2 binaries. Miscibility in the Zr-bearing binaries is limited. At 1400 °C, only 3.6 and 0.09 mol% ZrO2 is miscible in CeO2 and ThO2, respectively. The incorporation of minor amounts of Np5+,6+ into uranium alteration phases, e.g., studtite [UO2O2 (H2O)4] or boltwoodite [K(UO2)(SiO 3OH)(H2O)1.5] , may limit the mobility of aqueous neptunyl complexes released from oxidized nuclear fuels. Np6+-incorporation into studtite requires less energy than Np5+-incorporation (e.g., with source/sink = Np2O5/UO 3 DeltaEincorp(Np6+) = 0.42 eV and DeltaEincorp(Np5+) = 1.12 eV). In addition, Np6+ is completely miscible in studtite at room temperature with respect to a hypothetical Np6+-studtite. Electronic structure calculations provide insight into Np-bonding in studtite. The Np 5f orbitals are within the band gap of studtite, resulting in the narrowing of the band gap

  8. Comparative synergistic (technetium-actinide) extraction chemistry by tributylphosphate and some amide extractants

    International Nuclear Information System (INIS)

    Condamines, N.; Musikas, C.

    1993-01-01

    In nuclear fuel reprocessing, technetium (TcO 4 - ) leads to bad interferences in the extractions, being synergistically co-extracted with different actinide cations as Uranium (VI), Plutonium (IV) and Zirconium (IV). It destroys the hydrazine in the reductive partition of U and Pu, it decreases the decontamination of U and Pu from fission products. Thus, its extraction behaviour with new extractants as N,N-diakylamides is useful to be known. TcO 4 - extraction in nitric acid media is compared for TBP and different amides. The influence of nitric acidity is related to the amides formula

  9. Molecular dynamics simulations of ter-pyridine and bis-triazinyl-pyridine complexes with lanthanide cations; Etude de dynamique moleculaire de complexes de la bis-triazinyl-pyridine (BTP) et de la terpyridine avec des lanthanides(3)

    Energy Technology Data Exchange (ETDEWEB)

    Guilbaud, Ph. [CEA Valrho, (DCC/DRRV/SEMP), 30 - Marcoule (France)

    2000-07-01

    The search for ligands which specifically separate actinides(III) from lanthanides(III) by liquid-liquid extraction has prompted considerable research in the Process Design and Modeling Department ('Service d'Etude et de Modelisation des Procedes'- SEMP). Ligands with soft donor atoms AS) that are able to perform this separation have already been investigated and research is currently under way to improve their performance for high acidic feeds. Theoretical chemistry research is conducted in the Theoretical and Structural Chemistry Laboratory ('Laboratoire de Chimie Theorique et Structurale') to improve our understanding of the complexation and extraction of these cations with such ligands. Theoretical studies were first carried out for the ter-pyridine (TPY) and bis-triazinyl-pyridine (BTP) ligands that display fairly good ability to separate and extract actinide(III) from lanthanide(III) ions. Molecular dynamics simulations were performed on ter-pyridine and bis-triazinyl-pyridine complexes with three lanthanide cations (La{sup 3+}, Eu{sup 3+} and Lu{sup 3+}) for vacuum and for water solutions. These calculations were carried out without counter-ions, with three nitrate (NO{sub 3}{sup -}) ions, and, in the case of ter-pyridine, with three {alpha}-bromo-caprate anions that are likely to be used experimentally as synergistic agents for the separation and extraction of An(III) from Ln(III). Molecular dynamics simulations were first performed for vacuum to evaluate the distances between nitrogen and lanthanide atoms (Ln{sup 3+},N) and intrinsic interaction energies to poly-nitrogenous ligands with or without NO{sub 3} ions, and for both ligands. The (Ln{sup 3+},N) distances decrease and the cation/ligand interaction energies increase along the La{sup 3+}, Eu{sup 3+}, Lu{sup 3+} series, with decreasing Ln(III) ion radii. The introduction of nitrate counter-ions makes the (Ln{sup 3+},N) distances slightly higher, and the TPY/Ln{sup 3+} and BTP

  10. Interaction of selected actinides (U, Cm) with bacteria relevant to nuclear waste disposal

    Energy Technology Data Exchange (ETDEWEB)

    Luetke, Laura

    2013-07-01

    To assess the safety of a site destined for storage of nuclear waste enhanced research effort is demanded to investigate the complex interactions of released radionuclides with parts of the environment that includes indigenous microorganisms. This work aimed at assessing the interactions of two bacterial strains with the actinides uranium and curium with a focus on thermodynamics to provide stability constants of the actinide bacteria species formed usable for modelling the distribution of these actinides in the environment. The influences of Pseudomonas fluorescens (CCUG 32456A) isolated from the granitic aquifers at Aespoe(Sweden) and a novel isolate from Mont Terri Opalinus clay (Switzerland), Paenibacillus sp. MT-2.2, were investigated. A combined approach using microbiological and spectroscopic techniques as well as potentiometry was employed to characterize the U(VI) and Cm(III) binding onto the cell surface functional groups structurally and thermodynamically. Further, due to its similar ionic radius to Cm(III) also Eu(III) was studied as non-radioactive analog.

  11. Interaction of trivalent lanthanides and actinides with aluminium oxides and hydroxides; Wechselwirkung von dreiwertigen Lanthaniden und Actiniden mit Aluminiumoxiden und -hydroxiden

    Energy Technology Data Exchange (ETDEWEB)

    Kupcik, Tomas

    2011-10-28

    The subject of the present work is the interaction of trivalent actinides Cm(III) and lanthanides (Eu(III) and Gd(III)) with aluminium oxides and -hydroxides, namely corundum/sapphire (α-Al{sub 2}O{sub 3}), gibbsite (α-Al(OH){sub 3}) and bayerite (β-Al(OH){sub 3}), as well as the polyoxocations ''Al{sub 13}'' (Al{sub 13}O{sub 4}(OH){sub 24}(H{sub 2}O){sub 12}{sup 7+}) and ''GaAl{sub 12}'' (GaO{sub 4}Al{sub 12}(OH){sub 24}(H{sub 2}O){sub 12}{sup 7+}). These investigations should contribute to a sound understanding of the solution-mineral-interface reactions relevant for the migration of radionuclides (in particular the actinides) in the near and far field of a repository for high-level radioactive waste in deep geological formations, e.g. adsorption and structural incorporation. Batch sorption studies show similar logK{sub d} values for Eu(III) sorption onto corundum and bayerite at low metal ion concentrations ([M(III)] ∝ 7.10{sup -7} M). These similarities can be related to the formation of Al-OH groups on the aluminium oxide surfaces. Comparable logK{sub d} values could be found in earlier investigations for Gd(III) sorbed onto γ-Al{sub 2}O{sub 3}. In agreement with the batch sorption results at trace metal ion concentrations, time resolved laser fluorescence spectroscopy (TRLFS) studies on the interaction of Cm(III) with corundum and bayerite suggest a similar Cm(III) speciation between pH = 3 and 13. Three different surface sorbed Cm(III) species can be distinguished for these mineral phases ([surface..Cm(OH){sub x}(H{sub 2}O){sub 5-x}]{sup 3-x} with x = 0, 1, 2). Comparable TRLFS results can also be found for Cm(III) sorbed on the sapphire (001) single crystal surface and on ''Al{sub 13}'' and ''GaAl{sub 12}''. In the Cm(III)/gibbsite system, spectroscopic results show clear differences in comparison to bayerite, corundum and γ-Al{sub 2}O{sub 3}, e.g. a Cm(III) species of

  12. Isomerization of propargyl cation to cyclopropenyl cation ...

    Indian Academy of Sciences (India)

    step) for isomeri- zation of the linear propargyl cation to ..... C3, C4 and C5. The ZPE corrections in each case are derived from the. B3LYP calculations. ..... the converse of which gives the relative capacity of the. LPD's to stabilize TS6 with respect ...

  13. Methods for separation of actinides

    International Nuclear Information System (INIS)

    Keller, C.

    1976-01-01

    Methods of actinoids separation are reviewed, including precipitation, sublimation, paper chromatography and electrophoresis. Compounds typically used for co-precipitation of actinoid ions are listed. Ion-exchange methods considered include cation and ion exchange. Factors are described, which affect the efficiency of separation of transuranium elements in the same degrees of oxidation: complex-forming agents, temperature, ion-exchange resin, rate of elution, the size of the column, the influence of salts. Extraction of actinoid ions upon formation of solvate complexes, inner complex compounds and metal salts is discussed. Combining the advantages of ion exchange and extraction, the method of extraction chromatography can be widely used for separation of actinoids

  14. Critical analysis of the data on complexation of lanthanides and actinides by natural organic matter: particular case of humic substances

    International Nuclear Information System (INIS)

    Reiller, P.

    2010-01-01

    This document proposes a critical analysis of the models that describe the actinides and lanthanides complexation by natural organic matter in general and by humic substances in particular. In order to better delimit the particular properties of these substances the most influent physical and chemical properties on complexation are recalled as a preamble. Models as well as data that has been used are reviewed, compiled, and eventually compared to independent data in order to identify (i) their application domain, (ii) the possible simplifications which permit to obtain operational models, (iii) the conditions in which simplifications cannot be ascertained yet, and (iv) the data or fields of knowledge which are still too uncertain. A comparison between the different models is proposed in order to adapt parameters from one model to another minimising the experimental acquisitions, or at least to focus on missing data. Usually, data on the complexation of free ions M z+ are reliable; as soon as hydrolysis, or competition with another ligand in general, in at stake data are much less reliable. Predictions from models are much more uncertain: formation of mixed complexes with hydroxide or carbonate anions is not univocal whatever the modelling strategy. Hints for transfer functions between models which are believed to be incompatible could be explored in order to justify necessary simplifications for using operational modelling. Influence on the solubility of oxides could be quantified, but it is difficult to clearly separate it from colloidal particles stabilisation. The account of the competition between cations by the models has also been tested. In view of the small number of available experimental data there still lie some uncertainties especially for the media that are close to neutrality and in the case of competition with magnesium, but overall in the case of the competition with aluminium and iron. The influence of redox activity of humic substances is also

  15. Use of fast reactors for actinide transmutation

    International Nuclear Information System (INIS)

    1993-03-01

    The management of radioactive waste is one of the key issues in today's discussions on nuclear energy, especially the long term disposal of high level radioactive wastes. The recycling of plutonium in liquid metal fast breeder reactors (LMFBRs) would allow 'burning' of the associated extremely long life transuranic waste, particularly actinides, thus reducing the required isolation time for high level waste from tens of thousands of years to hundreds of years for fission products only. The International Working Group on Fast Reactors (IWGFR) decided to include the topic of actinide transmutation in liquid metal fast breeder reactors in its programme. The IAEA organized the Specialists Meeting on Use of Fast Breeder Reactors for Actinide Transmutation in Obninsk, Russian Federation, from 22 to 24 September 1992. The specialists agree that future progress in solving transmutation problems could be achieved by improvements in: Radiochemical partitioning and extraction of the actinides from the spent fuel (at least 98% for Np and Cm and 99.9% for Pu and Am isotopes); technological research and development on the design, fabrication and irradiation of the minor actinides (MAs) containing fuels; nuclear constants measurement and evaluation (selective cross-sections, fission fragments yields, delayed neutron parameters) especially for MA burners; demonstration of the feasibility of the safe and economic MA burner cores; knowledge of the impact of maximum tolerable amount of rare earths in americium containing fuels. Refs, figs and tabs

  16. Band structure studies of actinide systems

    International Nuclear Information System (INIS)

    Koelling, D.D.

    1976-01-01

    The nature of the f-orbitals in an actinide system plays a crucial role in determining the electronic properties. It has long been realized that when the actinide separation is small enough for the f-orbitals to interact directly, the system will exhibit itinerant electron properties: an absence of local moment due to the f-orbitals and sometimes even superconductivity. However, a number of systems with the larger actinide separation that should imply local moment behavior also exhibit intinerant properties. Such systems (URh 3 , UIr 3 , UGe 3 , UC) were examined to learn something about the other f-interactions. A preliminary observation made is that there is apparently a very large and ansiotropic mass enhancement in these systems. There is very good reason to believe that this is not solely due to large electron--electron correlations but to a large electron--phonon interaction as well. These features of the ''non-magnetic'', large actinide separation systems are discussed in light of our results to date. Finally, the results of some recent molecular calculations on actinide hexafluorides are used to illustrate the shielding effects on the intra-atomic Coulomb term U/sub f-f/ which would appear in any attempt to study the formation of local moments. As one becomes interested in materials for which a band structure is no longer an adequate model, this screened U/sub ff/ is the significant parameter and efforts must be made to evaluate it in solid state systems

  17. Hexagonal perovskites with cationic vacancies. 1. Compounds of the type Ba/sub 2/Bsub(1/3)sup(III) vacantsub(2/3) Resup(VII)O/sub 6/

    Energy Technology Data Exchange (ETDEWEB)

    Kemmler-Sack, S; Jooss, I [Tuebingen Univ. (Germany, F.R.). Inst. fuer Chemie

    1978-04-01

    Compounds of type Ba/sub 2/Bsub(1/3)sup(III)vacantsub(2/3)Resup(VII)O/sub 6/ are formed with Bsup(III) = Sm-Gd, Ho-Lu, Y, Sc, In (yellow); Tb (black-brown); Dy (yellow-orange). They crystallize with Bsup(III) = Sm-Lu, Y and Sc in a rhombohedral layer structure of 12 L-type (space group R3m; sequence: cchhcchhcchh) with 6 formula units in the unit cell.

  18. Nonaqueous method for dissolving lanthanide and actinide metals

    International Nuclear Information System (INIS)

    Crisler, L.R.

    1975-01-01

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

  19. Strategies for minority actinides transmutation in fast reactors

    International Nuclear Information System (INIS)

    Perez-Martin, S.; Martin-Fuertes, F.; Alvarez-Velarde, F.

    2010-01-01

    Presentation of the strategies that can be followed in fast reactors designed for the fourth generation to reduce the inventory of minority actinides generated in current light water reactors, as the actinides generation in fast reactor.

  20. Sigma Team for Advanced Actinide Recycle FY2015 Accomplishments and Directions

    Energy Technology Data Exchange (ETDEWEB)

    Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-09-30

    The Sigma Team for Minor Actinide Recycle (STAAR) has made notable progress in FY 2015 toward the overarching goal to develop more efficient separation methods for actinides in support of the United States Department of Energy (USDOE) objective of sustainable fuel cycles. Research in STAAR has been emphasizing the separation of americium and other minor actinides (MAs) to enable closed nuclear fuel recycle options, mainly within the paradigm of aqueous reprocessing of used oxide nuclear fuel dissolved in nitric acid. Its major scientific challenge concerns achieving selectivity for trivalent actinides vs lanthanides. Not only is this challenge yielding to research advances, but technology concepts such as ALSEP (Actinide Lanthanide Separation) are maturing toward demonstration readiness. Efforts are organized in five task areas: 1) combining bifunctional neutral extractants with an acidic extractant to form a single process solvent, developing a process flowsheet, and demonstrating it at bench scale; 2) oxidation of Am(III) to Am(VI) and subsequent separation with other multivalent actinides; 3) developing an effective soft-donor solvent system for An(III) selective extraction using mixed N,O-donor or all-N donor extractants such as triazinyl pyridine compounds; 4) testing of inorganic and hybrid-type ion exchange materials for MA separations; and 5) computer-aided molecular design to identify altogether new extractants and complexants and theory-based experimental data interpretation. Within these tasks, two strategies are employed, one involving oxidation of americium to its pentavalent or hexavalent state and one that seeks to selectively complex trivalent americium either in the aqueous phase or the solvent phase. Solvent extraction represents the primary separation method employed, though ion exchange and crystallization play an important role. Highlights of accomplishments include: Confirmation of the first-ever electrolytic oxidation of Am(III) in a

  1. Demonstration of innovative partitioning processes for minor actinide recycling from high active waste solutions

    International Nuclear Information System (INIS)

    Modolo, G.; Wilden, A.; Geist, A.; Malmbeck, R.; Taylor, R.

    2014-01-01

    The recycling of the minor actinides (MA) using the Partitioning and Transmutation strategy (P and T) could contribute significantly to reducing the volume of high level waste in a geological repository and to decreasing the waste's longterm hazards originating from the long half-life of the actinides. Several extraction processes have been developed worldwide for the separation and recovery of MA from highly active raffinates (HAR, e.g. the PUREX raffinate). A multi-cycle separation strategy has been developed within the framework of European collaborative projects. The multi-cycle processes, on the one hand, make use of different extractants for every single process. Within the recent FP7 European research project ACSEPT (Actinide reCycling by SEParation and Transmutation), the development of new innovative separation processes with a reduced number of cycles was envisaged. In the so-called 'innovative SANEX' concept, the trivalent actinides and lanthanides are co-extracted from the PUREX raffinate by a DIAMEX like process (e.g. TODGA). Then, the loaded solvent is subjected to several stripping steps. The first one concerns selectively stripping the actinides(III) with selective water-soluble ligands (SO3-Ph-BTB), followed by the subsequent stripping of trivalent lanthanides. A more challenging route studied also within our laboratories is the direct actinide(III) separation from a PUREX-type raffinate using a mixture of CyMe 4 BTBP and TODGA as extractants, the so-called One cycle SANEX process. A new approach, which was also studied within the ACSEPT project, is the GANEX (Grouped ActiNide EXtraction) concept addressing the simultaneous partitioning of all transuranium (TRU) elements for their homogeneous recycling in advanced generation IV reactor systems. Bulk uranium is removed in the GANEX 1st cycle, e.g. using a monoamide extractant and the GANEX 2nd cycle then separates the TRU. A solvent composed of TODGA + DMDOHEMA in kerosene has been shown to

  2. Room temperature electrodeposition of actinides from ionic solutions

    Science.gov (United States)

    Hatchett, David W.; Czerwinski, Kenneth R.; Droessler, Janelle; Kinyanjui, John

    2017-04-25

    Uranic and transuranic metals and metal oxides are first dissolved in ozone compositions. The resulting solution in ozone can be further dissolved in ionic liquids to form a second solution. The metals in the second solution are then electrochemically deposited from the second solutions as room temperature ionic liquid (RTIL), tri-methyl-n-butyl ammonium n-bis(trifluoromethansulfonylimide) [Me.sub.3N.sup.nBu][TFSI] providing an alternative non-aqueous system for the extraction and reclamation of actinides from reprocessed fuel materials. Deposition of U metal is achieved using TFSI complexes of U(III) and U(IV) containing the anion common to the RTIL. TFSI complexes of uranium were produced to ensure solubility of the species in the ionic liquid. The methods provide a first measure of the thermodynamic properties of U metal deposition using Uranium complexes with different oxidation states from RTIL solution at room temperature.

  3. 1981 Annual Status Report. Plutonium fuels and actinide programme

    International Nuclear Information System (INIS)

    1981-01-01

    In this 1981 report the work carried out by the European Institute for Transuranium elements is reviewed. Main topics are: operation limits of plutonium fuels: swelling of advanced fuels, oxide fuel transients, equation of state of nuclear materials; actinide cycle safety: formation of actinides (FACT), safe handling of plutonium fuel (SHAPE), aspects of the head-end processing of carbide fuel (RECARB); actinide research: crystal chemistry, solid state studies, applied actinide research

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

    Science.gov (United States)

    Miller, S.M.

    1983-10-31

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

  5. Special actinide nuclides: Fuel or waste?

    International Nuclear Information System (INIS)

    Srinivasan, M.; Rao, K.S.; Dingankar, M.V.

    1989-01-01

    The special actinide nuclides such as Np, Cm, etc. which are produced as byproducts during the operation of fission reactors are presently looked upon as 'nuclear waste' and are proposed to be disposed of as part of high level waste in deep geological repositories. The potential hazard posed to future generations over periods of thousands of years by these long lived nuclides has been a persistent source of concern to critics of nuclear power. However, the authors have recently shown that each and every one of the special actinide nuclides is a better nuclear fuel than the isotopes of plutonium. This finding suggests that one does not have to resort to exotic neutron sources for transmuting/incinerating them as proposed by some researchers. Recovery of the special actinide elements from the waste stream and recycling them back into conventional fission reactors would eliminate one of the stigmas attached to nuclear energy

  6. Interaction of actinides with natural microporous materials

    International Nuclear Information System (INIS)

    Misaelides, P.; Godelirsas, A.

    1998-01-01

    The existing studies mainly concern the sorption of thorium, uranium, neptunium, plutonium and americium from aqueous media by clay minerals and zeolites as well as the determination of the corresponding chemical processes taking place at the mineral-water interface. The investigation techniques applied for this purpose include, except the conventional wet-chemical and radiochemical methods, advanced spectroscopic methods such as extended X-ray absorption fine structure spectroscopy (EXAFS), Rutherford Backscattered Spectroscopy (RBS), X-ray photoelectron spectroscopy (XPS) and Raman Spectroscopy. These techniques significantly contribute to the characterization of the reacted mineral waters and to the explanation of the structural and compositional characteristics of the sorbed actinide species. Theoretical models regarding the aqueous chemistry and speciation of the actinides have also been developed aiming the elucidation of the complex actinide sorption mechanisms. This contribution will critically review of the existing literature, present recently obtained unpublished results and discuss the necessity of future work in the field. (authors)

  7. Actinide distribution in the human skeleton

    International Nuclear Information System (INIS)

    Kathren, R.L.; McInroy, J.F.; Swint, M.J.

    1985-05-01

    Radiochemical analysis of two half skeletons donated to the United States Transuranium Registry, one from an individual with an occupationally incurred deposition of 241 Am and the other with a deposition of 239 Pu, revealed an inverse linear relationship between the concentration of actinide in the bone ash and the fraction of ash. Two distinct relationships were noted, one for the cranium and the other for the remainder of the skeleton. The results suggest that the actinide content of the skeleton as a whole, Q, can be obtained with an uncertainty of +-50% from analysis of a single sample of any bone (except the cranium) by Q = [(830 C/sub sample/)/(0.61 - f/sub sample/)], in which C/sub sample/ refers to the actinide content per g of ash and f/sub sample/ the fraction of ash (i.e., ratio of dry to wet weight) in the sample. 5 figs., 3 tabs

  8. Neutron scattering studies of the actinides

    International Nuclear Information System (INIS)

    Lander, G.H.

    1979-01-01

    The electronic structure of actinide materials presents a unique example of the interplay between localized and band electrons. Together with a variety of other techniques, especially magnetization and the Mossbauer effect, neutron studies have helped us to understand the systematics of many actinide compounds that order magnetically. A direct consequence of the localization of 5f electrons is the spin-orbit coupling and subsequent spin-lattice interaction that often leads to strongly anisotropic behavior. The unusual phase transition in UO 2 , for example, arises from interactions between quadrupole moments. On the other hand, in the monopnictides and monochalcogenides, the anisotropy is more difficult to understand, but probably involves an interaction between actinide and anion wave functions. A variety of neutron experiments, including form-factor studies, critical scattering and measurements of the elementary excitations have now been performed, and the conceptual picture emerging from these studies will be discussed

  9. Monazite as a suitable actinide waste form

    Energy Technology Data Exchange (ETDEWEB)

    Schlenz, Hartmut; Heuser, Julia; Schmitz, Stephan; Bosbach, Dirk [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Energie und Klimaforschung (IEK), Nukleare Entsorgung und Reaktorsicherheit (IEK-6); Neumann, Andreas [Forschungszentrum Juelich GmbH (Germany). Inst. fuer Energie und Klimaforschung (IEK), Nukleare Entsorgung und Reaktorsicherheit (IEK-6); RWTH Aachen Univ. (Germany). Inst. for Crystallography

    2013-03-01

    The conditioning of radioactive waste from nuclear power plants and in some countries even of weapons plutonium is an important issue for science and society. Therefore the research on appropriate matrices for the immobilization of fission products and actinides is of great interest. Beyond the widely used borosilicate glasses, ceramics are promising materials for the conditioning of actinides like U, Np, Pu, Am, and Cm. Monazite-type ceramics with general composition LnPO{sub 4} (Ln = La to Gd) and solid solutions of monazite with cheralite or huttonite represent important materials in this field. Monazite appears to be a promising candidate material, especially because of its outstanding properties regarding radiation resistance and chemical durability. This article summarizes the most recent results concerning the characterization of monazite and respective solid solutions and the study of their chemical, thermal, physical and structural properties. The aim is to demonstrate the suitability of monazite as a secure and reliable waste form for actinides. (orig.)

  10. Actinide separations by supported liquid membranes

    International Nuclear Information System (INIS)

    Danesi, P.R.; Horwitz, E.P.; Rickert, P.; Chiarizia, R.

    1984-01-01

    The work has demonstrated that actinide removal from synthetic waste solutions using both flat-sheet and hollow-fiber SLM's is a feasible chemical process at the laboratory scale level. The process is characterized by the typical features of SLM's processes: very small quantities of extractant required; the potential for operations with high feed/strip volume ratios, resulting in a corresponding concentration factor of the actinides; and simplicity of operation. Major obstacles to the implementation of the SLM technology to the decontamination of liquid nuclear wastes are the probable low resistance of polypropylene supports to high radiation fields, which may prevent the application to high-level nuclear wastes; the unknown lifetime of the SLM; and the high Na content of the separated actinide solution

  11. Research on Actinides in Nuclear Fuel Cycles

    International Nuclear Information System (INIS)

    Song, Kyu Seok; Park, Yong Joon; Cho, Young Hwan

    2010-04-01

    The electrochemical/spectroscopic integrated measurement system was designed and set up for spectro-electrochemical measurements of lanthanide and actinide ions in high temperature molten salt media. A compact electrochemical cell and electrode system was also developed for the minimization of reactants, and consequently minimization of radioactive waste generation. By applying these equipment, oxidation and reduction behavior of lanthanide and actinide ions in molten salt media have been made. Also, thermodynamic parameter values are determined by interpreting the results obtained from electrochemical measurements. Several lanthanide ions exhibited fluorescence properties in molten salt. Also, UV-VIS measurement provided the detailed information regarding the oxidation states of lanthanide and actinide ions in high temperature molten salt media

  12. Research on Actinides in Nuclear Fuel Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Song, Kyu Seok; Park, Yong Joon; Cho, Young Hwan

    2010-04-15

    The electrochemical/spectroscopic integrated measurement system was designed and set up for spectro-electrochemical measurements of lanthanide and actinide ions in high temperature molten salt media. A compact electrochemical cell and electrode system was also developed for the minimization of reactants, and consequently minimization of radioactive waste generation. By applying these equipment, oxidation and reduction behavior of lanthanide and actinide ions in molten salt media have been made. Also, thermodynamic parameter values are determined by interpreting the results obtained from electrochemical measurements. Several lanthanide ions exhibited fluorescence properties in molten salt. Also, UV-VIS measurement provided the detailed information regarding the oxidation states of lanthanide and actinide ions in high temperature molten salt media

  13. Sorption of trivalent lanthanides and actinides onto montmorillonite: Macroscopic, thermodynamic and structural evidence for ternary hydroxo and carbonato surface complexes on multiple sorption sites.

    Science.gov (United States)

    Fernandes, M Marques; Scheinost, A C; Baeyens, B

    2016-08-01

    The credibility of long-term safety assessments of radioactive waste repositories may be greatly enhanced by a molecular level understanding of the sorption processes onto individual minerals present in the near- and far-fields. In this study we couple macroscopic sorption experiments to surface complexation modelling and spectroscopic investigations, including extended X-ray absorption fine structure (EXAFS) and time-resolved laser fluorescence spectroscopies (TRLFS), to elucidate the uptake mechanism of trivalent lanthanides and actinides (Ln/An(III)) by montmorillonite in the absence and presence of dissolved carbonate. Based on the experimental sorption isotherms for the carbonate-free system, the previously developed 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model needed to be complemented with an additional surface complexation reaction onto weak sites. The fitting of sorption isotherms in the presence of carbonate required refinement of the previously published model by reducing the strong site capacity and by adding the formation of Ln/An(III)-carbonato complexes both on strong and weak sites. EXAFS spectra of selected Am samples and TRLFS spectra of selected Cm samples corroborate the model assumptions by showing the existence of different surface complexation sites and evidencing the formation of Ln/An(III) carbonate surface complexes. In the absence of carbonate and at low loadings, Ln/An(III) form strong inner-sphere complexes through binding to three Al(O,OH)6 octahedra, most likely by occupying vacant sites in the octahedral layers of montmorillonite, which are exposed on {010} and {110} edge faces. At higher loadings, Ln/An(III) binds to only one Al octahedron, forming a weaker, edge-sharing surface complex. In the presence of carbonate, we identified a ternary mono- or dicarbonato Ln/An(III) complex binding directly to one Al(O,OH)6 octahedron, revealing that type-A ternary complexes form with the one

  14. Ground-state electronic structure of actinide monocarbides and mononitrides

    DEFF Research Database (Denmark)

    Petit, Leon; Svane, Axel; Szotek, Z.

    2009-01-01

    The self-interaction corrected local spin-density approximation is used to investigate the ground-state valency configuration of the actinide ions in the actinide monocarbides, AC (A=U,Np,Pu,Am,Cm), and the actinide mononitrides, AN. The electronic structure is characterized by a gradually increa...

  15. New strategies for the chemical separation of actinides and lanthanides

    International Nuclear Information System (INIS)

    Hudson, M.J.; Iveson, P.B.

    2002-01-01

    A general model is proposed for the effective design of ligands for partitioning. There is no doubt that the correct design of a molecule is required for the effective separation by separation of metal ions such as lanthanides(III) and actinides(III). Heterocyclic ligands with aromatic rings systems have a rich chemistry, which is only now becoming sufficiently well understood, in relation to the partitioning process. The synthesis, characterisation and structures of some chosen molecules will be introduced in order to illustrate some important features. For example, the molecule N-butyl-2-amino-4,6-di (2-pyridyl)-1,3,5-triazine (BADPTZ), which is an effective solvent extraction reagent for actinides and lanthanides, has been synthesised, characterised and its interaction with metal ions studied. The interesting and important features of this molecule will be compared with those of other heterocyclic molecules such as 2,6-bis(5-butyl-1,2,4-triazol-3-yl) pyridine (DBTZP), which is a candidate molecule for the commercial separation of actinides and lanthanide elements. Primary Coordination Sphere. One of the most critical features concerning whether a molecule is a suitable extraction reagent is the nature of the binding and co-ordination in the primary co-ordination sphere. This effect will be considered in depth for the selected heterocylic molecules. It will be shown how the bonding of the heterocyclic and nitrate ligands changes as the complete lanthanide series is traversed from lanthanum to lutetium. For effective solvent extraction, the ligand(s) should be able completely to occupy the primary co-ordination sphere of the metal ion to be extracted. Interactions in the secondary co-ordination sphere are of less importance. Inter-complex Hydrogen Bonding Interactions. Another feature that will be considered is the intermolecular binding between ligands when bound to the metal ion. Thus the intermolecular structures between complex molecules will be considered

  16. Sequential analysis of selected actinides in urine

    International Nuclear Information System (INIS)

    Kramer, G.H.

    1980-07-01

    The monitoring of personnel by urinalysis for suspected contamination by actinides necessitated the development and implementation of an analytical scheme that will separate and identify alpha emitting radionuclides of these elements. The present work deals with Pu, Am, and Th. These elements are separated from an ashed urine sample by means of coprecipitation and ion exchange techniques. The final analysis is carried out by electroplating the actinides and counting in a α-spectrometer. Mean recoveries of these elements from urine are: Pu 64%, Am 74% and Th 69%. (auth)

  17. Aqueous actinide complexes: A thermochemical assessment

    International Nuclear Information System (INIS)

    Fuger, J.; Khodakovsky, I.L.; Medvedev, V.A.; Navratil, J.D.

    1979-01-01

    The scope and purpose of an assessment of the thermodynamic properties of the aqueous actinide complexes are presented. This work which, at present, is limited to inorganic ligands and three selected organic ligands (formate, acetate and oxalate), is part of an effort established by the International Atomic Energy Agency to assess the thermodynamic properties of the actinides and their compounds. The problems involved in this work are illustrated by discussing the present status of the assessment as related to a few complex species, (hydroxyl-, fluoride-, carbonate complexes). (orig.) [de

  18. Actinide elements in aquatic and terrestrial environments

    International Nuclear Information System (INIS)

    Bondietti, E.A.; Bogle, M.A.; Brantley, J.N.

    1979-01-01

    Progress is reported on the following research projects: water-sediment interactions of U, Pu, Am, and Cm; relative availability of actinide elements from abiotic to aquatic biota; comparative uptake of transuranic elements by biota bordering Pond 3513; metabolic reduction of 239 Np from Np(V) to Np(IV) in cotton rats; evaluation of hazards associated with transuranium releases to the biosphere; predicting Pu in bone; adsorption--solubility--complexation phenomena in actinide partitioning between sorbents and solution; comparative soil extraction data; and comparative plant uptake data

  19. Hydrothermal processing of actinide contaminated organic wastes

    International Nuclear Information System (INIS)

    Worl, A.; Buelow, S.J.; Le, L.A.; Padilla, D.D.; Roberts, J.H.

    1997-01-01

    Hydrothermal oxidation is an innovative process for the destruction of organic wastes, that occurs above the critical temperature and pressure of water. The process provides high destruction and removal efficiencies for a wide variety of organic and hazardous substances. For aqueous/organic mixtures, organic materials, and pure organic liquids hydrothermal processing removes most of the organic and nitrate components (>99.999%) and facilitates the collection and separation of the actinides. We have designed, built and tested a hydrothermal processing unit for the removal of the organic and hazardous substances from actinide contaminated liquids and solids. Here we present results for the organic generated at the Los Alamos National Laboratory Plutonium Facility

  20. Actinide phosphonate complexes in aqueous solutions

    International Nuclear Information System (INIS)

    Nash, K.L.

    1993-01-01

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

  1. A worldwide perspective on actinide burning

    International Nuclear Information System (INIS)

    Burch, W.D.

    1991-01-01

    Worldwide interest has been evident over the past few years in reexamining the merits of recovering the actinides from spent light-water reactor (LWR) fuel and transmuting them in fast reactors to reduce hazards in geologic repositories. This paper will summarize some of the recent activities in this field. Several countries are embarked on programs of reprocessing and vitrification of present wastes, from which removal of the actinides is largely precluded. The United States is assessing the ideas related to the fast reactor program and the potential application to defense wastes. 18 refs., 2 figs

  2. Molecular dynamics studies of actinide nitrides

    International Nuclear Information System (INIS)

    Kurosaki, Ken; Uno, Masayoshi; Yamanaka, Shinsuke; Minato, Kazuo

    2004-01-01

    The molecular dynamics (MD) calculation was performed for actinide nitrides (UN, NpN, and PuN) in the temperature range from 300 to 2800 K to evaluate the physical properties viz., the lattice parameter, thermal expansion coefficient, compressibility, and heat capacity. The Morse-type potential function added to the Busing-Ida type potential was employed for the ionic interactions. The interatomic potential parameters were determined by fitting to the experimental data of the lattice parameter. The usefulness and applicability of the MD method to evaluate the physical properties of actinide nitrides were studied. (author)

  3. Actinide and fission product separation and transmutation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1993-07-01

    The second international information exchange meeting on actinide and fission product separation and transmutation, took place in Argonne National Laboratory in Illinois United States, on 11-13 November 1992. The proceedings are presented in four sessions: Current strategic system of actinide and fission product separation and transmutation, progress in R and D on partitioning processes wet and dry, progress in R and D on transmutation and refinements of neutronic and other data, development of the fuel cycle processes fuel types and targets. (A.L.B.)

  4. Static and dynamic deformations of actinide nuclei

    International Nuclear Information System (INIS)

    Rozmej, P.

    1985-09-01

    The zero-point quadrupole-hexadecapole vibrations have been taken into account to calculate dynamical deformations for even-even actinide nuclei. The collective and intrinsic motions are separated according to the Born-Oppenheimer approximation. The collective Hamiltonian is constructed using the macroscopic-microscopic method in the potential energy part and the cranking model in the kinetic energy part. The BCS theory with a modified oscillator potential is applied to describe the intrinsic motion of nucleons. A new set of Nilsson potential parameters, which produces a much better description of the properties of light actinide nuclei, has also been found. (orig.)

  5. Influence of additives on the structure and microstructure of lanthanides and actinides oxalates

    International Nuclear Information System (INIS)

    Haidon, Blaise; Vitart, Anne-Lise; Rivenet, Murielle; Arab-Chapelet, Benedicte; Roussel, Pascal; Delahaye, Thibaud; Grandjean, Stephane; Abraham, Francis

    2015-07-01

    Oxalic conversion is a well-known process in the nuclear industry where it is used for precipitating plutonium as an oxalate thereafter calcinated into an oxide. As there is a strong relationship between the morphology of the oxalate precursor and that of the resulting oxide, it is of interest to control the oxalate structure and microstructure during the precipitation step. The influence of additives on the precipitation of neodymium (III) oxalates, non-radioactive analogs of actinides (III) oxalates, was explored. With the use of nitrilotri-methylphosphonic acid (NTMP), the structure and microstructure of the neodymium oxalates are different from that obtained without additive. (authors)

  6. Liquid-liquid extraction of actinides by means of dibutil-N, N-diethylcarbamylphosphanate (DBDECP)

    International Nuclear Information System (INIS)

    Spezzano, P.; Giacomelli, R.; Sarzanini, C.; Volpe, P.; Benzi, P.

    1988-01-01

    The extraction of Th(IV), U(VI), Pu(IV), Am(III) and Cm(III) by dibutyl-N, N-diethilcarbamoylphosphonate (DBDECP) from notric, hydrochloric and perchloric acid solutions has been studies as a function of a number of parameters. The effect of size and structure of the extractant molecules has been investigated for lower homologues of carbamoyphosphonate. After evaluating the effect of the diluent, the extraction of inorganic acid HNO 3 , HCl and HClO 4 and the dipendence of the distribution ratios of the actinides from organic extractant concentration and aqueous acid concentration has been studied for the DBDECP-xilene system

  7. Thermodynamics and Structure of Actinide(IV) Complexes with Nitrilotriacetic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Bonin, L.; Guillaumont, D.; Jeanson, A.; Den Auwer, C.; Moisy, Ph. [CEA Marcoule, DEN, DRCP, SCPS, F-30207 Bagnols Sur Ceze (France); Grigoriev, M. [RAS, AN Frumkin Inst Phys Chem and Electrochem, Moscow 119991 (Russian Federation); Berthet, J.C. [CEA Saclay, DSM, IRAMIS, URA 331, Serv Chim Mol, CNRS, F-91191 Gif Sur Yvette (France); Hennig, C.; Scheinost, A. [Forschungszentrum Dresden Rossendorf, Inst Radiochem, D-01314 Dresden (Germany)

    2009-05-15

    Nitrilotriacetic acid, commonly known as NITA (N(CH{sub 2}CO{sub 2}H){sub 3}), can be considered a representative of the polyamino-carboxylic family. The results presented in this paper describe the thermodynamical complexation and structural investigation of An(IV) complexes with NTA in aqueous solution. In the first part, the stability constants of the An(IV) complexes (An = Pu, Np, U, and Th) have been determined by spectrophotometry. In the second part, the coordination spheres of the actinide cation in these complexes have been described using extended X-ray absorption fine structure spectroscopy and compared to the solid-state structure of (Hpy){sub 2}[U(NTA){sub 2}].H{sub 2}O. These data are further compared to quantum chemical calculations, and their evolution across the actinide series is discussed. In particular, an interpretation of the role of the nitrogen atom in the coordination mode is proposed. These results are considered to be model behavior of polyamino-carboxylic ligands such as diethylenetriamine pentaacetic acid, which is nowadays the best candidate for a chelating agent in the framework of actinide decorporation for the human body. (authors)

  8. Actinide, lanthanide and fission product speciation and electrochemistry in high and low temperature ionic melts

    Energy Technology Data Exchange (ETDEWEB)

    Bhatt, Anand I.; Kinoshita, Hajime; Koster, Anne L.; May, Iain; Sharrad, Clint A.; Volkovich, Vladimir A.; Fox, O. Danny; Jones, Chris J.; Lewin, Bob G.; Charnock, John M.; Hennig, Christoph

    2004-07-01

    There is currently a great deal of research interest in the development of molten salt technology, both classical high temperature melts and low temperature ionic liquids, for the electrochemical separation of the actinides from spent nuclear fuel. We are interested in gaining a better understanding of actinide and key fission product speciation and electrochemical properties in a range of melts. Our studies in high temperature alkali metal melts (including LiCl and LiCl-KCl and CsCl-NaCl eutectics) have focussed on in-situ species of U, Th, Tc and Ru using X-ray absorption spectroscopy (XAS, both EXAFS and XANES) and electronic absorption spectroscopy (EAS). We report unusual actinide speciation in high temperature melts and an evaluation of the likelihood of Ru or Tc volatilization during plant operation. Our studies in lower temperature melts (ionic liquids) have focussed on salts containing tertiary alkyl group 15 cations and the bis(tri-fluor-methyl)sulfonyl)imide anion, melts which we have shown to have exceptionally wide electrochemical windows. We report Ln, Th, U and Np speciation (XAS, EAS and vibrational spectroscopy) and electrochemistry in these melts and relate the solution studies to crystallographic characterised benchmark species. (authors)

  9. Actinide, lanthanide and fission product speciation and electrochemistry in high and low temperature ionic melts

    International Nuclear Information System (INIS)

    Bhatt, Anand I.; Kinoshita, Hajime; Koster, Anne L.; May, Iain; Sharrad, Clint A.; Volkovich, Vladimir A.; Fox, O. Danny; Jones, Chris J.; Lewin, Bob G.; Charnock, John M.; Hennig, Christoph

    2004-01-01

    There is currently a great deal of research interest in the development of molten salt technology, both classical high temperature melts and low temperature ionic liquids, for the electrochemical separation of the actinides from spent nuclear fuel. We are interested in gaining a better understanding of actinide and key fission product speciation and electrochemical properties in a range of melts. Our studies in high temperature alkali metal melts (including LiCl and LiCl-KCl and CsCl-NaCl eutectics) have focussed on in-situ species of U, Th, Tc and Ru using X-ray absorption spectroscopy (XAS, both EXAFS and XANES) and electronic absorption spectroscopy (EAS). We report unusual actinide speciation in high temperature melts and an evaluation of the likelihood of Ru or Tc volatilization during plant operation. Our studies in lower temperature melts (ionic liquids) have focussed on salts containing tertiary alkyl group 15 cations and the bis(tri-fluor-methyl)sulfonyl)imide anion, melts which we have shown to have exceptionally wide electrochemical windows. We report Ln, Th, U and Np speciation (XAS, EAS and vibrational spectroscopy) and electrochemistry in these melts and relate the solution studies to crystallographic characterised benchmark species. (authors)

  10. Actinide-specific complexing agents: their structural and solution chemistry

    International Nuclear Information System (INIS)

    Raymond, K.N.; Freeman, G.E.; Kappel, M.J.

    1983-07-01

    The synthesis of a series of tetracatecholate ligands designed to be specific for Pu(IV) and other actinide(IV) ions has been achieved. Although these compounds are very effective as in vivo plutonium removal agents, potentiometric and voltammetric data indicate that at neutral pH full complexation of the Pu(IV) ion by all four catecholate groups does not occur. Spectroscopic results indicate that the tetracatecholates, 3,4,3-LICAMS and 3,4,3-LICAMC, complex Am(III). The Am(IV)/(III)-catecholate couple (where catecholate = 3,4,3-LICAMS or 3,4,3-LICAMC) is not observed, but may not be observable due to the large currents associated with ligand oxidation. However, within the potential range where ligand oxidation does not occur, these experiments indicate that the reduction potential of free Am(IV)/(III) is probably greater than or equal to + 2.6 V vs NHE or higher. Proof of the complexation of americium in the trivalent oxidation state by 3,4,3-LICAMS and 3,4,3-LICAMC elimates the possibility of tetracatholates stabilizing Am(IV) in vivo

  11. Study of interactions between lanthanides/actinides and humic substances by a steric exclusion chromatographic method

    International Nuclear Information System (INIS)

    Moulin, V.

    1986-01-01

    The knowledge of cation-humic matter interactions has a great importance in order to have a better understanding of the contribution of these substances to the possible transport of radioactive elements in the geosphere via groundwaters. The method chosen to study the formation of soluble species between lanthanides/actinides ions and humic acids from different origins is a chromatographic technique of gel filtration. This dynamic equilibrium method is based on the separation of the formed complex and the free cation by the porous packing gel. Different elements have been studied by this method: UO 2 2+ , Eu 3+ , Th 4+ and global interaction constants have been calculated. The application to transuranic elements is undertaken. (orig.)

  12. Strategic Design and Optimization of Inorganic Sorbents for Cesium, Strontium and Actinides

    International Nuclear Information System (INIS)

    Maginn, Edward J.

    2009-01-01

    The primary objective of the Notre Dame component of the project was computational in nature. The goal was to provide a design tool for the synthesis of optimized sorbents for the removal of cesium, strontium and actinides from nuclear waste solutions. Molecular modeling enables us to observe and better understand the molecular level interactions that govern the selectivity of specific radionuclides in a particular sorbent. The research focused on the development and validation of a suitable and transferable model for all the cations and ion exchangers of interest, nd then subsequent simulations which determined the siting and mobility of water and cations. Speciic accomplishments include: (1) improving existing intermolecular force fields to accurately model the sorbents of interest; (2) utilizing energy-minimizations and molecular dynamics simulations for structural prediction of CST and niobium-substituted CST materials; (3) determining Na+/water positions in polyoxoniobate materials using molecular dynamics simulations; and (4) developing Hybrid Monte Carlo methods for improved structural prediction.

  13. Incorporation of tetravalent actinides in three phosphated matrices: britholite, monazite/brabandite and thorium phosphate diphosphate (β-TPD)

    International Nuclear Information System (INIS)

    Terra, O.

    2005-03-01

    Three phosphate based ceramics were studied for the immobilization of tri- and tetravalent actinides: britholite Ca 9 Nd 1-x An x IV (PO 4 ) 5-x (SiO 4 ) 1+x F 2 , monazite/brabantite solid solutions Ln 1-2x III Ca x An x IP O 4 and Thorium Phosphate Diphosphate (β-TPD) Th 4- xAn x IV (PO 4 ) 4 P 2 O 7 . For each material, the incorporation of thorium and uranium (IV) was studied as a surrogate of plutonium. This work was the early beginning of the incorporation of 239 Pu and/or 238 Pu in order to evaluate the effects of α-decay on the three crystallographic structures. The incorporation of tetravalent cations was carried out by dry chemistry methods, using mechanical grinding to improve the reactivity of the initial mixture then the homogeneity of final solid prepared after calcination at high temperature (1200-1400 deg C). For britholites, the thorium incorporation was complete for weight loading up to 20 wt.%, leading to the preparation of homogeneous and single phase solid solutions when using the coupled substitution (Nd 3+ , PO 4 3- ) ↔ (Th 4+ , SiO 4 4- ). Due to redox problems, the incorporation of uranium was limited to 5 to 8 wt.% and always led to a two-phase mixture of U-britholite and CaU 2 O 5+y . The preparation of homogeneous solid solutions of β-TUPD and of brabantites containing thorium and uranium samples was successfully obtained using three steps of mechanical grinding/calcination. For each matrix, dense pellets were prepared prior to the study of their chemical behaviour during leaching tests. The chemical durability of brabantites and β-TUPD were found to be close to that reported in literature. The formation of neo-formed phases was also evidenced onto the surface of Th-britholite samples. (author)

  14. The interaction of actinide and lanthanide ions with hemoglobin and its relevance to human and environmental toxicology

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Amit, E-mail: amitk@barc.gov.in [Radiation Biology and Health Sciences Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Ali, Manjoor [Radiation Biology and Health Sciences Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Ningthoujam, Raghumani S. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Gaikwad, Pallavi [Department of Zoology, Savitribai Phule Pune University, Pune 411 007, Mumbai (India); Kumar, Mukesh [Solid State, Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Nath, Bimalendu B. [Department of Zoology, Savitribai Phule Pune University, Pune 411 007, Mumbai (India); Pandey, Badri N. [Radiation Biology and Health Sciences Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

    2016-04-15

    Highlights: • The sites of Ln and An interaction in Hb depend upon their charge-to-ionic-radii ratio. • Th(IV), Ce(IV) and U(VI) altered structure and oxygen-binding of Hb. • Spectroscopic studies determined binding characteristics of actinides. • Metal–Hb interaction was tested in an environmentally-important aquatic midge, Chironomus. - Abstract: Due to increasing use of lanthanides/actinides in nuclear and civil applications, understanding the impact of these metal ions on human health and environment is a growing concern. Hemoglobin (Hb), which occurs in all the kingdom of living organism, is the most abundant protein in human blood. In present study, effect of lanthanides and actinides [thorium: Th(IV), uranium: U(VI), lanthanum: La(III), cerium: Ce(III) and (IV)] on the structure and function of Hb has been investigated. Results showed that these metal ions, except Ce(IV) interacted with carbonyl and amide groups of Hb, which resulted in the loss of its alpha-helix conformation. However, beyond 75 μM, these ions affected heme moiety. Metal–heme interaction was found to affect oxygen-binding of Hb, which seems to be governed by their closeness with the charge-to-ionic-radius ratio of iron(III). Consistently, Ce(IV) being closest to iron(III), exhibited a greater effect on heme. Binding constant and binding stoichiometry of Th(IV) were higher than that of U(VI). Experiments using aquatic midge Chironomus (possessing human homologous Hb) and human blood, further validated metal–Hb interaction and associated toxicity. Thus, present study provides a biochemical basis to understand the actinide/lanthanide-induced interference in heme, which may have significant implications for the medical and environmental management of lanthanides/actinides toxicity.

  15. The interaction of actinide and lanthanide ions with hemoglobin and its relevance to human and environmental toxicology

    International Nuclear Information System (INIS)

    Kumar, Amit; Ali, Manjoor; Ningthoujam, Raghumani S.; Gaikwad, Pallavi; Kumar, Mukesh; Nath, Bimalendu B.; Pandey, Badri N.

    2016-01-01

    Highlights: • The sites of Ln and An interaction in Hb depend upon their charge-to-ionic-radii ratio. • Th(IV), Ce(IV) and U(VI) altered structure and oxygen-binding of Hb. • Spectroscopic studies determined binding characteristics of actinides. • Metal–Hb interaction was tested in an environmentally-important aquatic midge, Chironomus. - Abstract: Due to increasing use of lanthanides/actinides in nuclear and civil applications, understanding the impact of these metal ions on human health and environment is a growing concern. Hemoglobin (Hb), which occurs in all the kingdom of living organism, is the most abundant protein in human blood. In present study, effect of lanthanides and actinides [thorium: Th(IV), uranium: U(VI), lanthanum: La(III), cerium: Ce(III) and (IV)] on the structure and function of Hb has been investigated. Results showed that these metal ions, except Ce(IV) interacted with carbonyl and amide groups of Hb, which resulted in the loss of its alpha-helix conformation. However, beyond 75 μM, these ions affected heme moiety. Metal–heme interaction was found to affect oxygen-binding of Hb, which seems to be governed by their closeness with the charge-to-ionic-radius ratio of iron(III). Consistently, Ce(IV) being closest to iron(III), exhibited a greater effect on heme. Binding constant and binding stoichiometry of Th(IV) were higher than that of U(VI). Experiments using aquatic midge Chironomus (possessing human homologous Hb) and human blood, further validated metal–Hb interaction and associated toxicity. Thus, present study provides a biochemical basis to understand the actinide/lanthanide-induced interference in heme, which may have significant implications for the medical and environmental management of lanthanides/actinides toxicity.

  16. Cation Exchange Water Softeners

    Science.gov (United States)

    WaterSense released a notice of intent to develop a specification for cation exchange water softeners. The program has made the decision not to move forward with a spec at this time, but is making this information available.

  17. Transmutation of waste actinides in light water reactors

    International Nuclear Information System (INIS)

    Gorrell, T.C.

    1979-04-01

    Actinide recycle and transmutation calculations were made for three irradiation options of a light water reactor (LWR). The cases considered were: all actinides recycled in regular uranium fuel assemblies; transuranic actinides recycled in separate MOX assemblies with 235 U enrichment of uranium; and transuranic actinides recycled in separate MOX assemblies with plutonium enrichment of natural uranium. When all actinides were recycled in a uniform lattice, the transuranic inventory after ten recycles was 38% of the inventory accumulated without recycle. When the transuranics from two regular uranium assemblies were combined with those recycled from a MOX assembly, the transuranic inventory was reduced 50% after five recycles

  18. Chemical compatibility of HLW borosilicate glasses with actinides

    International Nuclear Information System (INIS)

    Walker, C.T.; Scheffler, K.; Riege, U.

    1978-11-01

    During liquid storage of HLLW the formation of actinide enriched sludges is being expected. Also during melting of HLW glasses an increase of top-to-bottom actinide concentrations can take place. Both effects have been studied. Besides, the vitrification of plutonium enriched wastes from Pu fuel element fabrication plants has been investigated with respect to an isolated vitrification process or a combined one with the HLLW. It is shown that the solidification of actinides from HLLW and actinide waste concentrates will set no principal problems. The leaching of actinides has been measured in salt brine at 23 0 C and 115 0 C. (orig.) [de

  19. Actinide recycle in LMFBRs as a waste management alternative

    International Nuclear Information System (INIS)

    Beaman, S.L.

    1979-01-01

    A strategy of actinide burnup in fast reactor systems has been investigated as an approach for reducing the long term hazards and storage requirements of the actinide waste elements and their decay daughters. The actinide recycle studies also included plutonium burnup studies in the event that plutonium is no longer required as a fuel. Particular emphasis was placed upon the timing of the recycle program, the requirements for separability of the waste materials, and the impact of the actinides on the reactor operations and performance. It is concluded that actinide recycle and plutonium burnout are attractive alternative waste management concepts. 25 refs., 14 figs., 34 tabs

  20. Transmutation of LWR waste actinides in thermal reactors

    International Nuclear Information System (INIS)

    Gorrell, T.C.

    1979-01-01

    Recycle of actinides to a reactor for transmutation to fission products is being considered as a possible means of waste disposal. Actinide transmutation calculations were made for two irradiation options in a thermal (LWR) reactor. The cases considered were: all actinides recycled in regular uranium fuel assemblies, and transuranic actinides recycled in separate mixed oxide (MOX) assemblies. When all actinides were recycled in a uranium lattice, a reduction of 62% in the transuranic inventory was achieved after 10 recycles, compared to the inventory accumulated without recycle. When the transuranics from 2 regular uranium assemblies were combined with those recycled from a MOX assembly, the transuranic inventory was reduced 50% after 5 recycles

  1. Hexagonal perovskites with cationic vacancies. 19. The rhombohedral 12 L stacking polytypes Ba/sub 3/LaBsup(III) (W/sub 2/sup(VI)vacantO/sub 12/)

    Energy Technology Data Exchange (ETDEWEB)

    Rother, H J; Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.). Lehrstuhl fuer Anorganische Chemie 2

    1980-06-01

    Hexagonal perovskites are described for the new type Ba/sub 3/LaBsup(III)(W/sub 2/sup(VI)vacantO/sub 12/) with Bsup(III) = Sc, In, Lu, Yb. According to the intensity calculations for Ba/sub 3/LaIn(W/sub 2/vacantO/sub 12/) they crystallize in a rhombohedral 12 L structure with the sequence (3)(1) respectively (hhcc)/sub 3/; space group R3m. The refined, intensity related R' value is 6.7%.

  2. Lanthanides(3)/ actinides (3) separation by nano-filtration-complexation in aqueous medium

    International Nuclear Information System (INIS)

    Chitry, F.; Pellet-Rostaing, S.; Gozzi, C.; Lemaire, M.; Guy, A.; Foos, J.

    2000-01-01

    Lanthanides(III)/actinides(III) separation is a major research subject in matter of treatment of high activity liquid effluents. Liquid-liquid extraction actually gives the best results for this separation. In order to demonstrate that nano-filtration (NF) is a valuable alternative to liquid-liquid extraction, we tried to separate different lanthanides(III) with a nano-filtration process combined with a selective complexation step. At first DTPA (diethylene-triamine-pentaacetic acid) combined with a Sepa MG-17 (Osmonics) gave a 95% retention of Gd 3+ and a 50% retention of La 3+ . Then new hydrosoluble and more selective ligands derived from DTPA were synthesized. One of them combined with a Sepa MG-17 membrane allowed a 87% retention of Gd 3+ and a 5% retention of La 3+ . The same nano-filtration-complexation system was experimented with an equimolar aqueous solution of Gd 3+ , Pr 3+ and La 3+ . Other experiments in the field of actinides(III)/lanthanides(III) separation were also performed. (authors)

  3. Investigation of actinides speciation within the presence of ligands of interest for decorporation; Etude de la speciation des actinides vis-a-vis de ligands d'interet pour la decorporation

    Energy Technology Data Exchange (ETDEWEB)

    Bonin, L

    2008-01-15

    Data about the behaviour of actinides in biological media are required in order to investigate their decorporation. Those data are obtained through in vivo experiments and the study of chemical speciation of actinides within the presence of biological constituents. A part of this work consists in the development of a method leading to the determination of the speciation of actinides at the oxidation state +IV within the presence of a complexing species, as well as its structure. The method was applied to two types of ligands: 1) a constituent of blood plasma: the citrate anion. The various complexes formed were investigated and their formation constants were quantified. The coordination mode of the ligand was then clarified through a structural study of the complexes, underlining the role of only one carboxylic site and of the alcohol function. 2) chelating agents used for decorporation. The formation constants of complexes of An(IV) with NTA and DTPA were determined. The coordination number of the metallic cation in those complexes as well as the role of the nitrogen atom were proved. Lastly, the behaviour of Pu(IV) within the presence of LIHOPO was investigated. This chelating agent, more efficient than DTPA in the case of in vivo decorporation of Np, forms very stable complexes with the metallic cation. One of those complexes can be assumed to present a stoichiometry 2:3. (author)

  4. Heterogeneous all actinide recycling in LWR all actinide cycle closure concept

    International Nuclear Information System (INIS)

    Tondinelli, Luciano

    1980-01-01

    A project for the elimination of transuranium elements (Waste Actinides, WA) by neutron transmutation is developed in a commercial BWR with U-Pu (Fuel Actinides, FA) recycle. The project is based on the All Actinide Cycle Closure concept: 1) closure of the 'back end' of the fuel cycle, U-Pu coprocessing, 2) waste actinide disposal by neutron transmutation. The reactor core consists of Pu-island fuel assemblies containing WAs in target pins. Two parallel reprocessing lines for FAs and WAs are provided. Mass balance, hazard measure, spontaneous activity during 10 recycles are calculated. Conclusions are: the reduction in All Actinide inventory achieved by Heterogeneous All Actinide Recycling is on the order of 83% after 10 recycles. The U235 enrichment needed for a constant end of cycle reactivity decreases for increasing number of recycles after the 4th recycle. A diffusion-burnup calculation of the pin power peak factors in the fuel assembly shows that design limits can be satisfied. A strong effort should be devoted to the solution of the problems related to high values of spontaneous emission by the target pins

  5. Actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP): FY94 results

    Energy Technology Data Exchange (ETDEWEB)

    Novak, C.F. [ed.

    1995-08-01

    This document contains six reports on actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP). These reports, completed in FY94, are relevant to the estimation of the potential dissolved actinide concentrations in WIPP brines under repository breach scenarios. Estimates of potential dissolved actinide concentrations are necessary for WIPP performance assessment calculations. The specific topics covered within this document are: the complexation of oxalate with Th(IV) and U(VI); the stability of Pu(VI) in one WIPP-specific brine environment both with and without carbonate present; the solubility of Nd(III) in a WIPP Salado brine surrogate as a function of hydrogen ion concentration; the steady-state dissolved plutonium concentrations in a synthetic WIPP Culebra brine surrogate; the development of a model for Nd(III) solubility and speciation in dilute to concentrated sodium carbonate and sodium bicarbonate solutions; and the development of a model for Np(V) solubility and speciation in dilute to concentrated sodium Perchlorate, sodium carbonate, and sodium chloride media.

  6. Actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP): FY94 results

    International Nuclear Information System (INIS)

    Novak, C.F.

    1995-08-01

    This document contains six reports on actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP). These reports, completed in FY94, are relevant to the estimation of the potential dissolved actinide concentrations in WIPP brines under repository breach scenarios. Estimates of potential dissolved actinide concentrations are necessary for WIPP performance assessment calculations. The specific topics covered within this document are: the complexation of oxalate with Th(IV) and U(VI); the stability of Pu(VI) in one WIPP-specific brine environment both with and without carbonate present; the solubility of Nd(III) in a WIPP Salado brine surrogate as a function of hydrogen ion concentration; the steady-state dissolved plutonium concentrations in a synthetic WIPP Culebra brine surrogate; the development of a model for Nd(III) solubility and speciation in dilute to concentrated sodium carbonate and sodium bicarbonate solutions; and the development of a model for Np(V) solubility and speciation in dilute to concentrated sodium Perchlorate, sodium carbonate, and sodium chloride media

  7. Calculated investigation of actinide transmutation in the BOR-60 reactor

    International Nuclear Information System (INIS)

    Zhemkov, I.Yu.; Ishunina, O.V.; Yakovleva, I.V.

    2000-01-01

    One of the prospective actinide burner reactor type is the fast reactor with a 'hard' spectrum and small breeding factor, which is the BOR-60. The calculated investigations demonstrate that Loading up to 40% of minor-actinides to the BOR-60 reactor did not lead to the considerable change of neutron-physical characteristics. The performed calculations show that the BOR- 60 reactor possesses a high efficiency of the minor-actinide and plutonium bum-up (up to 37 kg/(TW · h)) hat is comparable with properties of the actinide burner-reactors under design. The BOR-60 reactor can provide a homogeneous minor-actinide Loading (minor-actinide addition to the standard fuel) to the core and heterogeneous Loading (as separate assemblies-targets with a high minor-actinide fraction) to the first rows of a radial blanket that allows the optimum usage of the reactor and its characteristics. (authors)

  8. ENDF/B-5 Actinides (Rev. 86)

    International Nuclear Information System (INIS)

    Lemmel, H.D.

    1986-05-01

    This document summarizes the contents of the Actinides part of the ENDF/B-5 nuclear data library released by the US National Nuclear Data Center. This library or selective retrievals of it, are available costfree from the IAEA Nuclear Data Section upon request. The present version of the library is the Revision of 1986. (author). Refs, figs and tabs

  9. Trends in actinide processing at Hanford

    International Nuclear Information System (INIS)

    Harmon, H.D.

    1993-09-01

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

  10. Report of the panel on inhaled actinides

    International Nuclear Information System (INIS)

    Anon.

    1978-01-01

    Some topics discussed are as follows: assessment of risks to man of inhaling actinides; use of estimates for developing protection standards; epidemiology of lung cancer in exposed human populations; development of respiratory tract models; and effects in animals: dose- and effect-modifying factors

  11. Actinide and fission product partitioning and transmutation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-07-01

    The third international information exchange meeting on actinide and fission product partitioning and transmutation, took place in Cadarache France, on 12-14 December 1994. The proceedings are presented in six sessions : an introduction session, the major programmes and international cooperation, the systems studies, the reactors fuels and targets, the chemistry and a last discussions session. (A.L.B.)

  12. Placental transfer of plutonium and other actinides

    International Nuclear Information System (INIS)

    Griessl, I.; Stieve, F.E.

    1988-10-01

    The report is based on an extensive literature search. All data available from studies on placental transfer of plutonium and other actinides in man and animals have been collected and analysed, and the report presents the significant results as well as unresolved questions and knowledge gaps which may serve as a waypost to future research work. (orig./MG) [de

  13. Partitioning and Transmutation of minor actinides

    International Nuclear Information System (INIS)

    Koch, L.; Wellum, R.

    1991-01-01

    The partitioning of minor actinides from spent fuels and their transmutation into short-lived fission products has been the topic of two dedicated meetings organized jointly by the European Commission and the OECD. The conclusion of the last meeting in 1980, in short, was that partitioning and transmutation of minor actinides, especially in fast reactors, seemed possible. However, the incentive, which would be a reduction of the radiological hazard to the public, was too small if long-lived fission products were not included. Furthermore this meeting showed that minor actinide targets or possible nuclear fuels containing minor actinides for transmutation had not yet been developed. The European Institute for Transuranium Elements took up this task and has carried it out as a small activity for several years. Interests expressed recently by an expert meeting of the OECD/NEA (Paris, 25 April 1989), which was initiated by the proposed Japanese project Omega, led us to the conclusion that the present state of knowledge should be looked at in a workshop environment. Since the Japanese proposal within the project Omega is based on a broader approach we needed this evaluation to assess the relevance of our present activity and wanted to identifiy additional studies which might be needed to cover possible future demands from the public. This workshop was therefore organized, and participants active in the field from EC countries, the USA and Japan were invited

  14. Supercritical fluid carbon dioxide extraction of actinides

    International Nuclear Information System (INIS)

    Rao, Ankita; Tomar, B.S.

    2016-01-01

    Supercritical fluid extraction (SFE) is a process akin to liquid-liquid or solvent extraction where a Supercritical fluid (SCF) is contacted with a solid/ liquid matrix for the purpose of separating the component of interest from the original matrix. Carbon dioxide is a preferred choice as supercritical fluid (SCF) owing to its moderate critical parameter (P c = 7.38 MPa and T c = 304.1K) coupled with radiation and chemical stability, non toxic nature and low cost. Despite widespread applications for extraction of organic compounds and associated advantages especially liquid waste minimization, the SFE of metal ions was left unexplored for quite some time, as direct metal ion extraction is inefficient due charge neutralization requirement and weak solute-solvent interaction. Neutral SCF soluble metal-ligand complexation is imperative and SFE of actinides was reported only in 1994. Several studies have been carried out on SFE of uranium, thorium and plutonium from nitric acid medium employing different sets of ligands (organophosphorus, diketones, amides). Especially attractive is the possibility of direct dissolution and extraction of actinides employing ligand-acid adducts (like TBP.HNO 3 adduct) from solid matrices of different stages of nuclear fuel cycle viz. ores, spent nuclear fuels and radioactive wastes. Also, partitioning of actinides from fission products has been explored in spent nuclear fuel. These studies on supercritical fluid extraction of actinides indicate a more efficient and environmentally sustainable technology. (author)

  15. Uranium (III)-Plutonium (III) co-precipitation in molten chloride

    Science.gov (United States)

    Vigier, Jean-François; Laplace, Annabelle; Renard, Catherine; Miguirditchian, Manuel; Abraham, Francis

    2018-02-01

    Co-management of the actinides in an integrated closed fuel cycle by a pyrochemical process is studied at the laboratory scale in France in the CEA-ATALANTE facility. In this context the co-precipitation of U(III) and Pu(III) by wet argon sparging in LiCl-CaCl2 (30-70 mol%) molten salt at 705 °C is studied. Pu(III) is prepared in situ in the molten salt by carbochlorination of PuO2 and U(III) is then introduced as UCl3 after chlorine purge by argon to avoid any oxidation of uranium up to U(VI) by Cl2. The oxide conversion yield through wet argon sparging is quantitative. However, the preferential oxidation of U(III) in comparison to Pu(III) is responsible for a successive conversion of the two actinides, giving a mixture of UO2 and PuO2 oxides. Surprisingly, the conversion of sole Pu(III) in the same conditions leads to a mixture of PuO2 and PuOCl, characteristic of a partial oxidation of Pu(III) to Pu(IV). This is in contrast with coconversion of U(III)-Pu(III) mixtures but in agreement with the conversion of Ce(III).

  16. Study of complex formation process between 4′-nitrobenzo-18-crown-6 and yttrium(III cation in some binary mixed non-aqueous solvents using the conductometry method

    Directory of Open Access Journals (Sweden)

    Mahboobeh Vafi

    2017-07-01

    Full Text Available The complexation reaction between Y3+ cation and macrocyclic ligand, 4′-nitrobenzo-18-crown-6 (4′NB18C6, was studied in acetonitrile–methanol (AN–MeOH, acetonitrile–1,2-dichloroethane (AN–DCE, acetonitrile–dimethylformamide (AN–DMF and acetonitrile–ethylacetate (AN–EtOAc binary mixed solvent solutions at different temperatures using the conductometric method. The conductance data show that in most cases, the stoichiometry of the complex formed between 4′NB18C6 and Y3+ cation is 1:1 [M:L], but in the case of AN-DCE binary solution (mol% DCE = 50 at 15, 25 and 35 °C, a 2:1 [M2:L] and also a 2:2 [M2:L2] complexes are formed in solution. The results show that the stoichiometry of the complex formed between 4′NB18C6 and Y3+ cation changes with the composition of the mixed solvents and even with temperature. The stability constant of the 1:1 complex was determined using a computer program, GENPLOT. The stability order of (4′NB18C6.Y3+ complex in pure studied solvents at 25 °C was found to be: EtOAc > AN > MeOH > DMF and in the case of the mixed solvent solutions with 25 mol percent of AN at 25 °C was: AN-DCE > AN-EtOAc > AN-MeOH ∼ AN-DMF. The values of stability constant (logKf of (4′NB18C6.Y3+ complex which were obtained from conductometric data, show that the stability of the complex is not only affected by the nature and composition of the solvent system, but it is also influenced by the temperature. In all cases, a non-linear behavior is observed for changes of logKf of the (4′NB18C6.Y3+ complex versus the composition of the binary mixed solvents. The values of standard thermodynamic quantities (ΔH°c and ΔS°c for the complexation process which were obtained from temperature dependence of the stability constant of (4′NB18C6.Y3+ complex, show that depending on the solvent system, in most cases, the complex is enthalpy and also entropy stabilized, but in some cases, it is stabilized or

  17. ACTINET: a European Network for Actinide Sciences

    International Nuclear Information System (INIS)

    Bernard Boullis; Pascal Chaix

    2006-01-01

    Full text of publication follows: The research in Actinide sciences appear as a strategic issue for the future of nuclear systems. Sustainability issues are clearly in connection with the way actinide elements are managed (either addressing saving natural resource, or decreasing the radiotoxicity of the waste). The recent developments in the field of minor actinide P and T offer convincing indications of what could be possible options, possible future processes for the selective recovery of minor actinides. But they point out, too, some lacks in the basic understanding of key-issues (such as for instance the control An versus Ln selectivity, or solvation phenomena in organic phases). Such lacks could be real obstacles for an optimization of future processes, with new fuel compounds and facing new recycling strategies. This is why a large and sustainable work appears necessary, here in the field of basic actinide separative chemistry. And similar examples could be taken from other aspects of An science, for various applications (nuclear fuel or transmutation targets design, or migration issues,): future developments need a strong, enlarged, scientific basis. The Network ACTINET, established with the support of the European Commission, has the following objectives: - significantly improve the accessibility of the major actinide facilities to the European scientific community, and form a set of pooled facilities, as the corner-stone of a progressive integration process, - improve mobility between the member organisations, in particular between Academic Institutions and National Laboratories holding the pooled facilities, - merge part of the research programs conducted by the member institutions, and optimise the research programs and infrastructure policy via joint management procedures, - strengthen European excellence through a selection process of joint proposals, and reduce the fragmentation of the community by putting critical mass of resources and expertise on

  18. European Europart integrated project on actinide partitioning

    International Nuclear Information System (INIS)

    Madic, C.; Hudson, M.J.

    2005-01-01

    This poster presents the objectives of EUROPART, a scientific integrated project between 24 European partners, mostly funded by the European Community within the FP6. EUROPART aims at developing chemical partitioning processes for the so-called minor actinides (MA) contained in nuclear wastes, i.e. from Am to Cf. In the case of dedicated spent fuels or targets, the actinides to be separated also include U, Pu and Np. The techniques considered for the separation of these radionuclides belong to the fields of hydrometallurgy and pyrometallurgy, as in the previous FP5 programs named PARTNEW and PYROREP. The two main axes of research within EUROPART will be: The partitioning of MA (from Am to Cf) from high burn-up UO x fuels and multi-recycled MOx fuels; the partitioning of the whole actinide family for recycling, as an option for advanced dedicated fuel cycles (and in connection with the studies to be performed in the EUROTRANS integrated project). In hydrometallurgy, the research is organised into five Work Packages (WP). Four WP are dedicated to the study of partitioning methods mainly based on the use of solvent extraction methods, one WP is dedicated to the development of actinide co-conversion methods for fuel or target preparation. The research in pyrometallurgy is organized into four WP, listed hereafter: development of actinide partitioning methods, study of the basic chemistry of trans-curium elements in molten salts, study of the conditioning of the wastes, some system studies. Moreover, a strong management team will be concerned not only with the technical and financial issues arising from EUROPART, but also with information, communication and benefits for Europe. Training and education of young researchers will also pertain to the project. EUROPART has also established collaboration with US DOE and Japanese CRIEPI. (authors)

  19. A new look at actinide recycle

    International Nuclear Information System (INIS)

    Burch, W.D.; Croff, A.G.; Rawlins, J.A.; Schulz, W.W.

    1991-01-01

    This paper will address the justification for reexamination of the value of recovering the minor actinides and certain fission products from spent light-water reactor fuels and describe some of the technical progress that has been made since the major studies of a decade ago. During this time, the US Environmental Protection Agency (EPA) and the Nuclear Regulatory Commission have begun establishing detailed criteria and regulations for geologic repositories. An examination of the hazards of waste disposal relative to the EPA release standards reveals that removal of 99.9% of the actinides (Pu, Am, and Np) reduces these hazards quite close to the EPA standards after 300 years' decay of the strontium and cesium. It may be also useful to remove and separately manage and dispose of certain of the long-lived fission products, such as 99 Tc and 129 I. Much additional work is required to fully assess the appropriate target recoveries as the hazards and risks are more closely examined and as the standards are reworked and refined. The two decades before the projected start of the US repository may present a window of opportunity to introduce several better management practices that act to simplify the repository safety issues. From a technical standpoint, significant progress has been made on recovery of the actinides from aqueous wastes though use of the TRUEX process. Additional work is required to demonstrate the application of the process to spent LWR fuels, but it appears straightforward. In addition, work at the Argonne National Laboratory on the liquid-metal reactor metal fuel cycle shows the relative simplicity of recycle of the actinides in that fast reactor cycle. Much work remains to fully demonstrate that actinides from all secondary waste streams can be removed to the target levels from both the aqueous reprocessing of LWR fuel and the pyro processes for the metal-fueled fast reactor. 9 refs., 2 figs

  20. Synroc tailored waste forms for actinide immobilization

    Energy Technology Data Exchange (ETDEWEB)

    Gregg, Daniel J.; Vance, Eric R. [Australian Nuclear Science and Technology Organisation, Kirrawee (Australia). ANSTOsynroc, Inst. of Materials Engineering

    2017-07-01

    Since the end of the 1970s, Synroc at the Australian Nuclear Science and Technology Organisation (ANSTO) has evolved from a focus on titanate ceramics directed at PUREX waste to a platform waste treatment technology to fabricate tailored glass-ceramic and ceramic waste forms for different types of actinide, high- and intermediate level wastes. The particular emphasis for Synroc is on wastes which are problematic for glass matrices or existing vitrification process technologies. In particular, nuclear wastes containing actinides, notably plutonium, pose a unique set of requirements for a waste form, which Synroc ceramic and glass-ceramic waste forms can be tailored to meet. Key aspects to waste form design include maximising the waste loading, producing a chemically durable product, maintaining flexibility to accommodate waste variations, a proliferation resistance to prevent theft and diversion, and appropriate process technology to produce waste forms that meet requirements for actinide waste streams. Synroc waste forms incorporate the actinides within mineral phases, producing products which are much more durable in water than baseline borosilicate glasses. Further, Synroc waste forms can incorporate neutron absorbers and {sup 238}U which provide criticality control both during processing and whilst within the repository. Synroc waste forms offer proliferation resistance advantages over baseline borosilicate glasses as it is much more difficult to retrieve the actinide and they can reduce the radiation dose to workers compared to borosilicate glasses. Major research and development into Synroc at ANSTO over the past 40 years has included the development of waste forms for excess weapons plutonium immobilization in collaboration with the US and for impure plutonium residues in collaboration with the UK, as examples. With a waste loading of 40-50 wt.%, Synroc would also be considered a strong candidate as an engineered waste form for used nuclear fuel and highly

  1. Autoradiographic study of actinide sorption on climax stock granite

    International Nuclear Information System (INIS)

    Beall, G.W.; O'Kelley, G.D.; Allard, B.

    1980-06-01

    An autoradiographic technique that employed an arrangement for placing in firm contact Polaroid sheet film, a scintillator screen, and the radioactive face of a specimen was applied to a study of the sorption of americium, neptunium, plutonium, and uranium on Climax Stock granite under varying conditions of pH and Eh. Qualitative agreement was found between the sorption of americium on crushed, pure minerals and on the minerals comprising the specimen of Climax Stock granite. The observations also supported a mechanism for reduction of Np(V) to Np(IV) and Pu(VI) to Pu(IV) by Fe(II)-containing minerals. There was no evidence for reduction of U(VI) by the Fe(II)-containing minerals, although the uranium, assumed to be present as UO 2 2+ , appeared to be the only actinide species to exhibit sorption by a simple, cation-exchange mechanism at particular mineral sites. Some implications of these results for nuclear waste isolation are discussed briefly

  2. Investigations on synthesis, coordination behaviour and actinide recovery of unexplored phosphine oxides

    International Nuclear Information System (INIS)

    Veerashekhar Goud, E.; Pavankumar, B.B.; Das, Dhrubajyothi

    2016-01-01

    The search for the development of an optimum extractant for effective separation of a particular metal from a mixture is an active field of research in both chemistry and chemical engineering. These extractants find extensive application in extractive metallurgy and in nuclear fuel cycle (for the separation of actinides from other fission products). In the case of the latter, solvent extraction and ion exchange are two widely employed separation techniques. In this connection, the present paper reports synthesis and structural characterization of various new phosphine oxide derivatives. The coordination behavior of these ligands is studied with some selected lanthanides and actinides shows the proposed structures of La(III) and Th(IV) metal complexes. The purity and structural characterization of the ligands and their corresponding metal complexes are analyzed by various analytical and spectroscopic techniques. Additionally, we have applied Density functional theory (DFT) calculations to understand the electronic structure of some metal complexes formed during the extraction process. (author)

  3. Hexagonal perovskites with cationic vacancies. 8. Vibrational spectroscopic investigations on rhombohedral 18 L-stacking polytypes Ba/sub 6/B/sub 2/sup(III)vacantW/sub 3/sup(VI)O/sub 18/

    Energy Technology Data Exchange (ETDEWEB)

    Schittenhelm, H J; Fadini, A; Kemmler-Sack, S [Tuebingen Univ. (Germany, F.R.)

    1979-10-01

    The vibrational spectra of the 18 L stacking polytypes Ba/sub 6/B/sub 2/sup(III)vacant W/sub 3/O/sub 18/ (space group R3m; sequence (hhcccc)/sub 3/) with Bsup(III) = Lu, Y are reported. The octahedral net consists of W/sub 2/vacantO/sub 12/ and WO/sub 6/ groups, which are isolated from each other by the Ba and B ions. An assignment of the vibrational frequencies has been made with the aid of factor group analysis. For the W/sub 2/vacantO/sub 12/ block a complete force constant calculation is reported.

  4. Hexagonal perovskites with cationic vacancies. 3. Structure determination on compounds of type Ba/sub 2/Bsub(1/3)sup(III)vacantsub(2/3)Resup(VII)O/sub 6/

    Energy Technology Data Exchange (ETDEWEB)

    Kemmler-Sack, S; Wischert, W; Treiber, U [Tuebingen Univ. (Germany, F.R.). Inst. fuer Chemie

    1978-09-01

    Compounds of type Ba/sub 2/Bsub(1/3)sup(III)vacantsub(2/3)Resup(VII)O/sub 6/ with Bsup(III) = rare earth, Y, Sc. In belong to the group of hexagonal perovskite stacking polytypes. For Bsup(III) = Gd, Y structure determinations with powder data have been performed. The refined R' factors are 9.11% for Ba/sub 2/Gdsub(1/3)vacantsub(2/3)ReO/sub 6/ and 12.07% for Ba/sub 2/Ysub(1/3)vacantsub(2/3)ReO/sub 6/. The structure represents a rhombohedral 12 L type (space group R3m) with the sequence hhcchhcchhcc. The lattice contains groups of three octahedra connected by common faces which are linked together by a single octahedron via common vertices. In the block of three face-sharing octahedra the central octahedral lattice site is vacant and the two outer positions are occupied by the rhenium atoms. According to this distribution direct contact of occupied face-sharing octahedra is absent.

  5. Development and demonstration of innovative partitioning processes (i-SANEX and 1-cycle SANEX) for actinide partitioning

    International Nuclear Information System (INIS)

    Wilden, Andreas; Modolo, Giuseppe; Geist, Andreas

    2015-01-01

    For the recovery of the trivalent actinides Am(III) and Cm(III) from PUREX raffinate, two innovative partitioning processes were developed within the European project ACSEPT. In the 'innovative-SANEX' concept, trivalent actinides (An(III)) and lanthanides (Ln(III)) are co-extracted by a TODGA-based solvent, which is then subjected to several stripping steps: selective stripping of An(III) with the hydrophilic ligand SO 3 -Ph-BTP, followed by subsequent stripping of Ln(III). A more challenging route studied also within our laboratories is the direct An(III) separation using a mixture of CyMe 4 BTBP and TODGA, the so-called '1-cycle SANEX' process. Both processes have been successfully demonstrated using spiked simulate solutions in laboratory-scale miniature annular centrifugal contactors using 32-stages flowsheets. The process development and results of the demonstration tests will be presented and discussed. Both processes showed a high recovery of An(III) with high fission-product decontamination factors. The safety of these processes is studied within the current European project SACSESS. (authors)

  6. Adventures in Actinide Chemistry: A Year of Exploring Uranium and Thorium in Los Alamos

    Energy Technology Data Exchange (ETDEWEB)

    Pagano, Justin [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-01-08

    The first part of this collection of slides is concerned with considerations when working with actinides. The topics discussed in the document as a whole are the following: Actinide chemistry vs. transition metal chemistry--tools we can use; New synthetic methods to obtain actinide hydrides; Actinide metallacycles: synthesis, structure, and properties; and Reactivity of actinide metallacycles.

  7. Actinide immobilization in the subsurface environment by in-situ treatment with a hydrolytically unstable organophosphorus complexant: Uranyl uptake by calcium phytate

    International Nuclear Information System (INIS)

    Nash, K.L.; Jensen, M.P.; Schmidt, M.A.

    1997-01-01

    In addition to naturally occurring uranium and thorium, actinide ions exist in the subsurface environment as a result of accidental releases and intentional disposal practices associated with nuclear weapons production. These species present a significant challenge to cost-effective remediation of contaminated environments. An attractive approach to decreasing the probability of actinide migration in the subsurface is to transform the ions into a less mobile form by remote treatment. We have under development a process which relies on a polyfunctional organophosphorus complexant to sequester the mobile metal ions by complexation/cation exchange in the near term, and to subsequently decompose, transforming the actinides into insoluble phosphate mineral forms in the long term. Studies to date include identification of a suitable organophosphorus reagent, profiling of its decomposition kinetics, verification of the formation of phosphate mineral phases upon decomposition of the reagent, and extensive comparison of the actinide uptake ability of the calcium salt of the reagent as compared with hydroxyapatite. In this report, we briefly describe the process with focus on the cation exchange behavior of the calcium salt of the organophosphorus sequestrant

  8. ACSEPT-Partitioning technologies and actinide science: Towards pilot facilities in Europe

    International Nuclear Information System (INIS)

    Bourg, S.; Hill, C.; Caravaca, C.; Rhodes, C.; Ekberg, C.; Taylor, R.; Geist, A.; Modolo, G.; Cassayre, L.; Malmbeck, R.; Harrison, M.; Angelis, G. de; Espartero, A.; Bouvet, S.; Ouvrier, N.

    2011-01-01

    Highlights: → ACSEPT works at developing actinide separation processes for advanced fuel cycles. → ACSEPT develops both aqueous and pyrochemical actinide separation processes. → Homogeneous and heterogeneous recycling strategies are both considered in ACSEPT. → Training and education in actinide chemistry are important issues addressed by ACSEPT. - Abstract: Actinide recycling by separation and transmutation is considered worldwide and particularly in several European countries as one of the most promising strategies to reduce the inventory of radioactive waste and to optimise the use of natural resources. With its multidisciplinary consortium of 34 partners from 12 European countries plus Australia and Japan, the European Research Project ACSEPT (Actinide reCycling by SEParation and Transmutation) aims at contributing to the development of this strategy by studying both hydrometallurgical and pyrochemical partitioning routes. ACSEPT is organised into three technical domains: (i)Considering technically mature aqueous separation processes, ACSEPT works to optimise and select the most promising ones dedicated either to actinide partitioning (for the heterogeneous recycling of actinides in ADS target or specific actinide bearing blanket fuels in fast reactor) or to grouped actinide separation (for the homogeneous recycling of the actinides in fast reactor fuels). In addition, dissolution and conversion studies are underway taking into account the specific requirements of these specific fuels. (ii)Concerning pyrochemical separation processes, ACSEPT focuses on the enhancement of the two reference cores processes selected within FP6-EUROPART. R and D efforts are also devoted to key scientific and technical issues compulsory to set up a complete separation process (head-end steps, salt treatment for recycling and waste management). (iii)By integrating all the experimental results in engineering and system studies, both in hydro and pyro domains, ACSEPT will

  9. A novel dipicolinamide-dicarbollide synergistic solvent system for actinide extraction

    Energy Technology Data Exchange (ETDEWEB)

    Patil, Ajay Bhagwan [Bhabha Atomic Research Centre, Mumbai (India). Radiochemistry Div.; Pune Univ. (India). Garware Research Centre; Pathak, Priyanath; Mohapatra, Prasanta Kumar [Bhabha Atomic Research Centre, Mumbai (India). Radiochemistry Div.; Shinde, Vaishali Sanjay [Pune Univ. (India). Garware Research Centre; Alyapyshev, M.Yu.; Babain, Vasiliy A. [Federal Agency for Atomic Energy, St. Petersburg (Russian Federation). V.G. Khlopin Radium Institute

    2014-09-01

    Solvent extraction studies of several actinide ions such as Am(III), U(VI), Np(IV), Np(VI), Pu(IV) were carried out from nitric acid medium using a synergistic mixture of N,N'-diethyl-N,N'-di(para)fluorophenyl-2,6-dipicolinamide, (DEtD(p)FPhDPA, DPA), and hydrogen dicarbollylcobaltate (H{sup +}CCD{sup -}) dissolved in phenyltrifluoromethylsulphone (PTMS). The effects of different parameters such as aqueous phase acidity (0.01-3 M HNO{sub 3}), oxidation states of metal ions, ligand concentration, nature of diluent and temperature on the extraction behavior of metal ions were studied. The extracted Am(III) species was determined as H{sup +}[Am(DPA){sub 2}(CCD){sub 4}]{sup -} With increasing aqueous phase acidities, the extractability of both Am(III) and Eu(III) was found to decrease. The synergistic mixture showed better extraction in mM concentrations as compared to previously studied dipicolinamides. The thermodynamic studies were performed to calculate heat of extraction reaction and the extraction constants. The proposed synergistic mixture showed good extraction for all the metal ions, though lanthanide actinide separation results are not encouraging. (orig.)

  10. Synthesis and characterisation of nitrogen-containing poly heterocyclic molecules for the complexation of polluting metal cations; Synthese et caracterisation de molecules polyheterocycliques azotees pour la complexation de cations metalliques polluants

    Energy Technology Data Exchange (ETDEWEB)

    Leconte, N

    2007-12-15

    The recovery of actinides(III) from the mixture actinides(III)/lanthanides(III) is a great deal of the nuclear waste management. Experiences have shown that derivatives of 2,6- bis(1,2,4-triazine-3-yl)pyridine (BTP) are able to extract selectively actinides(III) from lanthanides(III). But the properties of these molecules need to be reinforced to exhibit best extraction performances and to resist to the harsh conditions of the extracting processes. Originally functionalized ligands were synthesized and tested in a radioactive medium. In a second part, this work focuses on the control and the detection of actinides(III). This could be done thanks to the use of a chemical sensor such as quartz crystal microbalance. The study of this apparatus required the preliminary synthesis of original complexing BTP-derived structures. The last part of this work deals with the study of new synthetic ways to afford the BTP moiety. The palladium-catalyzed cross-coupling reaction of 3-methylthio-1,2,4-triazine with various 2-stannylated pyridines have been explored. Our investigations have also allowed to develop a method for synthesizing unsymmetrical 1,2,4,5-tetrazine from the cross-coupling reaction between 3-methylthio-6-(morpholine-N-yl)-1,2,4,5-tetrazine and organoboron / organo-stannane derivatives. (author)

  11. Selective extraction of trivalent actinides with hard-soft mixed donor ligands: role of intra-ligand synergism

    International Nuclear Information System (INIS)

    Ghanty, Tapan K.

    2016-01-01

    In recent years, considerable attention has been given to understand the coordination chemistry of trivalent lanthanide (Ln) and actinide (An) with various ligands because of its close link with the nuclear waste management processes. It is well known that lanthanide-actinide separation is a challenging and difficult task because of very similar chemical properties of these two series of ions, which are associated with similar ionic radii and coordination numbers. Recently, we have introduced a new concept, 'intra-ligand synergism', where hard donor atom, such as, oxygen preferentially binds to trivalent actinides (An(III)) as compared to the valence iso-electronic trivalent lanthanides (Ln(III)) in presence of another soft donor centre. In the present work, the conventional concept of selective complexation of actinides with soft donor ligands (either S or N donor) has been modified through exploiting this concept, and thereby the higher selectivity of 1,10-phenanthroline-2,9-dicarboxylamide (PDAM) based ligands, namely PDAM and its isobutyl and decyl derivatives towards Am(III) ion has been predicted theoretically through density functional calculations. Subsequently, several such amide derivatives have been synthesized to optimize the solubility of the ligands in organic phase. Finally, solvent extraction experiments have been carried out to validate the theoretical prediction on the selectivity of oxygen donor ligands towards Am(III) as compared to Eu(III), and a maximum separation factor of about 51 has been achieved experimentally using 2,9-bis(N-decylaminocarbonyl)-1,10-phenanthroline ligand. The separation factor is increased with the decrease in pH, which is very interesting since extraction of the Am 3+ ion is considered to be important under highly acidic conditions from the nuclear waste management point of view. (author)

  12. Selective Media for Actinide Collection and Pre-Concentration: Results of FY 2006 Studies

    Energy Technology Data Exchange (ETDEWEB)

    Lumetta, Gregg J.; Addleman, Raymond S.; Hay, Benjamin P.; Hubler, Timothy L.; Levitskaia, Tatiana G.; Sinkov, Sergey I.; Snow, Lanee A.; Warner, Marvin G.; Latesky, Stanley L.

    2006-11-17

    In this work, we have investigated new materials for potential use in automated radiochemical separations. The work can be divided into three primary tasks: (1) synthesis of new ligands with high affinity for actinide ions, (2) evaluation of new materials for actinide ion affinity, and (3) computational design of advanced ligand architectures for highly selective binding of actinide ions. Ligand Synthesis Work was conducted on synthesizing Kl?ui ligand derivatives containing functionalized pendant groups on the cyclopentadienyl ring. The functionalized pendent groups would allow these ligands to be attached to organic and inorganic solid supports. This work focused on synthesizing the compound Na[Cp?Co(PO(OC2H5)2)3], where Cp?= C5H4C(O)OCH3. Synthesizing this compound is feasible, but the method used in FY 2006 produced an impure material. A modified synthetic scheme has been developed and will be pursued in FY 2007. Work was also initiated on synthesizing bicyclic diamides functionalized for binding to polymeric resins or other surfaces. Researchers at the University of Oregon are collaborators in this work. To date, this effort has focused on synthesizing and characterizing a symmetrically substituted bicyclic diamide ligand with the ?COOH functionality. Again, this synthetic effort will continue into FY 2007. Separations Material Evaluation Work was conducted in FY 2006 to provide a more extensive set of data on the selectivity and affinity of extraction chromatography resins prepared by sorption of Kl?ui ligand onto an inert macroreticular polymeric support. Consistent with previous observations, it was found that these materials strongly bind tetravalent actinides. These materials also adsorb trivalent actinides at low nitric acid concentrations, but the affinity for the trivalent actinides decreases with increasing nitric acid concentration. These materials have relatively low affinity for U(VI), but they do sorb U(VI) to a greater extent than Am(III) at [HNO

  13. Selective Media for Actinide Collection and Pre-Concentration: Results of FY 2006 Studies

    International Nuclear Information System (INIS)

    Lumetta, Gregg J.; Addleman, Raymond S.; Hay, Benjamin P.; Hubler, Timothy L.; Levitskaia, Tatiana G.; Sinkov, Sergey I.; Snow, Lanee A.; Warner, Marvin G.; Latesky, Stanley L.

    2006-01-01

    In this work, we have investigated new materials for potential use in automated radiochemical separations. The work can be divided into three primary tasks: (1) synthesis of new ligands with high affinity for actinide ions, (2) evaluation of new materials for actinide ion affinity, and (3) computational design of advanced ligand architectures for highly selective binding of actinide ions. Ligand Synthesis Work was conducted on synthesizing Kl?ui ligand derivatives containing functionalized pendant groups on the cyclopentadienyl ring. The functionalized pendent groups would allow these ligands to be attached to organic and inorganic solid supports. This work focused on synthesizing the compound Na[Cp?Co(PO(OC2H5)2)3], where Cp?C5H4C(O)OCH3. Synthesizing this compound is feasible, but the method used in FY 2006 produced an impure material. A modified synthetic scheme has been developed and will be pursued in FY 2007. Work was also initiated on synthesizing bicyclic diamides functionalized for binding to polymeric resins or other surfaces. Researchers at the University of Oregon are collaborators in this work. To date, this effort has focused on synthesizing and characterizing a symmetrically substituted bicyclic diamide ligand with the ?COOH functionality. Again, this synthetic effort will continue into FY 2007. Separations Material Evaluation Work was conducted in FY 2006 to provide a more extensive set of data on the selectivity and affinity of extraction chromatography resins prepared by sorption of Kl?ui ligand onto an inert macroreticular polymeric support. Consistent with previous observations, it was found that these materials strongly bind tetravalent actinides. These materials also adsorb trivalent actinides at low nitric acid concentrations, but the affinity for the trivalent actinides decreases with increasing nitric acid concentration. These materials have relatively low affinity for U(VI), but they do sorb U(VI) to a greater extent than Am(III) at [HNO3

  14. Synthesis and characterisation of nitrogen-containing poly heterocyclic molecules for the complexation of polluting metal cations

    International Nuclear Information System (INIS)

    Leconte, N.

    2007-12-01

    The recovery of actinides(III) from the mixture actinides(III)/lanthanides(III) is a great deal of the nuclear waste management. Experiences have shown that derivatives of 2,6- bis(1,2,4-triazine-3-yl)pyridine (BTP) are able to extract selectively actinides(III) from lanthanides(III). But the properties of these molecules need to be reinforced to exhibit best extraction performances and to resist to the harsh conditions of the extracting processes. Originally functionalized ligands were synthesized and tested in a radioactive medium. In a second part, this work focuses on the control and the detection of actinides(III). This could be done thanks to the use of a chemical sensor such as quartz crystal microbalance. The study of this apparatus required the preliminary synthesis of original complexing BTP-derived structures. The last part of this work deals with the study of new synthetic ways to afford the BTP moiety. The palladium-catalyzed cross-coupling reaction of 3-methylthio-1,2,4-triazine with various 2-stannylated pyridines have been explored. Our investigations have also allowed to develop a method for synthesizing unsymmetrical 1,2,4,5-tetrazine from the cross-coupling reaction between 3-methylthio-6-(morpholine-N-yl)-1,2,4,5-tetrazine and organoboron / organo-stannane derivatives. (author)

  15. Actinide oxides synthesis in molten chloride. Structural studies and reaction mechanisms

    International Nuclear Information System (INIS)

    Vigier, J.F.

    2012-01-01

    Pyrochemical processes are studied as potential alternatives to hydrochemical processes for spent nuclear fuel treatment. The CEA pyrochemical process led to a molten LiCl-CaCl 2 (30-70% mol) salt at 700 C with solubilized actinides at the oxidation state (III). The study developed in this thesis concerns actinide oxides synthesis in this media for nuclear fuel re-fabrication. This synthesis was done by wet argon sparging. First, this conversion method is described for neodymium (III) and cerium (III) co-conversion. The conversion rates are around 99.9%. The obtained powders contain mixed oxychloride Ce 1-x Nd x OCl as main component, with a small amount of mixed oxide Ce 1-x Nd x O 2-0,5x for the high cerium ratio. A second oxychloride CeIV(Nd 0.7 Ce 0.3 ) III O 3 Cl is obtained in specific conditions and in very low quantity. The structure of this oxychloride is described in this study. The partially oxidative property of the conversion method induces the oxidation of a part of cerium (III) to oxidation state (IV). In the case of uranium (III) conversion by wet argon sparging, all the uranium is oxidized and give the oxide UO 2 as single compound. The conversion rate for this element is over 99.9% in the molten chloride, but significant amount of uranium is lost by volatilization during the conversion. The study shows the oxygen sensitivity of uranium during the conversion, inducing oxidation over the oxidation state (IV), and giving UO 2+x or uranate CaUO 4 . As a consequence, oxygen led to calcium pollution in the precipitate. Finally, the U(III) and Pu(III) co-conversion study shows the highest precipitation sensitivity of uranium (III) in comparison with plutonium (III), responsible of a successive conversion of the two elements, giving an oxide mixture of UO 2 et PuO 2 with quantitative conversion rate. Surprisingly, the conversion of Pu(III) in the same conditions led to a mixture of PuO 2 and PuOCl, characteristic of a partial oxidation from Pu (III) to Pu

  16. Recovery of actinides from actinide-aluminium alloys by chlorination: Part I

    Energy Technology Data Exchange (ETDEWEB)

    Cassayre, L., E-mail: cassayre@chimie.ups-tlse.fr [Laboratoire de Genie Chimique (LGC), Departement Procedes Electrochimiques, CNRS-UMR 5503, Universite de Toulouse III - Paul Sabatier, 31062 Toulouse (France); Soucek, P.; Mendes, E.; Malmbeck, R.; Nourry, C.; Eloirdi, R.; Glatz, J.-P. [European Commission, JRC, Institute for Transuranium Elements, Postfach 2340, 76125 Karlsruhe (Germany)

    2011-07-01

    Pyrochemical processes in molten LiCl-KCl are being developed in ITU for recovery of actinides from spent nuclear fuel. The fuel is anodically dissolved to the molten salt electrolyte and actinides are electrochemically reduced on solid aluminium cathodes forming solid actinide-aluminium alloys. A chlorination route is being investigated for recovery of actinides from the alloys. This route consists in three steps: Vacuum distillation for removal of the salt adhered on the electrode, chlorination of the actinide-aluminium alloys by chlorine gas and sublimation of the formed AlCl{sub 3}. A thermochemical study showed thermodynamic feasibility of all three steps. On the basis of the conditions identified by the calculations, experiments using pure UAl{sub 3} alloy were carried out to evaluate and optimise the chlorination step. The work was focused on determination of the optimal temperature and Cl{sub 2}/UAl{sub 3} molar ratio, providing complete chlorination of the alloy without formation of volatile UCl{sub 5} and UCl{sub 6}. The results showed high efficient chlorination at a temperature of 150 deg. C.

  17. Recovery of actinides from actinide-aluminium alloys by chlorination: Part I

    International Nuclear Information System (INIS)

    Cassayre, L.; Soucek, P.; Mendes, E.; Malmbeck, R.; Nourry, C.; Eloirdi, R.; Glatz, J.-P.

    2011-01-01

    Pyrochemical processes in molten LiCl-KCl are being developed in ITU for recovery of actinides from spent nuclear fuel. The fuel is anodically dissolved to the molten salt electrolyte and actinides are electrochemically reduced on solid aluminium cathodes forming solid actinide-aluminium alloys. A chlorination route is being investigated for recovery of actinides from the alloys. This route consists in three steps: Vacuum distillation for removal of the salt adhered on the electrode, chlorination of the actinide-aluminium alloys by chlorine gas and sublimation of the formed AlCl 3 . A thermochemical study showed thermodynamic feasibility of all three steps. On the basis of the conditions identified by the calculations, experiments using pure UAl 3 alloy were carried out to evaluate and optimise the chlorination step. The work was focused on determination of the optimal temperature and Cl 2 /UAl 3 molar ratio, providing complete chlorination of the alloy without formation of volatile UCl 5 and UCl 6 . The results showed high efficient chlorination at a temperature of 150 deg. C.

  18. Minor actinide transmutation on PWR burnable poison rods

    International Nuclear Information System (INIS)

    Hu, Wenchao; Liu, Bin; Ouyang, Xiaoping; Tu, Jing; Liu, Fang; Huang, Liming; Fu, Juan; Meng, Haiyan

    2015-01-01

    Highlights: • Key issues associated with MA transmutation are the appropriate loading pattern. • Commercial PWRs are the only choice to transmute MAs in large scale currently. • Considerable amount of MA can be loaded to PWR without disturbing k eff markedly. • Loading MA to PWR burnable poison rods for transmutation is an optimal loading pattern. - Abstract: Minor actinides are the primary contributors to long term radiotoxicity in spent fuel. The majority of commercial reactors in operation in the world are PWRs, so to study the minor actinide transmutation characteristics in the PWRs and ultimately realize the successful minor actinide transmutation in PWRs are crucial problem in the area of the nuclear waste disposal. The key issues associated with the minor actinide transmutation are the appropriate loading patterns when introducing minor actinides to the PWR core. We study two different minor actinide transmutation materials loading patterns on the PWR burnable poison rods, one is to coat a thin layer of minor actinide in the water gap between the zircaloy cladding and the stainless steel which is filled with water, another one is that minor actinides substitute for burnable poison directly within burnable poison rods. Simulation calculation indicates that the two loading patterns can load approximately equivalent to 5–6 PWR annual minor actinide yields without disturbing the PWR k eff markedly. The PWR k eff can return criticality again by slightly reducing the boric acid concentration in the coolant of PWR or removing some burnable poison rods without coating the minor actinide transmutation materials from PWR core. In other words, loading minor actinide transmutation material to PWR does not consume extra neutron, minor actinide just consumes the neutrons which absorbed by the removed control poisons. Both minor actinide loading patterns are technically feasible; most importantly do not need to modify the configuration of the PWR core and

  19. On the solvation of actinide ions

    International Nuclear Information System (INIS)

    Hagberg, D.

    2007-01-01

    Complete text of publication follows: Simulation of the universal ions in water solution is a standardized tool commonly used today. The route to simulation of actinide ions is normally tough because the evaluation of the simulation parameters are normally not given empirically and standard Hartree-Fock calculations are not accurate enough. We use multiconfigurational quantum chemical calculations when deriving the parameters for actinide ion-water potential [1]. The parameters are then simulated using classical molecular dynamics. A case study of the Cm 3+ ion will be presented on the poster. Results from the simulations will be also be discussed, e.g. the radial distribution functions and the coordination number. [1] D. Hagberg, G. Karlstrom, B.O. Roos and L. Gagliardi The coordination of uranyl in water: a combined quantum chemical and molecular simulation study J. Am. Chem. Soc. 127, 14250-14256 (2005)

  20. Actinide and fission product separation and transmutation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1991-07-01

    The first international information exchange meeting on actinide and fission product separation and transmutation, took place in Mito in Japan, on 6-8 November 1990. It starts with a number of general overview papers to give us some broad perspectives. Following that it takes a look at some basic facts about physics and about the quantities of materials it is talking about. Then it proceeds to some specific aspects of partitioning, starting with evolution from today commercially applied processes and going on to other possibilities. At the end of the third session it takes a look at the significance of partitioning and transmutation of actinides before it embarks on two sessions on transmutation, first in reactors and second in accelerators. The last session is designed to throw back into the discussion the main points which need to be looked at when considering future work in this area. (A.L.B.)

  1. Chemistry of the actinide elements. Second edition

    International Nuclear Information System (INIS)

    Katz, J.J.; Seaborg, G.T.; Morss, L.R.

    1987-01-01

    This is an exhaustive, updated discourse on the chemistry of Actinides, Volume 1 contains a systematic coverage of the elements Ac, Th, Pa, U, Np, and Pu, which constitutes Part 1 of the work. The characterization of each element is discussed in terms of its nuclear properties, occurrence, preparation, atomic and metallic properties, chemistry of specific compounds, and solution chemistry. The first part of Volume 2 follows the same format as Volume 1 but is confined to the elements Am, Cm, Bk, Cf, and Es, plus a more condensed coverage of the Transeinsteinium elements (Fm, Md, No, Lw, and 104-109). Part 2 of this volume is devoted to a discussion of the actinide elements in general, with a specific focus on electronic spectra, thermodynamic and magnetic properties, the metallic state, structural chemistry, solution kinetics, organometallic chemistry for σ- and π-bonded compounds, and some concluding remarks on the superheavy elements

  2. The thermodynamic functions of gaseous actinide elements

    International Nuclear Information System (INIS)

    Rand, M.H.

    1979-01-01

    The actinide gases have large number of unobserved energy states - up to 3 x 10 6 for Pu(g) - which could contribute to the partition function and its derivatives, from which the thermal functions of these gases are calculated. Existing compilations have simply ignored these levels. By making reasonable assumptions as to the distribution of these energy states, their effect on the functions can be calculated. It is concluded that the existing compilations will be inadequate above approximately 2000K. The effect is particularly marked on the heat capacity. For example, when unobserved levels for Pu(g) are included, the heat capacity of Pu(g) reaches a maximum value of more than 12R at 3200K. Similar considerations will apply to the gaseous actinide ions. (orig.) [de

  3. Actinide and fission product separation and transmutation

    International Nuclear Information System (INIS)

    1991-01-01

    The first international information exchange meeting on actinide and fission product separation and transmutation, took place in Mito in Japan, on 6-8 November 1990. It starts with a number of general overview papers to give us some broad perspectives. Following that it takes a look at some basic facts about physics and about the quantities of materials it is talking about. Then it proceeds to some specific aspects of partitioning, starting with evolution from today commercially applied processes and going on to other possibilities. At the end of the third session it takes a look at the significance of partitioning and transmutation of actinides before it embarks on two sessions on transmutation, first in reactors and second in accelerators. The last session is designed to throw back into the discussion the main points which need to be looked at when considering future work in this area. (A.L.B.)

  4. Minor actinide transmutation in accelerator driven systems

    Energy Technology Data Exchange (ETDEWEB)

    Friess, Friederike [IANUS, TU Darmstadt (Germany)

    2015-07-01

    Transmutation of radioactive waste, the legacy of nuclear energy use, gains rising interest. This includes the development of facilities able to transmute minor actinides (MA) into stable or short-lived isotopes before final disposal. The most common proposal is to use a double-strata approach with accelerator-driven-systems (ADS) for the efficient transmutation of MA and power reactors to dispose plutonium. An ADS consists of a sub-critical core that reaches criticality with neutrons supplied by a spallation target. An MCNP model of the ADS system Multi Purpose Research Reactor for Hightech Applications will be presented. Depletion calculations have been performed for both standard MOX fuel and transmutation fuel with an increased content of minor actinides. The resulting transmutation rates for MAs are compared to published values. Special attention is given to selected fission products such as Tc-99 and I-129, which impact the radiation from the spent fuel significantly.

  5. Actinides: from heavy fermions to plutonium metallurgy

    International Nuclear Information System (INIS)

    Smith, J.L.; Fisk, Z.; Hecker, S.S.

    1984-01-01

    The actinide elements mark the emergence of 5f electrons. The f electrons possess sufficiently unusual characteristics that their participation in atomic binding often result in dramatic changes in properties. This provides an excellent opportunity to study the question of localization of electrons; a question that is paramount in predicting the physical and chemical properties of d and f electron transition metals. The transition region between localized (magnetic) and itinerant (often superconducting) behavior provides for many interesting phenomena such as structural instabilities (polymorphism), spin fluctuations, mixed valences, charge density waves, exceptional catalytic activity and hydrogen storage. This region offers most interesting behavior such as that exhibited by the actinide compounds UBe 13 and UPt 3 . Both compounds are heavy-fermion superconductors in which both magnetic and superconducting behavior exist in the same electrons. The consequences of f-electron bonding (which appears greatest at Plutonium) show dramatic effects on phase stability, alloying behavior, phase transformations and mechanical behavior

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

    International Nuclear Information System (INIS)

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

    1994-01-01

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

  7. Actinides reduction by recycling in a thermal reactor

    International Nuclear Information System (INIS)

    Ramirez S, J. R.; Martinez C, E.; Balboa L, H.

    2014-10-01

    This work is directed towards the evaluation of an advanced nuclear fuel cycle in which radioactive actinides could be recycled to remove most of the radioactive material; firstly a production reference of actinides in standard nuclear fuel of uranium at the end of its burning in a BWR reactor is established, after a fuel containing plutonium is modeled to also calculate the actinides production in MOX fuel type. Also it proposes a design of fuel rod containing 6% of actinides in a matrix of uranium from the tails of enrichment, then four standard uranium fuel rods are replaced by actinides rods to evaluate the production and transmutation thereof, the same procedure was performed in the fuel type MOX and the end actinide reduction in the fuel was evaluated. (Author)

  8. Strength of Coriolis Coupling in actinide nuclei

    International Nuclear Information System (INIS)

    Peker, L.K.; Rasmussen, J.O.; Hamilton, J.H.

    1982-01-01

    Coriolis Coupling V/sub cor/ plays an important role in deformed nuclei. V/sub cor/ is proportional to h 2 /J[j (j + 1) -Ω (Ω + 1)]/sup 1/2/ and therefore is particularly significant in the nuclei with large j and low Ω Nilsson levels close to Fermi surface: n(i/sub 13/2/) in A = 150 to 170 rare-earth nuclei and p(i/sub 13/2/) and n(j/sub 15/2/) in A greater than or equal to 224 actinide nuclei. Because of larger j (n(j/sub 15/2/) versus n(i/sub 13/2/)) and smaller deformations (β approx. = 0.22 versus β 0.28) it was reasonable to expect that in actinide nuclei Coriolis effects are stronger than in the rare earth nuclei. Recently it was realized that the strength of observed Coriolis effects depends not only on the genuine Coriolis Coupling but also on the interplay between Coriolis ad pairing forces which leads to an interference between the wave functions of two mixing rotational bands. As a consequence the effective interaction V/sub eff/ of both bands is an oscillating function of the degree of shell filling (or chemical potential lambda F). It was shown that in the rare earth nuclei this interference strongly influenced conclusions about the trends in the Coriolis coupling strength and explained many of the observed band-mixing features (the sharpness of back banding curves, details of the blocking effect etc.). From theoretical analysis it was concluded that in the majority of actinide nuclei the effective interaction V/sub eff/ is strong, and therefore the Coriolis band-mixing have to be very strong. In this paper we would like to demonstrate that contrary to these predictions experimental data suggest that Coriolis band mixing in studied actinide nuclei is relatively weak and possibly significantly weaker than in rare earth nuclei

  9. Actinide and fission product partitioning and transmutation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-07-01

    The fourth international information exchange meeting on actinide and fission product partitioning and transmutation, took place in Mito City in Japan, on 111-13 September 1996. The proceedings are presented in six sessions: the major programmes and international cooperation, the partitioning and transmutation programs, feasibility studies, particular separation processes, the accelerator driven transmutation, and the chemistry of the fuel cycle. (A.L.B.)

  10. Actinide burning in the integral fast reactor

    International Nuclear Information System (INIS)

    Chang, Y.I.

    1993-01-01

    During the past few years, Argonne National Laboratory has been developing the integral fast reactor (IFR), an advanced liquid-metal reactor concept. In the IFR, the inherent properties of liquid-metal cooling are combined with a new metallic fuel and a radically different refining process to allow breakthroughs in passive safety, fuel cycle economics, and waste management. A key feature of the IFR concept is its unique pyroprocessing. Pyroprocessing has the potential to radically improve long-term waste management strategies by exploiting the following attributes: 1. Minor actinides accompany plutonium product stream; therefore, actinide recycling occurs naturally. Actinides, the primary source of long-term radiological toxicity, are removed from the waste stream and returned to the reactor for in situ burning, generating useful energy. 2. High-level waste volume from pyroprocessing call be reduced substantially as compared with direct disposal of spent fuel. 3. Decay heat loading in the repository can be reduced by a large factor, especially for the long-term burden. 4. Low-level waste generation is minimal. 5. Troublesome fission products, such as 99 Tc, 129 I, and 14 C, are contained and immobilized. Singly or in combination, the foregoing attributes provide important improvements in long-term waste management in terms of the ease in meeting technical performance requirements (perhaps even the feasibility of demonstrating that technical performance requirements can be met) and perhaps also in ultimate public acceptance. Actinide recycling, if successfully developed, could well help the current repository program by providing an opportunity to enhance capacity utilization and by deferring the need for future repositories. It also represents a viable technical backup option in the event unforeseen difficulties arise in the repository licensing process

  11. Cation radicals of xanthophylls.

    Science.gov (United States)

    Galinato, Mary Grace I; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R; Frank, Harry A

    2007-10-01

    Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, beta-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing pi-chain length. However, zeaxanthin and beta-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of beta-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

  12. Identifi cation of Sectarianism

    Directory of Open Access Journals (Sweden)

    Martinovich Vladimir

    2016-03-01

    Full Text Available «New religious movements and society» is traditionally one of the most sophisticated topics in the area of new religions studies. Its problem field is so huge that up to now by far not all important research themes where even touched by scientists from all over the world. The problem of the process of the identification of sectarianism by diff erent societal institutions is one of such untouched themes that is taken as the main subject of this article. This process by itself is an inseparable part of the every societal deliberate reaction to the very existence of unconventional religiosity, its unstructured and mainly structured types. The focal point of the article is step-by-step analysis of the general structure elements of the process of the identification of sectarianism without any reference to the specific time and place of its flow. Special attention is paid to the analysis of the subjects of the identification of sectarianism, to the criteria for religious groups to be qualified as new religious movements, and to the specific features of the process of documents filtration. The causes of selective perception of sectarianism are disclosed. Some main consequences and unpredictable outcomes of the process of the identification of sectarianism are described.

  13. BWR Assembly Optimization for Minor Actinide Recycling

    International Nuclear Information System (INIS)

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

    2010-01-01

    The Primary objective of the proposed project is to apply and extend the latest advancements in LWR fuel management optimization to the design of advanced boiling water reactor (BWR) fuel assemblies specifically for the recycling of minor actinides (MAs). A top-level objective of the Advanced Fuel Cycle Systems Analysis program element of the DOE NERI program is to investigate spent fuel treatment and recycling options for current light water reactors (LWRs). Accordingly, this project targets to expand the traditional scope of nuclear fuel management optimization into the following two complementary specific objectives: (1) To develop a direct coupling between the pin-by-pin within-bundle loading control variables and core-wide (bundle-by-bundle) optimization objectives, (2) to extend the methodology developed to explicitly encompass control variables, objectives, and constraints designed to maximize minor actinide incineration in BWR bundles and cycles. The first specific objective is projected to 'uncover' dormant thermal margin made available by employing additional degrees of freedom within the optimization process, while the addition of minor actinides is expected to 'consume' some of the uncovered thermal margin. Therefore, a key underlying goal of this project is to effectively invest some of the uncovered thermal margin into achieving the primary objective.

  14. Measurement of actinide neutron cross sections

    International Nuclear Information System (INIS)

    Firestone, Richard B.; Nitsche, Heino; Leung, Ka-Ngo; Perry, DaleL.; English, Gerald

    2003-01-01

    The maintenance of strong scientific expertise is critical to the U.S. nuclear attribution community. It is particularly important to train students in actinide chemistry and physics. Neutron cross-section data are vital components to strategies for detecting explosives and fissile materials, and these measurements require expertise in chemical separations, actinide target preparation, nuclear spectroscopy, and analytical chemistry. At the University of California, Berkeley and the Lawrence Berkeley National Laboratory we have trained students in actinide chemistry for many years. LBNL is a leader in nuclear data and has published the Table of Isotopes for over 60 years. Recently, LBNL led an international collaboration to measure thermal neutron capture radiative cross sections and prepared the Evaluated Gamma-ray Activation File (EGAF) in collaboration with the IAEA. This file of 35, 000 prompt and delayed gamma ray cross-sections for all elements from Z=1-92 is essential for the neutron interrogation of nuclear materials. LBNL has also developed new, high flux neutron generators and recently opened a 1010 n/s D+D neutron generator experimental facility

  15. Value of burnup credit beyond actinides

    International Nuclear Information System (INIS)

    Lancaster, D.; Fuentes, E.; Kang, Chi.

    1997-01-01

    DOE has submitted a topical report to the NRC justifying burnup credit based only on actinide isotopes (U-234, U-235, U-236, U-238, Pu-238, Pu-239, Pu-240, Pu-241, Pu-242, and Am-241). When this topical report is approved, it will allow a great deal of the commercial spent nuclear fuel to be transported in significantly higher capacity casks. A cost savings estimate for shipping fuel in 32 assembly (burnup credit) casks as opposed to 24 assembly (non-burnup credit) casks was previously presented. Since that time, more detailed calculations have been performed using the methodology presented in the Actinide-Only Burnup Credit Topical Report. Loading curves for derated casks have been generated using actinide-only burnup credit and are presented in this paper. The estimates of cost savings due to burnup credit for shipping fuel utilizing 32, 30, 28, and 24 assembly casks where only the 24 assembly cask does not burnup credit have been created and are discussed. 4 refs., 2 figs

  16. Study on remain actinides recovery in pyro reprocessing

    International Nuclear Information System (INIS)

    Suharto, Bambang

    1996-01-01

    The spent fuel reprocessing by dry process called pyro reprocessing have been studied. Most of U, Pu and MA (minor actinides) from the spent fuel will be recovered and be fed back to the reactor as new fuel. Accumulation of remain actinides will be separated by extraction process with liquid cadmium solvent. The research was conducted by computer simulation to calculate the stage number required. The calculation's results showed on the 20 stages extractor more than 99% actinides can be separated. (author)

  17. Successive change regularity of actinide properties with atomic number

    International Nuclear Information System (INIS)

    Yang Xuexian

    1990-08-01

    The development and achievements on chemistry of actinide elements are summarised. The relations of properties of actinides to their electronic configurations of valence electronic shells are discussed. Some anomalies of solid properties, the radius contraction, the stable state effect of f 7n -orbits (n = 0, 1, 2) and the tetrad effect of oxidation states, etc., with atomic number (Z) are described. 31 figures appended show directly the successive change regularity of actinide properties with Z

  18. Actinide recycle potential in the integral fast reactor

    International Nuclear Information System (INIS)

    Chang, Y.I.

    1993-01-01

    The Integral Fast Reactor (IFR) fuel cycle holds promise for substantial improvements in economics, diversion-resistance, and waste management. In the IFR pyroprocessing, minor actinides accompany plutonium product stream, and therefore, actinide recycle occurs naturally. The fast neutron spectrum of the IFR makes it an ideal actinide burner, as well. This paper discusses technical features of the IFR fuel cycle, its technical progress, the development status, and potential implications on long-term waste management

  19. Preparation, properties, and some recent studies of the actinide metals

    International Nuclear Information System (INIS)

    Haire, R.G.

    1985-01-01

    The actinide elements form a unique series of metals. The variation in their physial properties combined with the varying availability of the different elements offers a challenge to the preparative scientist. This article provides a brief review of selected methods used for preparing μg to kg amounts of the actinide metals and the properties of these metals. In addition, some recent studies on selected actinide metals are discussed. 62 refs

  20. Hydrothermal decomposition of actinide(IV oxalates: a new aqueous route towards reactive actinide oxide nanocrystals

    Directory of Open Access Journals (Sweden)

    Walter Olaf

    2016-01-01

    Full Text Available The hydrothermal decomposition of actinide(IV oxalates (An= Th, U, Pu at temperatures between 95 and 250 °C is shown to lead to the production of highly crystalline, reactive actinide oxide nanocrystals (NCs. This aqueous process proved to be quantitative, reproducible and fast (depending on temperature. The NCs obtained were characterised by X-ray diffraction and TEM showing their size to be smaller than 15 nm. Attempts to extend this general approach towards transition metal or lanthanide oxalates failed in the 95–250 °C temperature range. The hydrothermal decomposition of actinide oxalates is therefore a clean, flexible and powerful approach towards NCs of AnO2 with possible scale-up potential.

  1. Coprecipitation of the lanthanide and actinide elements with some carbonato and sulfato complexes

    International Nuclear Information System (INIS)

    Saito, A.; Morimoto, T.; Ueno, K.

    1980-01-01

    Coprecipitation of Eu(III), Th(IV), U(VI), Np(V), Am(III) and Cm(III) with carbonato and sulfato complexes of Nd(III), Th(IV) and U(VI) containing [Co(NH 3 ) 6 ] 3+ cation was investigated. Experiments were made using radioactive tracers. It is assumed that coprecipitation is mainly due to mixed crystal formation. The requirement for a large extent of coprecipitation is the similarity in ionic size, ionic charge and ionic species of the participating ions. In particular, Th(IV) sulfato complex carries tri- tetra- and hexavalent ions in quite high yields. (author)

  2. Position of actinide elements in the periodic table : evolution of a generalised form (Preprint no. SSC-33)

    International Nuclear Information System (INIS)

    Nathaniel, T.N.

    1991-01-01

    All the actinides and lanthanides are placed in III group and are shown separately, in the most popular forms of the periodic table, including the latest version of IUPAC. This has been leading to an avoidable debate i.e. whether to place La and Ac or Lu and Lw below Sc and Y in the III-B group. Apart from this, the group characteristic nature of most of the actinides elements, demands that a more appropriate position is to be given to these f block elements. The situation is more complex in the higher periods, in which new elements belonging to g block, h block, ... are to be included. Also, there seems to be no consensus in following a uniform and acceptable subgroup notation. The author arrived at a new form of the periodic table to successfully sort out all these issues. The table is presented. (author). 10 refs., 1 fig

  3. Partitioning of Minor Actinides from High Active Raffinates using Bis-Diglycol-amides (BisDGA) as new efficient Extractants

    Energy Technology Data Exchange (ETDEWEB)

    Modolo, G.; Vijgen, H. [Forschungszentrum Juelich GmbH, Institute for Energy Research, Safety Research and Reactor Technology, 52425 Juelich (Germany); Espartero, A.G. [Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas (CIEMAT), Avda. Complutense 22, 28040-Madrid (Spain); Prados, P. [Departamento de Quimica Organica, Facultad de Ciencias, Universidad Autonoma de Madrid - UAM, carretera de Colmenar Viejo km 15.3, 28049-Madrid (Spain); Mendoza, J. de [Departamento de Quimica Organica, Facultad de Ciencias, Universidad Autonoma de Madrid - UAM, carretera de Colmenar Viejo km 15.3, 28049-Madrid (Spain); Institut Catala d' Investigacio Quimica (ICIQ) Av. Paisos Catalans 16, 43007-Tarragona (Spain)

    2008-07-01

    Two new polyamide extractants has been selected, namely UAM-069 and UAM-081, both synthesized at the University of Madrid (UAM), to develop a new separation process. These two ligands are bis-diglycol-amides, consisting of two diglycol-amides moieties grafted on an aromatic platform (UAM-069) or on an aliphatic linker (UAM-081), respectively. The extraction of actinides and fission products was studied from synthetic PUREX raffinate. Actinides(III) and lanthanides(III) are highly extracted from acidities > 1 mol/L HNO{sub 3}. The extraction of Zr, Mo and Pd could be suppressed with complexing agents such as oxalic acid and HEDTA. In the present paper the results of the batch extraction results are presented which serve for the development of a new continuous counter current process to be tested in centrifugal contactors. (authors)

  4. Biotransformation of uranium and other actinides in radioactive wastes

    International Nuclear Information System (INIS)

    Francis, A.J.

    1998-01-01

    Microorganisms affect the solubility, bioavailability, and mobility of actinides in radioactive wastes. Under appropriate conditions, actinides are solubilized or stabilized by the direct enzymatic or indirect nonenzymatic actions of microorganisms. Biotransformation of various forms of uranium (ionic, inorganic, and organic complexes) by aerobic and anaerobic microorganisms has been extensively studied, whereas limited information is available on other important actinides (Th, Np, Pu, and Am). Fundamental information on the mechanisms of biotransformation of actinides by microbes under various environmental conditions will be useful in predicting the long-term performance of waste repositories and in developing strategies for waste management and remediation of contaminated sites. (orig.)

  5. Extraction of trivalent lanthanides and actinides by a synergistic mixture of thenoyltrifluoroacetone and a linear polyether

    International Nuclear Information System (INIS)

    Ensor, D.D.; Shah, A.H.

    1984-01-01

    Mixtures of a two component system, a linear polyether, 1,13-bis[8-quinolyl]-1,4,7,10,13-pentaoxatridecane, K-5, and thenoyltrifluoroacetone, HTTA, have been shown to exhibit synergistic character in the extraction of trivalent lanthanides and actinides. The effect of the addition of K-5 to the organic phase on the extractions of Ce(III), Eu(III), Tm(III), Am(III), Cm(III), Bk(III), and Cf(III) by HTTA in chloroform from 0.5M NaNO 3 at 25 0 C has been measured. These results indicate the extraction is enhanced by the formation of M(TTA) 3 K-5 adduct in the organic phase. The organic phase stability constants for the formation of these synergistic species have been calculated for all the metals studied. The magnitude of these organic phase stability constants for K-5 are similar to other common neutral donors. The order of stability does not follow the normal trend based on charge-to-radius ratio, but follows a pattern based on size, with Am(III) being the most stable

  6. Interactions of Microbes found at Aespoe Underground Lab with Actinides such as Curium, Plutonium and Uranium

    Energy Technology Data Exchange (ETDEWEB)

    Moll, H.; Merroun, M.; Geipel, G.; Rossberg, A.; Hennig, C.; Selenska-Pobell , S.; Bernhard, G. [Forschungszentrum Dresden-Rossendorf e.V., Inst. fuer Radioc hemie, 01314 Dresden (Germany)]. e-mail: h.moll@fzd.de; Stumpf, Th. [Forschungszentru m Karlsruhe, Inst. fuer Nukleare Entsorgung, 76021 Karlsruhe (Germany)

    2007-06-15

    Sulfate-reducing bacteria (SRB) frequently occur in the deep granitic rock aquifers at the Aespoe Hard Rock Laboratory (Aespoe HRL), Sweden. The new SRB strain Desulfovibrio aespoeensis could be isolated. Results describing the basic interaction mechanisms of uranium, curium, and plutonium with cells of D. aespoeensis DSM 10631T will be presented. The interaction experiments with the actinides showed that the cells are able to remove all three actinides from the surrounding solution. The amount of removed actinide and the interaction mechanism varied among the different actinides. The main U(VI) removal occurred after the first 24 h. The contact time, pH and [U(VI)]initial influence the U removal efficiency. The presence of uranium caused a damaging of the cell membranes. TEM revealed an accumulation of U inside the bacterial cell. D. aespoeensis are able to form U(IV). A complex interaction mechanism takes place consisting of biosorption, bioreduction and bioaccumulation. In the case of {sup 242}Pu, solvent extractions, UV-vis- and XANES spectroscopy were used to determine the speciation of the Pu oxidation states. In the first step, the Pu(VI) and Pu(IV)-polymers are bound to the biomass. Solvent extractions showed that 97 % of the initially present Pu(VI) is reduced to Pu(V) due to the activity of the cells within the first 24 h. Most of the formed Pu(V) dissolves from the cell envelope back to the aqueous solution due to the weak complexing properties of this plutonium oxidation state. In the case of curium at a much lower metal concentration of 3x10{sup -7} M, a pure biosorption of Cm(III) on the cell envelope forming an inner-sphere surface complex most likely with organic phosphate groups was detected. To summarize, the strength of the interaction of D. aespoeensis with the selected actinides at pH 5 and actinide concentrations = 10 mg/L ([Cm] 0.07 mg/L) follows the pattern: Cm > U > Pu >> Np.

  7. 3 and 4 oxidation state element solubilities in borosilicate glasses. Implement to actinides in nuclear glasses

    International Nuclear Information System (INIS)

    Cachia, J.N.

    2005-12-01

    In order to ensure optimal radionuclides containment, the knowledge of the actinide loading limits in nuclear waste glasses and also the comprehension of the solubilization mechanisms of these elements are essential. A first part of this manuscript deals with the study of the differences in solubility of the tri and tetravalent elements (actinides and surrogates) particularly in function of the melting temperature. The results obtained indicate that trivalent elements (La, Gd, Nd, Am, Cm) exhibit a higher solubility than tetravalent elements (Hf, Th, Pu). Consequently, it was planned to reduce plutonium at the oxidation state (III), the later being essentially tetravalent in borosilicate glasses. An innovating reduction process of multi-valent elements (cerium, plutonium) using silicon nitride has been developed in a second part of this work. Reduced plutonium-bearing glasses synthesized by Si 3 N 4 addition made it possible to double the plutonium solubility from 2 to 4 wt% at 1200 deg C. A structural approach to investigate the differences between tri and tetravalent elements was finally undertaken. These investigations were carried out by X-rays Absorption Spectroscopy (EXAFS) and NMR. Trivalent rare earth and actinide elements seem to behave as network modifiers while tetravalent elements rather present true intermediaries' behaviour. (author)

  8. Programme and Abstracts. 38. Journees des Actinides together with the 7. School on the Physics and Chemistry of the Actinides

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2008-07-01

    Journees des Actinides (JdA) is a traditional informal actinide forum, including physics, chemistry, and materials research. It regularly brings together experts from fields involved, taking place in a very informal way, emphasizing exchanges and discussions on current issues in actinide science. At the 38{sup th} JdA (10-15 April 2008; Wroclaw, Poland) scientific communications on the following topics on physics and chemistry of the actinides were presented: (a) inorganic and organometallic chemistry; (b) strongly correlated behaviour, superconductivity, quantum criticality; (c) materials science; (d) theory, electronic structure; (e) nuclear fuel cycle, environment.

  9. Programme and Abstracts. 38. Journees des Actinides together with the 7. School on the Physics and Chemistry of the Actinides

    International Nuclear Information System (INIS)

    2008-01-01

    Journees des Actinides (JdA) is a traditional informal actinide forum, including physics, chemistry, and materials research. It regularly brings together experts from fields involved, taking place in a very informal way, emphasizing exchanges and discussions on current issues in actinide science. At the 38 th JdA (10-15 April 2008; Wroclaw, Poland) scientific communications on the following topics on physics and chemistry of the actinides were presented: (a) inorganic and organometallic chemistry; (b) strongly correlated behaviour, superconductivity, quantum criticality; (c) materials science; (d) theory, electronic structure; (e) nuclear fuel cycle, environment

  10. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-06-01

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy’s (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (i) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (ii) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (iii) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  11. Plutonium Management, Minor Actinides Partitioning and Transmutation R and D in France

    International Nuclear Information System (INIS)

    Cavedon, Jean-Marc; Courtois, Charles

    2003-01-01

    Jean-Marc Cavedon (CEA, France) then presented the developments concerning Plutonium management and minor actinides P and T research and development in France. By the 1991 law on high-level long-lived radioactive waste a research programme was launched in the areas: (i) geological disposal, (ii) conditioning and long-term storage, and (iii) radiotoxicity reduction by P and T. The results of the work in these areas will be presented to the French Government and Parliament in 2006. The control of Plutonium stocks generated by the French PWRs is proposed to increase Plutonium consumption in reactors and minimise radioactive waste production, and requires the recycling of actinides, especially Plutonium. In the long term, CEA intends to develop a new technology based on gas cooled reactors and their associated fuel cycle, including multiple recycling of Plutonium. The advantages of this development consist in the optimisation of the use of natural resources and the concentration of Plutonium in limited quantities of fuel rods. If needed, the minor actinides could also be recycled. The planned CEA developments depend on new fuel types and will lead to novel waste types (light glasses) with a reduction of long-term radiotoxicity. Radiotoxicity reductions by a factor of 3 to 5 are expected for Plutonium recycling scenarios, and by up to a factor of a few hundreds for Plutonium and minor actinides recycling scenarios. This gain is nearly independent on the reactor type used, but needs about 100 years of application to become effective in terms of making a difference in the total waste inventory to be disposed of

  12. The role of humic acid on the formation of HAS (hydroxy-aluminosilicate) colloid-borne actinides

    Energy Technology Data Exchange (ETDEWEB)

    Priemyshev, A.; Kim, M.A. [Inst. fuer Radiochemie, Technische Universitaet Muenchen, D-85748 Garching (Germany); Breban, D.; Panak, P.J.; Yun, J.I.; Kim, J.I.; Fanghanel, Th. [Inst. fuer Nukleare Entsorgung, Forschungszentrum Karlsruhe, D-76021 Karlsruhe (Germany); Mansel, A. [Inst. fuer Interdisziplinaere Isotopenforschung, Georadiochemie, Leipzig, D-04318 Leipzig (Germany)

    2005-07-01

    Full text of publication follows: One of the major unknowns in the process of actinide migration is the formation of their colloid-borne species. Previous studies have been directed to the incorporation of actinides into HAS (hydroxy-aluminosilicate) colloids generated by the nucleation of Si and Al. The present work further pursues the behaviour of actinides at HAS colloid formation but in the presence of humic acid that is known to be an ubiquitous groundwater constituent. The formation and degree of stability of the aluminosilicate binding for the generation of HAS colloids are investigated at first in the absence of actinides. Free and complexed Al resulting from ligand competitions reactions for the complexation of Al with mono-silicic acid, poly-silicic acid and EDTA are monitored spectroscopically by colour reaction. The second part of the study concentrates on the formation and stability of humic colloids using {sup 14}C-labeled humic acid. The activity distribution is ascertained in the ionic, colloidal and precipitated fractions under different conditions of colloid formation, e.g. as a function of pH, time, humic acid and Al concentration. The third part follows the appraisal of appropriate conditions under which stable HAS and humic colloids are formed, and their interaction with actinides, either separately or in competition. Trace actinides of different oxidation states {sup 241}Am(III), {sup 234}Th(IV) and {sup 233}U(VI) are taken for the purpose. HAS colloids generated from poly-silicic acid at neutral pH show EDTA-resistance, whereas HAS colloids formed from mono-silicic acid become EDTA-resistant only by aging (> one month). Humic acid appears to stabilize HAS colloids, unless the loading capacity of humic acid for the Al ion is exceeded. The incorporation of actinides into the colloidal phase is generally enhanced in the presence of humic acid. Synergic effects produce chimeric HAS-humic colloids into which tri-, tetra- and hexavalent actinides

  13. Non-compound nucleus fission in actinide and pre-actinide regions

    Indian Academy of Sciences (India)

    Data on the evaporation residue cross-sections, in addition to those on mass and angular distributions, are necessary for better understanding of the contribution from non-compound nucleus fission in the pre-actinide region. Measurement of mass-resolved angular distribution of fission products in 20Ne+232Th reaction ...

  14. Synergistic extraction of actinides : Part I. Hexa-and pentavalent actinides

    International Nuclear Information System (INIS)

    Patil, S.K.; Ramakrishna, V.V.

    1980-01-01

    A detailed discussion on the reported literature on the synergistic extraction of hexa- and pentavalent actinide ions, by different combinations of extractants and from different aqueous media, is presented. Structural aspects of the various complexes involved in synergism also are reviewed. A short account of the applications based on synergistic extraction is also given. (author)

  15. Afrikaans Syllabification Patterns

    Directory of Open Access Journals (Sweden)

    Tilla Fick

    2010-01-01

    note that the frequency of words ending with s is even higher than for words starting with s. The two and three letter patterns that occur most are er (10% of all two letter patterns and ing (4% of all three letter patterns. In an analysis of syllables in Afrikaans words, we found that (as for complete words syllables most often start with the letter s and end with e, while the frequency of syllables ending with s is almost as high as the frequency of syllables starting with s. This indicates that problems with hyphenation can be expected around the letter s. The two and three letter syllables that occur most often are -ge- and -ver-, respectively.In an attempt to decide on the window length to use to generate training data for machine-learning techniques we also analysed the length of syllables. The results show that two and three letter syllables occur most often, but that four letter syllables have the most unique instances. We also analysed a spectrum of window configurations and found that the ideal configuration will have to be determined empirically. One major problem we identified in this study is that irregular syllabification often occurs where letter patterns include the letter s. The reasons being (i the use of the combining s when joining words, (ii almost equal frequencies of syllables starting and ending with s and (iii vague hyphe- nation rules for letter combinations containing s. To effectively address automatic syllabification in Afrikaans, it is necessary to develop more sophisticated methods to handle vagueness around the letter s. 

  16. Research needs in metabolism and dosimetry of the actinides

    International Nuclear Information System (INIS)

    Richmond, C.R.

    1978-01-01

    The following topics are discussed: uranium mine and mill tailings; environmental standards; recommendations of NCRP and ICRP; metabolic models and health effects; life-time exposures to actinides and other alpha emitters; high-specific-activity actinide isotopes versus naturally occurring isotopic mixtures of uranium isotopes; adequacy of the n factor; and metabolism and dosimetry;

  17. ACTINET - EU network of excellence for actinide sciences

    International Nuclear Information System (INIS)

    Gompper, K.

    2006-01-01

    ACTINET, the Network of Excellence for Actinide Sciences within the 6th EU Framework Program, was launched in March 2004 for an initial period of four years. A number of tools are available in ACTINET to serve the purposes of the project, i.e. stimulate and coordinate actinide research in Europe, promote integration, train young scientists and, in this way, ensure and enhance European competence. The large European actinide laboratories with their unique experimental and analytical equipment are available to scientists from Europe as so-called 'pool facilities' within the framework of joint research projects. Setting up a 'theoretical user lab' has turned out to be a promising way of exploiting the synergies of theory and experiment in various fields of actinide science. Joint research projects are supported within the network, working with actinides being made possible in the pool facilities. Training and instruction are ensured by seminars, workshops, and schools organized annually. In familiarizing young scientists with actinide work, ACTINET exercises training functions and contributes to ensuring and enhancing European competence in the field on the medium and long term. Even after only half of its term, ACTINET is developing into a live network, thus decisively contributing towards promoting, coordinating and integrating European actinide research. As actinides play a key role in the use of nuclear power, this benefits European industries, research centers, operators of nuclear power plants and nuclear facilities as well as licensing and regulatory authorities. (orig.)

  18. Transmutation of minor actinide using thorium fueled BWR core

    International Nuclear Information System (INIS)

    Susilo, Jati

    2002-01-01

    One of the methods to conduct transmutation of minor actinide is the use of BWR with thorium fuel. Thorium fuel has a specific behaviour of producing a little secondary minor actinides. Transmutation of minor actinide is done by loading it in the BWR with thorium fuel through two methods, namely close recycle and accumulation recycle. The calculation of minor actinide composition produced, weigh of minor actinide transmuted, and percentage of reminder transmutation was carried SRAC. The calculations were done to equivalent cell modeling from one fuel rod of BWR. The results show that minor actinide transmutation is more effective using thorium fuel than uranium fuel, through both close recycle and accumulation recycle. Minor actinide transmutation weight show that the same value for those recycle for 5th recycle. And most of all minor actinide produced from 5 unit BWR uranium fuel can transmuted in the 6 t h of close recycle. And, the minimal value of excess reactivity of the core is 12,15 % Δk/k, that is possible value for core operation

  19. Separations chemistry for actinide elements: Recent developments and historical perspective

    International Nuclear Information System (INIS)

    Nash, K.L.; Choppin, G.R.

    1997-01-01

    With the end of the cold war, the principal mission in actinide separations has changed from production of plutonium to cleanup of the immense volume of moderately radioactive mixed wastes which resulted from fifty years of processing activities. In order to approach the cleanup task from a proper perspective, it is necessary to understand how the wastes were generated. Most of the key separations techniques central to actinide production were developed in the 40's and 50's for the identification and production of actinide elements. Total actinide recovery, lanthanide/actinide separations, and selective partitioning of actinides from inert constituents are currently of primary concern. To respond to the modern world of actinide separations, new techniques are being developed for separations ranging from analytical methods to detect ultra-trace concentrations (for bioassay and environmental monitoring) to large-scale waste treatment procedures. In this report, the history of actinide separations, both the basic science and production aspects, is examined and evaluated in terms of contemporary priorities

  20. Potential carcinogenic effects of actinides in the environment

    International Nuclear Information System (INIS)

    Harley, N.H.; Pasternack, B.S.

    1979-01-01

    Inhalation of alpha emitting actinides delivers a dose to critical cancer sites in the human body. These sites are the bronchial epithelium and cells near bone surfaces. Inhalation of the naturally occurring actinides uranium and thorium in resuspended soil in the air results in a continuous exposure for the global population of about 0.1 fCi/m 3 for each of these actinides. The highest dose is from the natural actinide 230 Th. Over 50 yr, the dose to bronchial epithelium is 0.05 mrad and to bone surfaces 0.4 mrad. In the case of accidental environmental contamination (e.g. near a nuclear fuel reprocessing plant) the man-made actinides plutonium, americium and curium could deliver about the same alpha dose to these sites if the soil is contaminated to the same level as the natural actinides (approximately 1 pCi/g). Two nuclear accidents have already produced contamination of about this level. Exposures in this case, however, are to small local populations compared with global exposure for the natural actinides. Significant enhancement of the natural radioactive actinide pollution by combustion of all types of fossil fuel is suspected but not enough data are available to estimate total population doses. (author)

  1. Solubility of actinides and surrogates in nuclear glasses

    International Nuclear Information System (INIS)

    Lopez, Ch.

    2003-01-01

    The nuclear wastes are currently incorporated in borosilicate glass matrices. The resulting glass must be perfectly homogeneous. The work discussed here is a study of actinide (thorium and plutonium) solubility in borosilicate glass, undertaken to assess the extent of actinide solubility in the glass and to understand the mechanisms controlling actinide solubilization. Glass specimens containing; actinide surrogates were used to prepare and optimize the fabrication of radioactive glass samples. These preliminary studies revealed that actinide Surrogates solubility in the glass was enhanced by controlling the processing temperature, the dissolution kinetic of the surrogate precursors, the glass composition and the oxidizing versus reducing conditions. The actinide solubility was investigated in the borosilicate glass. The evolution of thorium solubility in borosilicate glass was determined for temperatures ranging from 1200 deg C to 1400 deg C.Borosilicate glass specimens containing plutonium were fabricated. The experimental result showed that the plutonium solubility limit ranged from 1 to 2.5 wt% PuO 2 at 1200 deg C. A structural approach based on the determination of the local structure around actinides and their surrogates by EXAFS spectroscopy was used to determine their structural role in the glass and the nature of their bonding with the vitreous network. This approach revealed a correlation between the length of these bonds and the solubility of the actinides and their surrogates. (author)

  2. Pyrochlore as nuclear waste form. Actinide uptake and chemical stability

    Energy Technology Data Exchange (ETDEWEB)

    Finkeldei, Sarah Charlotte

    2015-07-01

    Radioactive waste is generated by many different technical and scientific applications. For the past decades, different waste disposal strategies have been considered. Several questions on the waste disposal strategy remain unanswered, particularly regarding the long-term radiotoxicity of minor actinides (Am, Cm, Np), plutonium and uranium. These radionuclides mainly arise from high level nuclear waste (HLW), specific waste streams or dismantled nuclear weapons. Although many countries have opted for the direct disposal of spent fuel, from a scientific and technical point of view it is imperative to pursue alternative waste management strategies. Apart from the vitrification, especially for trivalent actinides and Pu, crystalline ceramic waste forms are considered. In contrast to glasses, crystalline waste forms, which are chemically and physically highly stable, allow the retention of radionuclides on well-defined lattice positions within the crystal structure. Besides polyphase ceramics such as SYNROC, single phase ceramics are considered as tailor made host phases to embed a specific radionuclide or a specific group. Among oxidic single phase ceramics pyrochlores are known to have a high potential for this application. This work examines ZrO{sub 2} based pyrochlores as potential nuclear waste forms, which are known to show a high aqueous stability and a high tolerance towards radiation damage. This work contributes to (1) understand the phase stability field of pyrochlore and consequences of non-stoichiometry which leads to pyrochlores with mixed cationic sites. Mixed cationic occupancies are likely to occur in actinide-bearing pyrochlores. (2) The structural uptake of radionuclides themselves was studied. (3) The chemical stability and the effect of phase transition from pyrochlore to defect fluorite were probed. This phase transition is important, as it is the result of radiation damage in ZrO{sub 2} based pyrochlores. ZrO{sub 2} - Nd{sub 2}O{sub 3} pellets

  3. Pyrochlore as nuclear waste form. Actinide uptake and chemical stability

    International Nuclear Information System (INIS)

    Finkeldei, Sarah Charlotte

    2015-01-01

    Radioactive waste is generated by many different technical and scientific applications. For the past decades, different waste disposal strategies have been considered. Several questions on the waste disposal strategy remain unanswered, particularly regarding the long-term radiotoxicity of minor actinides (Am, Cm, Np), plutonium and uranium. These radionuclides mainly arise from high level nuclear waste (HLW), specific waste streams or dismantled nuclear weapons. Although many countries have opted for the direct disposal of spent fuel, from a scientific and technical point of view it is imperative to pursue alternative waste management strategies. Apart from the vitrification, especially for trivalent actinides and Pu, crystalline ceramic waste forms are considered. In contrast to glasses, crystalline waste forms, which are chemically and physically highly stable, allow the retention of radionuclides on well-defined lattice positions within the crystal structure. Besides polyphase ceramics such as SYNROC, single phase ceramics are considered as tailor made host phases to embed a specific radionuclide or a specific group. Among oxidic single phase ceramics pyrochlores are known to have a high potential for this application. This work examines ZrO 2 based pyrochlores as potential nuclear waste forms, which are known to show a high aqueous stability and a high tolerance towards radiation damage. This work contributes to (1) understand the phase stability field of pyrochlore and consequences of non-stoichiometry which leads to pyrochlores with mixed cationic sites. Mixed cationic occupancies are likely to occur in actinide-bearing pyrochlores. (2) The structural uptake of radionuclides themselves was studied. (3) The chemical stability and the effect of phase transition from pyrochlore to defect fluorite were probed. This phase transition is important, as it is the result of radiation damage in ZrO 2 based pyrochlores. ZrO 2 - Nd 2 O 3 pellets with pyrochlore and defect

  4. Chemistry of neptunium and of other actinides in carbonate medium

    International Nuclear Information System (INIS)

    Riglet, C.

    1990-01-01

    This work is a contribution to the establishment of a thermodynamic data base in order to forecast the behaviour of Np and other actinides in natural waters that might come into contact with a nuclear waste repository. Redox potentials and complexation constants in acidic and carbonate media are measured in aqueous solutions, in the presence of an inert salt (sodium perchlorate) of variable concentrations. The activity coefficients are calculated, from the variation of thermodynamic measurements with the ionic strength, with the Specific Interaction Theory (S.I.T.). The electrochemical data, obtained by polarography and voltamperometry, are interpreted, for irreversible systems, with numerical and graphical methods based on the Koutecky-Weber's and S.I.T. equations. The equilibrium constants in carbonate medium are measured by absorption spectrophotometry and a graphical method is proposed to determine the stoichiometries of polynuclear species. In this work are proposed numerical data relative to: - the redox potentials of the systems: M(VI/V) and M(IV/III) in acidic medium where M = U, Np, Pu; U(VI/V) in carbonate medium; Np(VI/V) in bicarbonate medium of ionic strength 3 M. - the formation constants of the hexakis (carbonato) tris [dioxoneptunate (VI)] complex in 3 M medium - the formation constants of the mono, di and tri (carbonato) dioxoneptunate (V) complexes - the influence of the ionic strength on some of the studied chemical equilibria by using, when necessary, literature results. All specific interaction coefficients (activity coefficients) of these species are also measured or calculated [fr

  5. Thermodynamic analysis of light-actinide elements

    International Nuclear Information System (INIS)

    Brosh, Eli; Makov, Guy; Shneck, Roni Z.

    2005-01-01

    The thermophysical properties of the alpha phases of the light actinide elements Th, U, Np and Pu were analysed. For each of the analysed elements, the Gibbs free-energy was modelled by an explicit function of temperature T and pressure P over the whole relevant T-P range, in a manner compatible with the CALPHAD (Calculation of Alloy Phase Diagrams) method. Several adjustable model-parameters were fitted to available experimental results. The model is based on a new semi-empirical equation of state, which interpolates with Thomas-Fermi type models for the volume and with the Dulong-Petit value for the heat capacity, at extreme pressures

  6. Photofissility of actinide nuclei at intermediate energies

    International Nuclear Information System (INIS)

    Deppman, A.; Tavares, O.A.P.; Duarte, S.B.; Oliveira, E.C. de; Arruda-Neto, J.D.T.; Pina, S.R. de; Likhachev, V.P.; Mesa, J.; Goncalves, M.

    2001-08-01

    We analyze the recent experimental data on photofissility for 237 Np, 238 U, and 232 Th at incident photon energies above 200 MeV. For this analysis, we developed a Monte carlo algorithm for the nuclear evaporation process in photonuclear reactions. This code is used in association with the multi-collisional model for the photon-induced intranuclear cascade process. Our results show a good quantitative and qualitative agreement with the experimental data. It is shown that the emission of protons and alpha particles at the evaporation stage is an important component for the non-saturation of the actinides photofissility up to, at least, 1GeV. (author)

  7. Thermal decomposition of lanthanide and actinide tetrafluorides

    International Nuclear Information System (INIS)

    Gibson, J.K.; Haire, R.G.

    1988-01-01

    The thermal stabilities of several lanthanide/actinide tetrafluorides have been studied using mass spectrometry to monitor the gaseous decomposition products, and powder X-ray diffraction (XRD) to identify solid products. The tetrafluorides, TbF 4 , CmF 4 , and AmF 4 , have been found to thermally decompose to their respective solid trifluorides with accompanying release of fluorine, while cerium tetrafluoride has been found to be significantly more thermally stable and to congruently sublime as CeF 4 prior to appreciable decomposition. The results of these studies are discussed in relation to other relevant experimental studies and the thermodynamics of the decomposition processes. 9 refs., 3 figs

  8. Electronic structure of the light actinides

    International Nuclear Information System (INIS)

    Dunlap, B.D.

    1976-01-01

    In the last few years, considerable advances have been made in our understanding of the properties of the light actinides. Although these are 5f transition elements formally equivalent to the lanthanide (4f) elements, these materials show a much more varied behavior due to the larger spatial extent and ionizability of the 5f electrons. A review is given of some areas of current interest, especially where hyperfine measurements have played an active role. These include studies of a variety of magnetic phenomena, systematics of isomer shift measurements, and studies of paramagnetic relaxation

  9. Fission cross section measurements for minor actinides

    Energy Technology Data Exchange (ETDEWEB)

    Fursov, B. [IPPE, Obninsk (Russian Federation)

    1997-03-01

    The main task of this work is the measurement of fast neutron induced fission cross section for minor actinides of {sup 238}Pu, {sup 242m}Am, {sup 243,244,245,246,247,248}Cm. The task of the work is to increase the accuracy of data in MeV energy region. Basic experimental method, fissile samples, fission detectors and electronics, track detectors, alpha counting, neutron generation, fission rate measurement, corrections to the data and error analysis are presented in this paper. (author)

  10. Status of nuclear data for actinides

    Energy Technology Data Exchange (ETDEWEB)

    Guzhovskii, B.Y.; Gorelov, V.P.; Grebennikov, A.N. [Russia Federal Nuclear Centre, Arzamas (Russian Federation)] [and others

    1995-10-01

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

  11. Compilation of actinide neutron nuclear data

    International Nuclear Information System (INIS)

    1979-01-01

    The Swedish nuclear data committee has compiled a selected set of neutron cross section data for the 16 most important actinide isotopes. The aim of the report is to present available data in a comprehensible way to allow a comparison between different evaluated libraries and to judge about the reliability of these libraries from the experimental data. The data are given in graphical form below about 1 ev and above about 10 keV shile the 2200 m/s cross sections and resonance integrals are given in numerical form. (G.B.)

  12. Thermodynamics of carbothermic synthesis of actinide mononitrides

    International Nuclear Information System (INIS)

    Ogawa, T.; Shirasu, Y.; Minato, K.; Serizawa, H.

    1997-01-01

    Carbothermic synthesis will be further applied to the fabrication of nitride fuels containing minor actinides (MA) such as neptunium, americium and curium. A thorough understanding of the carbothermic synthesis of UN will be beneficial in the development of the MA-containing fuels. Thermodynamic analysis was carried out for conditions of practical interest in order to better understand the recent fabrication experiences. Two types of solution phases, oxynitride and carbonitride phases, were taken into account. The Pu-N-O ternary isotherm was assessed for the modelling of M(C, N, O). With the understanding of the UN synthesis, the fabrication problems of Am-containing nitrides are discussed. (orig.)

  13. Calculated Bulk Properties of the Actinide Metals

    DEFF Research Database (Denmark)

    Skriver, Hans Lomholt; Andersen, O. K.; Johansson, B.

    1978-01-01

    Self-consistent relativistic calculations of the electronic properties for seven actinides (Ac-Am) have been performed using the linear muffin-tin orbitals method within the atomic-sphere approximation. Exchange and correlation were included in the local spin-density scheme. The theory explains...... the variation of the atomic volume and the bulk modulus through the 5f series in terms of an increasing 5f binding up to plutonium followed by a sudden localisation (through complete spin polarisation) in americium...

  14. Impact of minor actinide recycling on sustainable fuel cycle options

    Energy Technology Data Exchange (ETDEWEB)

    Heidet, F.; Kim, T. K.; Taiwo, T. A.

    2017-11-01

    The recent Evaluation and Screening study chartered by the U.S. Department of Energy, Office of Nuclear Energy, has identified four fuel cycle options as being the most promising. Among these four options, the two single-stage fuel cycles rely on a fast reactor and are differing in the fact that in one case only uranium and plutonium are recycled while in the other case minor actinides are also recycled. The two other fuel cycles are two-stage and rely on both fast and thermal reactors. They also differ in the fact that in one case only uranium and plutonium are recycled while in the other case minor actinides are also recycled. The current study assesses the impact of recycling minor actinides on the reactor core design, its performance characteristics, and the characteristics of the recycled material and waste material. The recycling of minor actinides is found not to affect the reactor core performance, as long as the same cycle length, core layout and specific power are being used. One notable difference is that the required transuranics (TRU) content is slightly increased when minor actinides are recycled. The mass flows are mostly unchanged given a same specific power and cycle length. Although the material mass flows and reactor performance characteristics are hardly affected by recycling minor actinides, some differences are observed in the waste characteristics between the two fuel cycles considered. The absence of minor actinides in the waste results in a different buildup of decay products, and in somewhat different behaviors depending on the characteristic and time frame considered. Recycling of minor actinides is found to result in a reduction of the waste characteristics ranging from 10% to 90%. These results are consistent with previous studies in this domain and depending on the time frame considered, packaging conditions, repository site, repository strategy, the differences observed in the waste characteristics could be beneficial and help improve

  15. The electronic structure of the lanthanides and actinides, a comparison

    International Nuclear Information System (INIS)

    Edelstein, N.M.

    1998-01-01

    Full text: Optical spectra of the two f-element series (the lanthanides and actinides) are comparable in many respects. For the trivalent ions isolated in single crystals, both series exhibit rich, narrow line spectra. These data can be analysed in terms of a parametric model based on a free-ion Hamiltonian plus the addition of a crystal field Hamiltonian. For most systems the agreement between the calculated and experimental energy levels is quite good. In the actinide series there appears to be a correlation between the magnitude of the crystal field and the inadequacy of the fits. The early actinides exhibit multiple oxidation states for which there is no precedent in the lanthanide series. The parametric model mentioned earlier has been utilized for some tetravalent actinide systems with reasonably good results. A selective survey of results describing the similarities and differences of various lanthanide and actinide systems will be given

  16. Actinide recovery from waste and low-grade sources

    International Nuclear Information System (INIS)

    Navratil, J.D.; Schulz, W.W.

    1982-01-01

    Actinide and nuclear fuel cycle operations generate a variety of process waste streams. New methods are needed to remove and recover actinides. More interest is also being expressed in recovering uranium from oceans, phosphoric acid, and other low grade sources. To meet the need for an up-to-date status report in the area of actinide recovery from waste and low grade sources, these papers were brought together. The papers provide an authoritative, in-depth coverage of an important area of nuclear and industrial and engineering chemistry which cover the following topics: uranium recovery from oceans and phosphoric acid; recovery of actinides from solids and liquid wastes; plutonium scrap recovery technology; and other new developments in actinide recovery processes

  17. Experimental and theoretical studies on extraction of actinides and lanthanides by alicyclic H-phosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Annam, Suresh; Sivaramakrishna, Akella; Vijayakrishna, Kari [VIT Univ., Tamil Nadu (India). Dept. of Chemistry; Gopakumar, Gopinadhanpillai; Rao, C.V.S. Brahmmananda; Sivaraman, N. [Indira Gandhi Centre for Atomic Research (IGCAR), Tamil Nadu (India). Chemistry Group

    2017-06-01

    Three different alicyclic substituents H-phosphonates, namely, dicyclopentyl H-phosphonate, dicyclohexyl H-phosphonate and dimenthyl H-phosphonate were synthesized and used for liquid-liquid extraction of actinide elements (U, Am and Th) and lanthanide (Gd) in n-dodecane from nitric acid medium. The physicochemical properties of the extractants, such as density, viscosity, solubility were determined. At lower acidities, these H-phosphonates exhibit higher distribution values and the extraction following cation exchange mechanism through P-OH group of tri-coordinated phosphite form. At higher acidities (2N), the extraction is primarily via solvation mechanism through P=O group of penta-coordinated phosphonate form. Amongst the three H-phosphonates, examined dimenthyl H-phosphonate showed the best results for the actinide extraction. Density functional theory (DFT) calculations were applied to understand the electronic structure of the ligands and the metal complexes. The calculated large complexation energy of UO{sub 2}(NO{sub 3}){sub 2}.@2DMnHP is in agreement with the observed trend in experimental distribution ratio data.

  18. Rapid Separation Methods to Characterize Actinides and Metallic Impurities in Plutonium Scrap Materials at SRS

    International Nuclear Information System (INIS)

    Maxwell, S.L. III; Jones, V.D.

    1998-07-01

    The Nuclear Materials Stabilization and Storage Division at SRS plans to stabilize selected plutonium scrap residue materials for long term storage by dissolution processing and plans to stabilize other plutonium vault materials via high-temperature furnace processing. To support these nuclear material stabilization activities, the SRS Analytical Laboratories Department (ALD) will provide characterization of materials required prior to the dissolution or the high-firing of these materials. Lab renovations to install new analytical instrumentation are underway to support these activities that include glove boxes with simulated-process dissolution and high- pressure microwave dissolution capability. Inductively-coupled plasma atomic emission spectrometry (ICP-AES), inductively- coupled mass spectrometry (ICP-MS) and thermal-ionization mass spectrometry (TIMS) will be used to measure actinide isotopics and metallic impurities. New high-speed actinide separation methods have been developed that will be applied to isotopic characterization of nuclear materials by TIMS and ICP-MS to eliminate isobaric interferences between Pu-238 /U- 238 and Pu-241/Am-241. TEVA Resin, UTEVA Resin, and TRU Resin columns will be used with vacuum-assisted flow rates to minimize TIMS and ICP-MS sample turnaround times. For metallic impurity analysis, rapid column removal methods using UTEVA Resin, AGMP-1 anion resin and AG MP-50 cation resin have also been developed to remove plutonium and uranium matrix interferences prior to ICP-AES and ICP- MS measurements

  19. Novel Reactivity Of The Cationic Complex

    International Nuclear Information System (INIS)

    Wang, J.; Dash, A.K.; Eisen, AM.; Berthet, J.C.; Ephritikhine, M.

    2002-01-01

    The catalytic chemistry of electrophilic d 0 /f organometallic complexes is nowadays under intense investigation, reaching a high level of sophistication. General aspects concerning these complexes are concentrated for most studies to the functionalization of unsaturated organic molecules. To cite an instance, the actinide-promoted oligomerization of terminal alkynes is of essential present concern since it may introduce to a diversity of organic enynes and oligoacetylene products that are valuable synthons for the synthesis of natural products. Enynes are the simplest oligomerization products of alkynes. We have demonstrated that organoactinides complexes of the type [Cp* 2 AnMe 2 AnMe 2 ] (Cp* = C 5 Me 5 ; An = U, Th) are active catalysts for the linear oligomerization of terminal alkynes and the extent of oligomerization was found to be strongly dependent on the electronic and steric properties of the alkyne substituents. Bulky alkynes were reacted with high regioselectivity toward dimer and/or trimers whereas for non-bulky alkynes, these compounds were transformed into oligomers with a total deficiency of regioselectivity. The addition of primary amines to the catalytic cycle, for An = Th, granted the chemoselective formation of dimers, chemoselectively, whereas for An = U, this control was not succeeded. In distinction to the neutral organoactinide complexes, homogeneous cationic d 0 /f n actinide complexes have been used as in the homogeneous polymerization of olefins as extremely active catalysts. Hence, the catalytic alkyne oligomerization is a opportune route to explore insertions and σ-bond metathesis reactivity of complexes. We have recently shown that the reaction of terminal alkynes (RC≡CH), promoted by [(Et 2 N) 3 U][BPh 4 ], in toluene, produces efficiently mostly the gem dimers (for R = Me, i Pr and n Bu) as the major products, whereas for bulky alkynes (R = t MS or t Bu) small amounts of the cis dimer was concomitantly obtained. A plausible

  20. The radiological impact of actinides discharged to the Irish Sea

    International Nuclear Information System (INIS)

    Hunt, G.J.; Smith, B.D.

    1999-01-01

    This paper describes the radiological effects of releases of actinides to the Irish Sea from Sellafield, the major source. Exposure pathways to man since the commencement of discharges in 1952 are reviewed; the importance of actinides began to increase with increased discharges in the 1970s. With the demise of the porphyra/laverbread pathway due to transport difficulties, the pathway due to fish and shellfish consumption became critical, particularly for actinides through molluscan shellfish. A reassessment on the current basis of effective dose shows that peak exposures to the critical group of about 2 mSv yr -1 were received in the mid-1970s, about 30% of which was due to actinides. Effective doses have since reduced but the relative importance of actinides is greater, due to the interplay of discharges of radionuclides from Sellafield and their behaviour in the environment. Additive doses through sea food due to releases of natural radionuclides from the Marchon phosphate plant at Whitehaven are also considered, although the actinide component from this source has been small. Exposures due to actinides from Sellafield via other pathways are shown to be much lower than those involving sea food. Collective doses are also considered; these peaked at about 300 man-Sv to the European population (including the UK) in 1979, with only a few percent due to actinides. As in the case of critical group doses, the relative importance of actinides has increased in recent years within the decreasing total collective dose. For both critical group and collective doses, therefore, the actinide component needs to be kept under review. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  1. Coupling of terminal alkynes and isonitriles by organo-actinide complexes: Scope and mechanistic insights

    International Nuclear Information System (INIS)

    Barnea, E.; Andrea, T.; Eisen, M. S.; Berthet, J.C.; Ephritikhine, M.

    2008-01-01

    The coupling reaction of terminal alkynes with several isonitriles, catalyzed by the neutral organo-actinide complexes Cp * 2 AnMe 2 (Cp * = C 5 Me 5 , An = Th, U) or the cationic complex [(Et 2 N) 3 U][BPh 4 ], yielded substituted α, β-acetylenic aldimines, in good to excellent yields. The reaction proceeded via a 1,1-insertion of the isonitrile carbon into a metal-acetylide bond, followed by a protonolysis by the acidic proton of the terminal alkyne. Additional insertion products were obtained by altering the catalyst and the reactant ratios. A plausible mechanism for the catalytic reaction is also presented, based on kinetics measurements and thermodynamic studies of the coupling reaction with Cp * 2 ThMe 2 or [(Et 2 N) 3 U][BPh 4 ] as catalysts. The reaction is first-order in catalyst and isonitrile and zero-order in alkyne. (authors)

  2. An independent method for data selection of long-life radionuclides (actinides and fission products) in the geosphere

    International Nuclear Information System (INIS)

    Henry, M.; Merceron, T.

    1994-01-01

    An independent method for data selection of long-life radio-nuclides based on the electronegativity equalization principle is proposed to predict the speciation of metal cations as a function of the solution pH. Hydrolysis, condensation and complexation reactions of metal cations in aqueous media are, by this simple model, unified and can be analyzed in terms of electronegativities, oxidation states and coordination numbers with a specific PC software. This paper describes the thermodynamical basis and the underlying concepts of the model in relation to aqueous actinide chemistry of elements such as U and Tc. It is then shown that the model could provide a complementary approach to existing softwares based on thermodynamic data bases allowing to make intelligent and reasonnable choices for the various complexes to consider in complex geochemical codes. (orig.)

  3. Two new octahedral/pyramidal frameworks containing both cation channels and lone-pair channels: syntheses and structures of Ba2MnIIMn2III(SeO3)6 and PbFe2(SeO3)4

    International Nuclear Information System (INIS)

    Johnston, Magnus G.; Harrison, William T.A.

    2004-01-01

    The hydrothermal syntheses, single crystal structures, and some properties of Ba 2 Mn II Mn 2 III (SeO 3 ) 6 and PbFe 2 (SeO 3 ) 4 are reported. These related phases contain three-dimensional frameworks of vertex (FeO 6 ) and vertex/edge linked (MnO 6 ) octahedra and SeO 3 pyramids. In each case, the MO 6 /SeO 3 framework encloses two types of 8 ring channels, one of which encapsulates the extra-framework cations and one of which provides space for the Se IV lone pairs. Crystal data: Ba 2 Mn 3 (SeO 3 ) 6 , M r =1201.22, monoclinic, P2 1 /c (No. 14), a=5.4717 (3)A, b=9.0636 (4)A, c=17.6586 (9)A, β=94.519 (1) o , V=873.03 (8)A 3 , Z=2, R(F)=0.031, wR(F 2 )=0.070; PbFe 2 (SeO 3 ) 4 , M r =826.73, triclinic, P1-bar (No. 2), a=5.2318 (5)A, b=6.7925 (6)A, c=7.6445 (7)A, α=94.300 (2) o , β=90.613 (2) o , γ=95.224 (2) o , V=269.73 (4)A 3 , Z=1, R(F)=0.051, wR(F 2 )=0.131

  4. Enhancing VVER annular proliferation resistance fuel with minor actinides

    International Nuclear Information System (INIS)

    Chang, G. S.

    2007-01-01

    Key aspects of the Global Nuclear Energy Partnership (GNEP) are to significantly advance the science and technology of nuclear energy systems and the Advanced Fuel Cycle (AFC) program. It consists of both innovative nuclear reactors and innovative research in separation and transmutation. To accomplish these goals, international cooperation is very important and public acceptance is crucial. The merits of nuclear energy are high-density energy, with low environmental impacts (i.e. almost zero greenhouse gas emission). Planned efforts involve near term and intermediate-term improvements in fuel utilization and recycling in current light water reactors (LWRs) as well as the longer-term development of new nuclear energy systems that offer much improved fuel utilization and proliferation resistance, along with continued advances in operational safety. The challenges are solving the energy needs of the world, protection against nuclear proliferation, the problem of nuclear waste, and the global environmental problem. To reduce spent fuel for storage and enhance the proliferation resistance for the intermediate-term, there are two major approaches (a) increase the discharged spent fuel burnup in the advanced LWR (Gen-III Plus), which not only can reduce the spent fuel for storage, but also increase the 2 38Pu and 2 40Pu isotopes ratio to enhance the proliferation resistance, and (b) use of transuranic nuclides ( 2 37Np and 2 41Am) in the high burnup fuel, which can drastically increase the proliferation resistance isotope ratio of 2 38Pu /Pu. For future advanced nuclear systems, the minor actinides (MA) are viewed more as a resource to be recycled, or transmuted to less hazardous and possibly more useful forms, rather than simply as a waste stream to be disposed of in expensive repository facilities. As a result, MAs play a much larger part in the design of advanced systems and fuel cycles, not only as additional sources of useful energy, but also as direct contributors

  5. Enhancing BWR proliferation resistance fuel with minor actinides

    Science.gov (United States)

    Chang, Gray S.

    2009-03-01

    To reduce spent fuel for storage and enhance the proliferation resistance for the intermediate-term, there are two major approaches (a) increase the discharged spent fuel burnup in the advanced light water reactor- LWR (Gen-III Plus), which not only can reduce the spent fuel for storage, but also increase the 238Pu isotopes ratio to enhance the proliferation resistance, and (b) use of transuranic nuclides ( 237Np and 241Am) in the high burnup fuel, which can drastically increase the proliferation resistance isotope ratio of 238Pu/Pu. For future advanced nuclear systems, minor actinides (MA) are viewed more as a resource to be recycled, and transmuted to less hazardous and possibly more useful forms, rather than simply disposed of as a waste stream in an expensive repository facility. As a result, MAs play a much larger part in the design of advanced systems and fuel cycles, not only as additional sources of useful energy, but also as direct contributors to the reactivity control of the systems into which they are incorporated. In the study, a typical boiling water reactor (BWR) fuel unit lattice cell model with UO 2 fuel pins will be used to investigate the effectiveness of minor actinide reduction approach (MARA) for enhancing proliferation resistance and improving the fuel cycle performance in the intermediate-term goal for future nuclear energy systems. To account for the water coolant density variation from the bottom (0.76 g/cm 3) to the top (0.35 g/cm 3) of the core, the axial coolant channel and fuel pin were divided to 24 nodes. The MA transmutation characteristics at different elevations were compared and their impact on neutronics criticality discussed. The concept of MARA, which involves the use of transuranic nuclides ( 237Np and/or 241Am), significantly increases the 238Pu/Pu ratio for proliferation resistance, as well as serves as a burnable absorber to hold-down the initial excess reactivity. It is believed that MARA can play an important role in

  6. Recycle of LWR actinides to an IFR

    International Nuclear Information System (INIS)

    Pierce, R.D.; Ackerman, J.P.; Johnson, G.K.; Mulcahey, T.P.; Poa, D.S.

    1991-01-01

    Large quantities of actinide elements are present in irradiated light water reactor fuel that is stored throughout the world. Because of the high fission to capture ratio for the transuranium (TRU) elements with the high energy neutrons in metal-fueled integral fast reactors (IFR), that reactor can consume these elements effectively. The stored fuel may represent valuable resource for the expanding application of fast power reactors. In addition, the removal of TRU elements from spent LWR fuel has the potential for increasing the capacity of high level waste facilities by reducing the heat load and may increase the margin of safety in meeting licensing requirement. Argonne National Laboratory is developing a pyrochemical process, which is compatible with the IFR fuel cycle for the recovery of TRU elements from LWR fuel. The proposed product is a metallic actinide ingot, which can be introduced into the electrorefining step of the IFR process. Two pyrochemical processes, that is, salt transport process and blanket processing study, are discussed in this paper. Also the experimental studies are reported. (K.I.)

  7. Subcritical limits for special fissile actinides

    International Nuclear Information System (INIS)

    Clark, H.K.

    1980-01-01

    Critical masses and subcritical mass limits in oxide-water mixtures were calculated for actinide nuclides other than 233 U, 235 U, and 239 Pu that have an odd number of neutrons in the nucleus: S/sub n/ transport theory was used together with cross sections, drawn from the GLASS multigroup library, developed to provide accurate forecasts of actinide production at Savannah River. The subcritical limits are 201 g for 241 Pu, 13 g for 242 /sup m/Am, 90 g for 243 Cm, 30 g for 245 Cm, 900 g for 247 Cm, 10 g for 249 Cf, and 5 g for 251 Cf. Association of 241 Pu with an equal mass of 240 Pu increases the 241 Pu limit to a value greater than that for pure 239 Pu. Association of 242 /sup m/Am with 241 Am increases the limit for the mixture to that for dry, theoretical density AmO 2 at isotopic concentrations of 242 /sup m/Am less than approx. 6%. Association of 245 Cm with 244 Cm increases the limit according to the formula 30 + 0.3 244 Cm/ 245 Cm up to the limit for dry CmO 2 . A limiting mass of 8.15 kg for plutonium containing at least 67% 238 Pu as oxide was calculated that applies (provided 240 Pu exceeds 241 Pu) with no limit on moderation. 1 figure, 5 tables

  8. The dose from actinides in the environment

    International Nuclear Information System (INIS)

    Harley, Naomi H.; Pasternack, Bernard S.

    1978-01-01

    We attempt to evaluate the health effects on local populations from the nuclear power industry. The nuclides which are thought to be most hazardous are the long-lived, alpha-emitting isotopes of plutonium, americium and curium. These long-lived alpha emitters will almost certainly be dispersed in the environment during fuel reprocessing. Their effect is local, not global and at worst a single community could be affected. The most important pathway for exposure to the actinides is through inhalation following resuspension of contaminated soil particles. The most important alpha dose estimates are to cells in bronchial epithelium and cells on bone surfaces. These alpha dose estimates are calculated for a dispersal which contaminates soil with 1 pCi/g of each of the nuclides Pu 238,239 , Am 241 , Cm 242,244 . These bronchial and bone cell dose estimates are compared with those from the naturally occurring actinide 232 Th (and daughters) which are normally found in soil at a level of about 1 pCi/g. (author)

  9. Consistent biokinetic models for the actinide elements

    International Nuclear Information System (INIS)

    Leggett, R.W.

    2001-01-01

    The biokinetic models for Th, Np, Pu, Am and Cm currently recommended by the International Commission on Radiological Protection (ICRP) were developed within a generic framework that depicts gradual burial of skeletal activity in bone volume, depicts recycling of activity released to blood and links excretion to retention and translocation of activity. For other actinide elements such as Ac, Pa, Bk, Cf and Es, the ICRP still uses simplistic retention models that assign all skeletal activity to bone surface and depicts one-directional flow of activity from blood to long-term depositories to excreta. This mixture of updated and older models in ICRP documents has led to inconsistencies in dose estimates and interpretation of bioassay for radionuclides with reasonably similar biokinetics. This paper proposes new biokinetic models for Ac, Pa, Bk, Cf and Es that are consistent with the updated models for Th, Np, Pu, Am and Cm. The proposed models are developed within the ICRP's generic model framework for bone-surface-seeking radionuclides, and an effort has been made to develop parameter values that are consistent with results of comparative biokinetic data on the different actinide elements. (author)

  10. New strategy for minor actinides partitioning preliminary results on the electrovolatilization of ruthenium and on the stabilization of Am(IV) in nitric acid with phosphotunsgstate ligand

    International Nuclear Information System (INIS)

    Adnet, J.M.; Madic, C.

    1989-01-01

    On problems related to the long term storage in deep geological repositories of high active wastes (H.A.W.) is due to the presence of minor actinide isotopes. Thus after the decay of the fission products (≅ 300 years) the toxicity of these H.A.W. is mainly due to the minor actinides. One solution is based on actinide partitioning followed by transmutation into fission products with short half-lives. A simpler processes than those developed previously, can be based on the possible oxidation of minor actinides to the + IV or + VI oxidation states and their selective extraction. The first step to study is the elimination of the ruthenium (whose presence would be detrimental to oxidize minor actinides) which can be done by electrovolatilization of Ru on the RuO 4 form. The rate of electrovolatilization can be increased by the use of the following electronic mediators, AgI/AgII(1); CeIII/Ce(2), and CoII/CoIII(3), the efficiency of which decreases in the order: 1 > 2 > 3. The effectiveness of that process has been proven when treating real H.A.W solution produced during the study of the reprocessing of a MOX fuel irradiated to as burn-up of 52 GWd/t in a LWR: complete Ru removal was obtained. The second part of the study concerns the electrochemical oxidation of AmIII in nitric acid solutions in the presence of a strong complexing agent: P 2 W 17 O 61 K 10 (P.W.).Total americium oxidation to AmIV can be obtained in nitric acid solution with a concentration up to 8 M. No particular drawback was induced by the presence of an amount of lanthanide III (NdIII) in 6 fold excess vs P.W. The stability of AmIV was studied. The other actinides will be present in these solutions, after the electrochemical oxidation step, in the + VI or+ IV oxidation states, thus a selective extraction (vs fission products) could be performed. A possible way to extract actinide IV/P.W complexes is to use dodecylamine nitrate as extractant

  11. Burning minor actinides in a HTR energy spectrum

    International Nuclear Information System (INIS)

    Pohl, Christoph; Rütten, H. Jochem

    2012-01-01

    Highlights: ► Burn-up analysis for varying plutonium/minor actinide fuel compositions. ► The influence of varying heavy metal fuel element loads is investigated. ► Significant burn-up via radiative capture and subsequently fission is observed. ► Difference observed between fuel element burn-up and total actinide burning rate. - Abstract: The generation of nuclear energy by means of the existing nuclear reactor systems is based mainly on the fission of U-235. But this comes along with the capture of neutrons by the U-238 faction and results in a build-up of plutonium isotopes and minor actinides as neptunium, americium and curium. These actinides are dominant for the long time assessment of the radiological risk of a final disposal therefore a minimization of the long living isotopes is aspired. Burning the actinides in a high temperature helium cooled graphite moderated reactor (HTR) is one of these options. The use of plutonium isotopes to sustain the criticality of the system is intended to avoid on the one hand highly enriched uranium because of international regulations and on the other hand low enriched uranium because of the build up of new actinides from neutron capture in the U-238 fraction. Because initial minor actinide isotopes are typically not fissionable by thermal neutrons the idea is to fission instead the intermediate isotopes generated by the first neutron capture. This paper comprises calculations for plutonium/minor actinides/thorium fuel compositions and their correlated final burn-up for a generic pebble bed HTR based on the reference design of the 400 MW PBMR. In particular the cross sections and the neutron balance of the different minor actinide isotopes in the higher thermal energy spectrum of a HTR will be discussed. For a fuel mixture of plutonium and minor actinides a significant burn-up of these actinides up to 20% can be achieved but at the expense of a higher residual fraction of plutonium in the burned fuel. Combining

  12. QSAR studies of multidentate nitrogen ligands used in lanthanide and actinide extraction processes

    International Nuclear Information System (INIS)

    Drew, Michael G.B.; Hudson, Michael J.; Youngs, Tristan G.A.

    2004-01-01

    Quantitative structure activity relationships (QSARs) have been developed to optimise the choice of nitrogen heterocyclic molecules that can be used to separate the minor actinides such as americium(III) from europium(III) in the aqueous PUREX raffinate of nuclear waste. Experimental data on distribution coefficients and separation factors (SFs) for 47 such ligands have been obtained and show SF values ranging from 0.61 to 100. The ligands were divided into a training set of 36 molecules to develop the QSAR and a test set of 11 molecules to validate the QSAR. Over 1500 molecular descriptors were calculated for each heterocycle and the Genetic Algorithm was used to select the most appropriate for use in multiple regression equations. Equations were developed fitting the separation factors to 6-8 molecular descriptors which gave r 2 values of >0.8 for the training set and values of >0.7 for the test set, thus showing good predictive quality. The descriptors used in the equations were primarily electronic and steric. These equations can be used to predict the separation factors of nitrogen heterocycles not yet synthesised and/or tested and hence obtain the most efficient ligands for lanthanide and actinide separation

  13. Separation of minor actinides from a genuine MA/LN fraction

    International Nuclear Information System (INIS)

    Satmark, B.; Courson, O.; Malmbeck, R.; Pagliosa, G.; Romer, K.; Glatz, J.P.

    2001-01-01

    Separation of the trivalent Minor Actinides (MA), Am and Cm, has been performed from a genuine MA(III) + Ln(III) solution using Bis-Triazine-Pyridine (BTP) as organic extractant. The representative MA/Ln fraction was obtained from a dissolved commercial LWR fuel (45.2 GWd/tM) submitted subsequently too a PUREX process followed by a DIAMEX process. A centrifugal extractor set-up (16-stages), working in a continuous counter-current mode, was used for the liquid-liquid separation. In the nPr-BTP process, feed decontamination factors for Am and Cm above 96 and 65, respectively were achieved. The back-extraction was more efficient for Am (99.1% recovery) than for Cm (97.5%). This experiment, using the Bis-Triazine-Pyridine molecule is the first successful demonstration of the separation of MA from lanthanides in a genuine MA/Ln fraction with a nitric acid concentration of ca. 1 M. It represents an important break through in the difficult field of minor actinide partitioning of high level liquid waste. (author)

  14. Application of multi-step excitation schemes for detection of actinides and lanthanides in solutions by luminescence/chemiluminescence laser spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Izosimov, I. [Joint Institute for Nuclear Research, Joliot Curie 6, Dubna 141980 (Russian Federation)

    2016-07-01

    The use of laser radiation with tunable wavelength allows the selective excitation of actinide/lanthanide species with subsequent registration of luminescence/chemiluminescence for their detection. This work is devoted to applications of the time-resolved laser-induced luminescence spectroscopy and time-resolved laser-induced chemiluminescence spectroscopy for the detection of lanthanides and actinides. Results of the experiments on U, Eu, and Sm detection by TRLIF (Time Resolved Laser Induced Fluorescence) method in blood plasma and urine are presented. Data on luminol chemiluminescence in solutions containing Sm(III), U(IV), and Pu(IV) are analyzed. It is shown that appropriate selectivity of lanthanide/actinide detection can be reached when chemiluminescence is initiated by transitions within 4f- or 5f-electron shell of lanthanide/actinide ions corresponding to the visible spectral range. In this case chemiluminescence of chemiluminogen (luminol) arises when the ion of f element is excited by multi-quantum absorption of visible light. The multi-photon scheme of chemiluminescence excitation makes chemiluminescence not only a highly sensitive but also a highly selective tool for the detection of lanthanide/actinide species in solutions. (author)

  15. NMR study of rare earth and actinide complexes

    International Nuclear Information System (INIS)

    Villardi de Montlaur de, G.C.

    1978-01-01

    Proton magnetic resonance studies of lanthanide shift reagents with olefin-transition metal complexes, monoamines and diamines as substrates are described. Shift reagents for olefins are reported: Lnsup(III)(fod) 3 can induce substantial shifts in the nmr spectra of a variety of olefins when silver 1-heptafluororobutyrate is used to complex the olefin. The preparation, properties and efficiency of such systems are described. Configurational aspects and exchange processes of Lnsup(III)(fod) 3 complexes with secondary and tertiary monoamines are analysed by means of dynamic nmr. Factors influencing the stability and the stoichiometry of these complexes and various processes such as nitrogen inversion and ligand exchange are discussed. At low temperature, ring inversion can be slow on an nmr time-scale for Lnsup(III)(fod) 3 -diamino chelates. Barriers to ring inversion in substituted ethylenediamines and propanediamines are obtained. Steric factors appear to play an important role in the stability and kinetics of these bidentate species. The synthesis of uranium-IV crown-ether and cryptate complexes is described. A conformational study of these compounds show evidence of an insertion of the paramagnetic cation as witnessed by the large induced shifts observed. The insertion of uranium in the macrocyclic ligand of a UCl 4 -dicyclohexyl-18-crown-6 complex is confirmed by an X-ray structural determination [fr

  16. X-ray absorption spectroscopic study of trivalent and tetravalent actinides in solution at varying pH values

    Energy Technology Data Exchange (ETDEWEB)

    Brendebach, B.; Banik, N.L.; Marquardt, C.M.; Rothe, J.; Denecke, M.A.; Geckeis, H. [Forschungszentrum Karlsruhe (Germany). Inst. fuer Nukleare Entsorgung

    2009-07-01

    We perform X-ray absorption spectroscopy (XAS) investigations to monitor the stabilization of redox sensitive trivalent and tetravalent actinide ions in solution at acidic conditions in a pH range from 0 to 3 after treatment with holding reductants, hydroxylamine hydrochloride (NH{sub 2}OHHCl) and Rongalite (sodium hydroxymethanesulfinate, CH{sub 3}NaO{sub 3}S). X-ray absorption near edge structure (XANES) measurements clearly demonstrate the stability of the actinide species for several hours under the given experimental conditions. Hence, structural parameters can be accurately derived by extended X-ray absorption fine structure (EXAFS) investigations. The coordination structure of oxygen atoms belonging to water ligands surrounding the actinide ions does not change with increasing pH value (approximately 11 O atoms at 2.42 A in the case of U(IV) at pH 1, 9 0 atoms at 2.52 A for Np(III) at pH 1.5, and 10 O atoms at 2.49 A for Pu(III) up to pH 3), indicating that hydrolysis reactions are suppressed under the given chemical conditions. (orig.)

  17. End point control of an actinide precipitation reactor

    International Nuclear Information System (INIS)

    Muske, K.R.

    1997-01-01

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

  18. On the suitability of lanthanides as actinide analogs

    International Nuclear Information System (INIS)

    Raymond, Kenneth; Szigethy, Geza

    2008-01-01

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

  19. Managing Zirconium Chemistry and Phase Compatibility in Combined Process Separations for Minor Actinide Partitioning

    Energy Technology Data Exchange (ETDEWEB)

    Wall, Nathalie [Washington State Univ., Pullman, WA (United States); Nash, Ken [Washington State Univ., Pullman, WA (United States); Martin, Leigh [Washington State Univ., Pullman, WA (United States)

    2017-03-17

    In response to the NEUP Program Supporting Fuel Cycle R&D Separations and Waste Forms call DEFOA- 0000799, this report describes the results of an R&D project focusing on streamlining separation processes for advanced fuel cycles. An example of such a process relevant to the U.S. DOE FCR&D program would be one combining the functions of the TRUEX process for partitioning of lanthanides and minor actinides from PUREX(UREX) raffinates with that of the TALSPEAK process for separating transplutonium actinides from fission product lanthanides. A fully-developed PUREX(UREX)/TRUEX/TALSPEAK suite would generate actinides as product(s) for reuse (or transmutation) and fission products as waste. As standalone, consecutive unit-operations, TRUEX and TALSPEAK employ different extractant solutions (solvating (CMPO, octyl(phenyl)-N,Ndiisobutylcarbamoylmethylphosphine oxide) vs. cation exchanging (HDEHP, di-2(ethyl)hexylphosphoric acid) extractants), and distinct aqueous phases (2-4 M HNO3 vs. concentrated pH 3.5 carboxylic acid buffers containing actinide selective chelating agents). The separate processes may also operate with different phase transfer kinetic constraints. Experience teaches (and it has been demonstrated at the lab scale) that, with proper control, multiple process separation systems can operate successfully. However, it is also recognized that considerable economies of scale could be achieved if multiple operations could be merged into a single process based on a combined extractant solvent. The task of accountability of nuclear materials through the process(es) also becomes more robust with fewer steps, providing that the processes can be accurately modeled. Work is underway in the U.S. and Europe on developing several new options for combined processes (TRUSPEAK, ALSEP, SANEX, GANEX, ExAm are examples). There are unique challenges associated with the operation of such processes, some relating to organic phase chemistry, others arising from the

  20. Development of a system for simultaneous - sequential determinations of major and minor actinides (Th, Np, U, Pu, Am, Cm) by on-line extraction chromatography - ion concentration - inductively coupled plasma mass spectrometry

    International Nuclear Information System (INIS)

    Trivellone, E.; Mariani, M.; Carlos-Marquez, R.; Aldave de las Heras, L.; Betti, M.; )

    2009-01-01

    Full text: Because of the great complexity and time consuming of traditional methods for actinides determination, a procedure for their simultaneous and sequential separation and quantification was developed. A complete circuit constituted by three analytical chromatographic columns packed with TEVA, UTEVA and TRU resins (Eichrom Inc) for retention of tetra-, hexa- and tri-valent actinides and three cation concentrator columns TCC-II (from Dionex Corporation) connected by six (4-way and 6-way) valves is coupled on-line to an ICPMS detector. The use of TCC-II columns just prior of the ICPMS determination allows to improve sensitivity and detection limits down to the ng/l level. The use of a coupled HPLC to an ICPMS system enables the complete analysis of all the six actinides in almost 2 hours. (author)

  1. Actinide separation chemistry in nuclear waste streams and materials

    International Nuclear Information System (INIS)

    1997-12-01

    The separation of actinide elements from various waste materials, produced either in nuclear fuel cycles or in past nuclear weapons production, represents a significant issue facing developed countries. Improvements in the efficiencies of the separation processes can be expected to occur as a result of better knowledge of the elements in these complex matrices. The Nuclear Science Committee of the OECD/NEA has established a task force of experts in actinide separation chemistry to review current and developing separation techniques and chemical processes. The report consist of eight chapters. In Chapter 1 the importance of actinide separation chemistry in the fields of waste management and its background are summarized.In Chapter 2 the types of waste streams are classified according to their relative importance, by physical form and by source of actinides. The basic data of actinide chemical thermodynamics, such as oxidation states, hydrolysis, complexation, sorption, Gibbs energies of formation, and volatility, were collected and are presented in Chapter 3. Actinide analyses related to separation processes are also mentioned in this chapter. The state of the art of actinide separation chemistry is classified in three groups, including hydrometallurgy, pyrochemical process and process based on fields, and is described in Chapter 4 along with the relationship of kinetics to separations. In Chapter 5 basic chemistry research needs and the inherent limitation on separation processes are discussed. Prioritization of research and development is discussed in Chapter 6 in the context of several attributes of waste management problems. These attributes include: mass or volume of waste; concentration of the actinide in the waste; expected difficulty of treating the wastes; short-term hazard of the waste; long-term hazard of the waste; projected cost of treatment; amount of secondary waste. Based on the priority, recommendations were made for the direction of future research

  2. Actinide separation chemistry in nuclear waste streams and materials

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-01

    The separation of actinide elements from various waste materials, produced either in nuclear fuel cycles or in past nuclear weapons production, represents a significant issue facing developed countries. Improvements in the efficiencies of the separation processes can be expected to occur as a result of better knowledge of the elements in these complex matrices. The Nuclear Science Committee of the OECD/NEA has established a task force of experts in actinide separation chemistry to review current and developing separation techniques and chemical processes. The report consist of eight chapters. In Chapter 1 the importance of actinide separation chemistry in the fields of waste management and its background are summarized.In Chapter 2 the types of waste streams are classified according to their relative importance, by physical form and by source of actinides. The basic data of actinide chemical thermodynamics, such as oxidation states, hydrolysis, complexation, sorption, Gibbs energies of formation, and volatility, were collected and are presented in Chapter 3. Actinide analyses related to separation processes are also mentioned in this chapter. The state of the art of actinide separation chemistry is classified in three groups, including hydrometallurgy, pyrochemical process and process based on fields, and is described in Chapter 4 along with the relationship of kinetics to separations. In Chapter 5 basic chemistry research needs and the inherent limitation on separation processes are discussed. Prioritization of research and development is discussed in Chapter 6 in the context of several attributes of waste management problems. These attributes include: mass or volume of waste; concentration of the actinide in the waste; expected difficulty of treating the wastes; short-term hazard of the waste; long-term hazard of the waste; projected cost of treatment; amount of secondary waste. Based on the priority, recommendations were made for the direction of future research

  3. Interaction of Eu(III) and Cm(III) with mucin. A key component of the human mucosa

    Energy Technology Data Exchange (ETDEWEB)

    Wilke, Claudia; Barkleit, Astrid [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Chemistry of the F-Elements

    2017-06-01

    To evaluate the potential health risks caused by the ingestion of lanthanides (Ln) and actinides (An), investigations into the chemical behavior of these metals in the human gastrointestinal tract are necessary. Mucin is an important part of the protective mucosa layer in the digestive system. We have recently reported that mucin interacts strongly with Eu(III) and Cm(III), representatives of Ln(III) and An(III), respectively, under in vivo conditions. In order to investigate the complexation behavior of this protein with Ln(III)/An(III), TRLFS measurements were performed on Eu(III)/Cm(III)-mucin solutions with different protein concentrations and at different pH. The results indicate the formation of at least two independent mucin species. At higher pH, the formation of hydroxide species was also observed.

  4. Interaction of Eu(III) and Cm(III) with mucin. A key component of the human mucosa

    International Nuclear Information System (INIS)

    Wilke, Claudia; Barkleit, Astrid

    2017-01-01

    To evaluate the potential health risks caused by the ingestion of lanthanides (Ln) and actinides (An), investigations into the chemical behavior of these metals in the human gastrointestinal tract are necessary. Mucin is an important part of the protective mucosa layer in the digestive system. We have recently reported that mucin interacts strongly with Eu(III) and Cm(III), representatives of Ln(III) and An(III), respectively, under in vivo conditions. In order to investigate the complexation behavior of this protein with Ln(III)/An(III), TRLFS measurements were performed on Eu(III)/Cm(III)-mucin solutions with different protein concentrations and at different pH. The results indicate the formation of at least two independent mucin species. At higher pH, the formation of hydroxide species was also observed.

  5. Lanthanide and actinide extractions with anionic ligands based on cobalt bis(dicarbollide) ions with covalently bonded CMPO functions

    Energy Technology Data Exchange (ETDEWEB)

    Selucky, P.; Rais, J.; Lucanikova, M. [Nuclear Research Inst. plc., Rez near Prague (Czech Republic); Gruener, B.; Kvicalova, M. [Inst. of Inorganic Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Husinec-Rez near Prague (Czech Republic); Fejfarova, K. [Inst. of Physics, Academy of Sciences of the Czech Republic, Prague (Czech Republic); Cisarova, I. [Charles Univ., Prague (Czech Republic). Dept. of Chemistry

    2008-07-01

    Compounds were synthesized with the aim to develop efficient extraction agents for liquid-liquid extraction of polyvalent cations, i.e. lanthanides and actinides from high-level activity nuclear waste. Compounds of general formulation [(8-CMPO-(CH{sub 2}-CH{sub 2}O){sub 2}-1,2-C{sub 2}B{sub 9}H{sub 10})(1',2'-C{sub 2}B{sub 9}H{sub 11})-3.3'-Co(III)] with different phosphorus and nitrogen substitution (CMPO={sup 2}R,{sup 3}R P(O)-(CH{sub 2}){sub n}C(O)N{sup 1}R, {sup 1}R = t-octyl, H, Ph, {sup 2}R=Ph, n-octyl, {sup 3}R=Ph, n = 1,2)-(4a to 4e), were prepared and characterized by combination of {sup 11}B NMR, {sup 1}H high field NMR, ESI-M.S., HPLC and other techniques. Molecular structure of the sodium complex of ligand 4a ({sup 1}R = t-octyl, {sup 2}R = {sup 3}R = Ph, n = 1) was determined by single crystal X-ray diffraction analysis. Effect of several modifications in the structure of 4a-4e on the extraction properties was outlined. The study resulted in the definition of ionic ligand with enhanced extraction efficiency for 4a,b (t-octyl and H on the amidic nitrogen atom) and a better solubility of 4a and 4d ({sup 1}R = t-octyl, {sup 2}R = n-Oct, {sup 1}R=Ph, n = 1) in less polar solvents. Low polar mixtures of hydrogenated tetrapropylene (TPH) hexyl methyl ketone (HMK) can be applied as an auxiliary solvent for 4a, selected for detailed studies, replacing thus the polar and less environmentally friendly nitro-, fluoro- and chloro- solvents used in the current dicarbollide liquid-liquid extraction process. Results of the fission products separation from the simulated PUREX feed using 4a are presented inclusive procedures for Eu{sup 3+} stripping. (orig.)

  6. Process for denitrating waste solutions containing nitrates and actinides with simultaneous separation of the actinides

    International Nuclear Information System (INIS)

    Gompper, K.

    1986-01-01

    The invention is intended to reduce the acid and nitrate content of nitrate waste solutions, to reduce the total salt content of the waste solution, to remove the actinides contained in it by precipitation, without any danger of violent reactions or an increase in the volume of the waste solution. The invention achieves this by mixing the waste solution with diethyl oxalate at room temperature and heating the mixture to at least 80 0 C. (orig./PW) [de

  7. General survey of applications which require actinide nuclear data

    International Nuclear Information System (INIS)

    Raman, S.

    1976-01-01

    This review paper discusses the actinide waste problem, the buildup of toxic isotopes in the fuel, the neutron activity associated with irradiated fuel, the 252 Cf buildup problem, and the production of radioisotope power sources as broad areas that require actinide cross-section data. Decay data enter into the area of radiological safety and health physics. This paper also discusses a few cross-section measurements in progress at the Oak Ridge Electron Linear Accelerator. The availability of actinide samples through the Transuranium Program at Oak Ridge is discussed in considerable detail. The present data status with respect to the various applications is reviewed along with recommendations for improving the data base

  8. Review of actinide nitride properties with focus on safety aspects

    Energy Technology Data Exchange (ETDEWEB)

    Albiol, Thierry [CEA Cadarache, St Paul Lez Durance Cedex (France); Arai, Yasuo [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    2001-12-01

    This report provides a review of the potential advantages of using actinide nitrides as fuels and/or targets for nuclear waste transmutation. Then a summary of available properties of actinide nitrides is given. Results from irradiation experiments are reviewed and safety relevant aspects of nitride fuels are discussed, including design basis accidents (transients) and severe (core disruptive) accidents. Anyway, as rather few safety studies are currently available and as many basic physical data are still missing for some actinide nitrides, complementary studies are proposed. (author)

  9. Minor Actinide Laboratory at JRC-ITU: Fuel fabrication facility

    International Nuclear Information System (INIS)

    Fernandez, A.; McGinley, J.; Somers, J.

    2008-01-01

    The Minor Actinide Laboratory (MA-lab) of the Institute for Transuranium Elements is a unique facility for the fabrication of fuels and targets containing minor actinides (MA). It is of key importance for research on Partitioning and Transmutation in Europe, as it is one of the only dedicated facilities for the fabrication of MA containing materials, either for property measurements or for the production of test pins for irradiation experiments. In this paper a detailed description of the MA-Lab facility and the fabrication processes developed to fabricate fuels and samples containing high content of minor actinides is given. In addition, experience gained and improvements are also outlined. (authors)

  10. Status report on actinide and fission product transmutation studies

    International Nuclear Information System (INIS)

    1997-06-01

    The management of radioactive waste is one of the key issues in today's political and public discussions on nuclear energy. One of the fields that looks into the future possibilities of nuclear technology is the neutronic transmutation of actinides and of some most important fission products. Studies on transmutation of actinides are carried out in various countries and at an international level. This status report which gives an up-to-date general overview of current and planned research on transmutation of actinides and fission products in non-OECD countries, has been prepared by a Technical Committee meeting organized by the IAEA in September 1995. 168 refs, 16 figs, 34 tabs

  11. Report of the panel on practical problems in actinide biology

    International Nuclear Information System (INIS)

    Anon.

    1978-01-01

    Practical problems are classified as the need to make operational decisions, the need for regulatory assessment either of individual facilities or of generic actions, and the overt appearance of radiobiological effects in man or radioactivity in man or the environment. Topics discussed are as follows: simulated reactor accident; long term effects of low doses; effects of repeated exposures to actinides; inhaled uranium mine air contaminants; metabolism and dosimetry; environmental equilibrium models; patterns of alpha dosimetry; internal dose calculations; interfaces between actinide biology and environmental studies; removal of actinides deposited in the body; and research needs related to uranium isotopes

  12. Critical masses for the even-neutron-numbered transuranium actinides

    International Nuclear Information System (INIS)

    Westfall, R.M.

    1981-01-01

    As part of a standards effort of the American Nuclear Society to establish subcritical mass limits for the transuranium actinides, critical masses were calculated for seven actinides, critical masses were calculated for seven actinide elements in bare, water-reflected, and steel-reflected metal systems. For the nuclides /sup 242/Pu and /sup 241/Am, values obtained with ENDF/B-V cross-section data were in much better agreement with values inferred from experimental measurement than were initial values calculated with ENDF/B-IV data. A brief description of the analytical methods employed is followed by a presentation of the results. 10 refs

  13. Actinide and Xenon reactivity effects in ATW high flux systems

    International Nuclear Information System (INIS)

    Woosley, M.; Olson, K.; Henderson, D.L.

    1995-01-01

    In this paper, initial system reactivity response to flux changes caused by the actinides and xenon are investigated separately for a high flux ATW system. The maximum change in reactivity after a flux change due to the effect of the changing quantities of actinides is generally at least two orders of magnitude smaller than either the positive or negative reactivity effect associated with xenon after a shutdown or start-up. In any transient flux event, the reactivity response of the system to xenon will generally occlude the response due to the actinides

  14. Actinide and xenon reactivity effects in ATW high flux systems

    International Nuclear Information System (INIS)

    Woosley, M.; Olson, K.; Henderson, D. L.; Sailor, W. C.

    1995-01-01

    In this paper, initial system reactivity response to flux changes caused by the actinides and xenon are investigated separately for a high flux ATW system. The maximum change in reactivity after a flux change due to the effect of the changing quantities of actinides is generally at least two orders of magnitude smaller than either the positive or negative reactivity effect associated with xenon after a shutdown or start-up. In any transient flux event, the reactivity response of the system to xenon will generally occlude the response due to the actinides

  15. Self-interaction corrected local spin density calculations of actinides

    DEFF Research Database (Denmark)

    Petit, Leon; Svane, Axel; Szotek, Z

    2010-01-01

    We use the self-interaction corrected local spin-density approximation in order to describe localization-delocalization phenomena in the strongly correlated actinide materials. Based on total energy considerations, the methodology enables us to predict the ground-state valency configuration...... of the actinide ions in these compounds from first principles. Here we review a number of applications, ranging from electronic structure calculations of actinide metals, nitrides and carbides to the behaviour under pressure of intermetallics, and O vacancies in PuO2....

  16. Actinide and Xenon reactivity effects in ATW high flux systems

    Energy Technology Data Exchange (ETDEWEB)

    Woosley, M. [Univ. of Virginia, Charlottesville, VA (United States); Olson, K.; Henderson, D.L. [Univ. of Wisconsin, Madison, WI (United States)] [and others

    1995-10-01

    In this paper, initial system reactivity response to flux changes caused by the actinides and xenon are investigated separately for a high flux ATW system. The maximum change in reactivity after a flux change due to the effect of the changing quantities of actinides is generally at least two orders of magnitude smaller than either the positive or negative reactivity effect associated with xenon after a shutdown or start-up. In any transient flux event, the reactivity response of the system to xenon will generally occlude the response due to the actinides.

  17. Extraction chromatographic method for the separation of actinides and lanthanides using EDHBA grafted AXAD-16 polymer

    Energy Technology Data Exchange (ETDEWEB)

    Akhila Maheswari, M.; Subramanian, M.S. [Department of Chemistry, Indian Institute of Technology, Chennai (India)

    2005-02-15

    A new extraction chromatographic method has been developed by grafting chloromethylated polymer support with 4-ethoxy-N,N-dihexylbutanamide (EDHBA), for the selective extraction of U(VI), Th(IV), La(III) and Nd(III) from highly acidic matrices. The developed grafted polymer has been characterized using {sup 13}C-CPMAS NMR spectroscopy, FT-NIR spectroscopy and also by CHN elemental analysis. The water regaining capacity of the grafted polymer is studied by TGA measurements and the active participation of the amide moiety towards metal ion complexation has been confirmed by Far IR spectroscopy. For the quantitative extraction of metal ions to the resin phase, various physico-chemical parameters are optimized by both static and dynamic methods. The developed amide grafted polymeric matrix shows good distribution ratio values even at high acidities, with the maximum metal sorption capacity values being 0.36, 0.69, 0.32 and 0.42mmolg{sup -1} for U(VI), Th(IV), La(III) and Nd(III), respectively, at 6M HNO{sub 3} medium. The kinetics of metal ion phase equilibration is found to be moderately fast, with t{sub 1/2} values of <6min, for all the analytes of interest. The limits of analyte quantification (LOQ) using the developed method are in the range of 15-30{mu}gL{sup -1}. Moreover, the sequential separation of the sorbed actinides and lanthanides could be achieved by first eluting with 100mL of distilled water (for actinides) followed by elution with 20mL of 0.1M EDTA (for lanthanides). The selectivity behavior and the practical applicability of the developed resin are tested using synthetic low level nuclear reprocessing mixtures and also with monazite sand. The analytical data are within 3.8% relative standard deviation, reflecting the reproducibility and reliability of the developed method.

  18. Sorption by cation exchange

    International Nuclear Information System (INIS)

    Bradbury, M.H.; Baeyens, B.

    1994-04-01

    A procedure for introducing exchange into geochemical/surface complexation codes is described. Beginning with selectivity coefficients, K c , defined in terms of equivalent fractional ion occupancies, a general expression for the molar based exchange code input parameters, K ex , is derived. In natural systems the uptake of nuclides onto complex sorbents often occurs by more than one mechanism. The incorporation of cation exchange and surface complexation into a geochemical code therefore enables sorption by both mechanisms to be calculated simultaneously. The code and model concepts are tested against sets of experimental data from widely different sorption studies. A proposal is made to set up a data base of selectivity coefficients. Such a data base would form part of a more general one consisting of sorption mechanism specific parameters to be used in conjunction with geochemical/sorption codes to model and predict sorption. (author) 6 figs., 6 tabs., 26 refs

  19. Energy Transfer between U(VI) and Eu(III) Ions Adsorbed on a Silica Surface

    Energy Technology Data Exchange (ETDEWEB)

    Park, K. K.; Cha, W.; Cho, H. R.; Im, H. J.; Jung, E. C.; Song, K. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2011-05-15

    Understanding of chemical behavior of actinide in a groundwater flow is important for assessing the possibility of their migration with water flows in a radioactive waste disposal site. Uranium is ubiquitous in the environment and a major actinide in a nuclear fuel cycle. Americium and curium having isotopes of long half life are minor actinides in a spent fuel. If a minor actinide coexists with uranium in a groundwater flow, some interactions between them could be expected such as minor actinide adsorption onto uranium precipitates and competition with each other for an adsorption to a mineral surface site. Eu(III) ion is frequently used as a chemical analogue of Am(III) and Cm(III) ions in a migration chemistry. The luminescent spectra of U(VI) and Eu(III) ions show a dependency on the coordination symmetry around them, and the changes in intensity or bandwidth of spectra can yield valuable information on their local environment. The luminescent lifetime also strongly depends on the coordination environment, and its measurement is valuable in probe studies on micro-heterogeneous systems. The excited U(VI) ion can be quenched through Stern.Volmer process, hydrolysis of excited species, exciplex formation, electron transfer or energy transfer. In case of U(VI)-Eu(III) system, the interaction between two ions can be studied by measuring the effect of Eu(III) ion on the quenching of U(VI) ion luminescence. There are only a few investigations on the interaction between an excited U(VI) ion and a lanthanide(III) ion. In perchlorate solution, the energy transfer to Eu(III) ion occurred only in solutions of pH>3.87. In this study, the quenching of U(VI) luminescence by Eu(III) on a silica surface was measured. The results will be discussed on the basis of a chemical interaction between them

  20. Fission properties of very heavy actinides

    International Nuclear Information System (INIS)

    Hoffman, D.C.

    1979-01-01

    The existing data on neutron-emission, kinetic-energy and mass distributions, and half-lives for spontaneous fission of the heavy actinides are reviewed. A comparison of the data for the Fm isotopes with heavier and lighter nuclides suggests that the properties of the heavy Fm isotopes may be unique and can qualitatively be explained on the basis of fragment shell effects, i.e., symmetric fission results in two fragments with configurations close to the doubly magic 132 Sn nucleus. The effect of excitation energy and the use of systematics and theoretical predictions of fission properties and half-lives in the identification of new heavy element isotopes is discussed. 54 references