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Sample records for actinide chemistry

  1. Radiochemistry and actinide chemistry

    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 1012, 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

  2. Actinide separative chemistry

    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

  3. Actinide environmental chemistry

    In order to predict release and transport rates, as well as design cleanup and containment methods, it is essential to understand the chemical reactions and forms of the actinides under aqueous environmental conditions. Four important processes that can occur with the actinide cations are: precipitation, complexation, sorption and colloid formation. Precipitation of a solid phase will limit the amount of actinide in solution near the solid phase and have a retarding effect on release and transport rates. Complexation increases the amount of actinide in solution and tends to increase release and migration rates. Actinides can sorb on to mineral or rock surfaces which tends to retard migration. Actinide ions can form or become associated with colloidal sized particles which can, depending on the nature of the colloid and the solution conditions, enhance or retard migration of the actinide. The degree to which these four processes progress is strongly dependent on the oxidation state of the actinide and tends to be similar for actinides in the same oxidation state. In order to obtain information on the speciation of actinides in solution, i.e., oxidation state, complexation form, dissolved or colloidal forms, the use of absorption spectroscopy has become a method of choice. The advent of the ultrasensitive, laser induced photothermal and fluorescence spectroscopies has made possible the detection and study of actinide ions at the parts per billion level. With the availability of third generation synchrotrons and the development of new fluorescence detectors, X-ray absorption spectroscopy (XAS) is becoming a powerful technique to study the speciation of actinides in the environment, particularly for reactions at the solid/solution interfaces. (orig.)

  4. Research in actinide chemistry

    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-, CO32-, PO43-, humates). The research undertakes fundamental studies of actinide complexes which can increase understanding of the environmental behavior of these elements

  5. Research in actinide chemistry

    1991-01-01

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

  6. Actinide chemistry in ionic liquids.

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

    2013-04-01

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

  7. Environmental chemistry of the actinide elements

    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

  8. Chemistry of actinides and fission products

    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

  9. Actinide chemistry in the far field

    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)

  10. Overview of actinide chemistry in the WIPP

    Borkowski, Marian [Los Alamos National Laboratory; Lucchini, Jean - Francois [Los Alamos National Laboratory; Richmann, Michael K [Los Alamos National Laboratory; Reed, Donald T [Los Alamos National Laboratory; Khaing, Hnin [Los Alamos National Laboratory; Swanson, Juliet [Los Alamos National Laboratory

    2009-01-01

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

  11. Recent progress in actinide borate chemistry.

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

    2011-10-21

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

  12. Coordination chemistry for new actinide separation processes

    The amount of wastes and the number of chemical steps can be decreased by replacing the PUREX process extractant (TBP) by, N.N- dialkylamides (RCONR'2). Large amounts of deep underground storable wastes can be stored into sub-surface disposals if the long lived actinide isotopes are removed. Spent nuclear fuels reprocessing including the partitioning of the minor actinides Np, Am, Cm and their transmutation into short half lives fission products is appealing to the public who is not favorable to the deep underground storage of large amounts of long half lived actinide isotopes. In this paper coordination chemistry problems related to improved chemical separations by solvent extraction are presented. 2 tabs.; 4 refs

  13. Actinide coordination chemistry: towards the limits of the periodic table

    Actinide elements represent a distinct chemical family at the bottom of the periodic table. Among the major characteristics of this 14 element family is their high atomic numbers and their radioactivity. Actinide chemistry finds its roots in the history of the 20. century and plays a very important role in our contemporary world. Energetic as well as technical challenges are facing the development of nuclear energy. In this pedagogical introduction to actinide chemistry, the authors draw a comparison between the actinides family and the chemistry of two other families, lanthanides and transition metals. This article focuses on molecular and aqueous chemistry. It has been based on class notes aiming to present an overview of the chemical diversity of actinides, and its future challenges for modern science. (authors)

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

    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.

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

    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.

  16. Actinide separation chemistry in nuclear waste streams and materials

    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

  17. Programme and Abstracts. 38. Journees des Actinides together with the 7. School on the Physics and Chemistry of the Actinides

    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 38th 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

  18. Recent progress in actinide borate chemistry

    Wang, S.; Alekseev, E .V.; Depmeier, W.; Albrecht-Schmitt, T.E.

    2011-01-01

    The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties. [ThB(5)O(6)(OH)(6)][BO(OH)(2)]·2.5H(2)O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO(4)(-). Uranyl borates form noncentrosymmetric structures with extraordinarily rich topol...

  19. Chemistry of tetravalent actinides phosphates. The thorium phosphate-diphosphate as immobilisation matrix of actinides

    The author presents in this document its scientific works from 1992 to 2001, in order to obtain the enabling to manage scientific and chemical researches at the university Paris Sud Orsay. The first part gives an abstract of the thesis on the characterizations, lixiviation and synthesis of uranium and thorium based phosphate matrix in the framework of the search for a ceramic material usable in the radioactive waste storage. The second part presents briefly the researches realized at the CEA, devoted to a reliable, independent and accurate measure of some isotopes activity. The last part presents the abstracts of researches activities from 1996 to 2001 on the tetravalent actinides phosphates chemistry, the sintering of PDT and solid solutions of PDTU and the kinetic and thermodynamical studies of the PDT dissolution. Many references and some publication in full text are provided. (A.L.B.)

  20. Actinide Sciences at ITN - Basic Studies in Chemistry with Potential Interest for Partitioning, Fuel Fabrication and More

    The current activities in the area of actinide chemistry at ITN, comprising basic research studies in inorganic and organometallic chemistry, catalysis, gas-phase ion chemistry, thermochemistry, and solid state chemistry, are briefly described. Actinide (and lanthanide) chemistry studies at ITN will be pursued connecting basic research with potential applications in nuclear and non-nuclear areas. (authors)

  1. Computational chemistry for nuclear waste characterization and processing. Relativistic quantum chemistry of actinides

    This paper describes some of the motivations and accomplishments of our grand challenge project of the same title and focuses upon the activities at Pacific Northwest National Laboratory. The United States Department of Energy (DOE) funded the project, which finishes this fiscal year. Its objectives were to develop and apply the methods of relativistic quantum chemistry to assists in the understanding and prediction of the chemistry of actinide and lanthanide compounds. This is important to the DOE because the production of nuclear weapons at DOE facilities has left a serious legacy of environmental contamination, including millions of gallons of highly radioactive waste stored in hundreds of tanks that have exceeded their life expectancy. Much of the radioactive waste involves actinides, and their large atomic number implies that relativistic effects have important chemical consequences. By using modern non-relativistic quantum chemistry techniques, it is now possible to calculate to high accuracy the structures, energetics, and properties of molecules containing light elements. Our implementation of relativistic quantum chemical methods will, for the first time on massively parallel computers, provide capabilities for modeling heavy-element compounds similar to those currently available for light-element compounds. (author)

  2. Actinide coordination chemistry: towards the limits of the periodic table; Chimie de coordination des actinides: vers les frontieres du tableau periodique

    Den Auwer, C.; Moisy, P. [CEA Marcoule (DEN/DRCP/SCPS), 30 (France); Simoni, E. [Paris-11 Univ., 91 - Orsay (France). Inst. de Physique Nucleaire

    2009-05-15

    Actinide elements represent a distinct chemical family at the bottom of the periodic table. Among the major characteristics of this 14 element family is their high atomic numbers and their radioactivity. Actinide chemistry finds its roots in the history of the 20. century and plays a very important role in our contemporary world. Energetic as well as technical challenges are facing the development of nuclear energy. In this pedagogical introduction to actinide chemistry, the authors draw a comparison between the actinides family and the chemistry of two other families, lanthanides and transition metals. This article focuses on molecular and aqueous chemistry. It has been based on class notes aiming to present an overview of the chemical diversity of actinides, and its future challenges for modern science. (authors)

  3. Separations chemistry for actinide elements: Recent developments and historical perspective

    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

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

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

    2012-08-22

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

  5. Research on the actinide chemistry in Nuclear Fuel Cycle

    Fundamental technique to measure chemical behaviors and properties of lanthanide and actinide in radioactive waste is necessary for the development of pryochemical process. First stage, 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 equipments, 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. In the second stage, measurement system for physical properties at pyrochemical process such as viscosity, melting point and conductivity is established, and property database at different compositions of lanthanide and actinide is collected. And, both interactions between elements and properties with different potential are measured at binary composition of actinide-lanthanide in molten salt using electrochemical/spectroscopic integrated measurement system.

  6. Review and needs in actinide chemistry in relation with biological purposes

    Ansoborlo, E.; Moulin, V.; Bion, L.; Doizi, D.; Moulin, C.; Cote, G.; Madic, C.; Van der Lee, J

    2004-07-01

    In case of accidental release of radionuclides in the environment, actinides could occur and may present an healthy risk for human beings. In order to study their behavior in human organism (metabolism, retention, excretion), it is of prime importance to know solution actinide chemistry, and more particularly thermodynamic constants, which will allow to determine their speciation: speciation governs biological availability and toxicity of elements and is also of great interest for decorporation purposes. In this framework, a CEA working group on speciation has been created in order to share data both on thermodynamic constants and on speciation analytical methods, interesting chemists, environmentalists and biologists. It has been focused, in a first time, on actinides. The purpose of this paper is to present the state of the art on actinide speciation within biological media and to focus on the lack of information in order to orientate future research. (authors)

  7. Review and needs in actinide chemistry in relation with biological purposes

    In case of accidental release of radionuclides in the environment, actinides could occur and may present an healthy risk for human beings. In order to study their behavior in human organism (metabolism, retention, excretion), it is of prime importance to know solution actinide chemistry, and more particularly thermodynamic constants, which will allow to determine their speciation: speciation governs biological availability and toxicity of elements and is also of great interest for decorporation purposes. In this framework, a CEA working group on speciation has been created in order to share data both on thermodynamic constants and on speciation analytical methods, interesting chemists, environmentalists and biologists. It has been focused, in a first time, on actinides. The purpose of this paper is to present the state of the art on actinide speciation within biological media and to focus on the lack of information in order to orientate future research. (authors)

  8. Multiconfigurational quantum chemistry for actinide containing systems: from isolated molecules to condensed phase

    Complete text of publication follows: Ab initio quantum chemistry is a mature science that allows the study of molecular species containing any of the atoms in the periodic system. In this lecture I will describe our latest achievements in the prediction of novel chemical bonds and chemical species, including the multiple bond in the early-di-actinide series [1] and some novel inorganic compounds containing the di-uranium moiety [2]. In nature most of actinide chemistry occurs in solution. We try to combine ab initio quantum chemistry with classical molecular dynamics simulations in order to understand the behavior of highly charged ions in solution. Our recent studies of uranyl [3] and Cm(III) [4] in water will be presented. References: [1] B. O. Roos, P.-A. Malmqvist and L. Gagliardi, Exploring the actinide-actinide bond: Theoretical studies of the chemical bond in Ac2, Th2, Pa2, and U2 J. Am. Chem. Soc. 128, 17000-17006 (2006) [2] G. La Macchia, M. Brynda, and L. Gagliardi, Quantum chemical calculations predict the diphenyl di-uranium compound, PhUUPh, to have a stable 1Ag ground state Angew. Chem. Int. Ed. 45, 6210-6213 (2006); [3] 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); [4] E. Bednarz, D. Hagberg, L. Gagliardi in preparation

  9. Physical chemistry and modelling of the sintering of actinide oxides

    This report gives a synthesis of the work I have carried out or to which I have numerically contributed to from 1996 up to 2012 in the Department of Plutonium Uranium and minor Actinides in Cadarache CEA Center. Their main goal is the study and the modeling of the sintering process of nuclear fuels which is the unifying thread of this document. Both in order to take into account the physical and chemical features of the actinide bearing oxide material and in order to combine the different transport phenomena leading to sintering, a sub-granular scale model is under development. Extension to a varying chemical composition as well as exchanges with the gaseous phase are foreseen. A simulation on a larger scale (pellet scale) is ongoing in the framework of a PhD thesis. Validation means have been tested with (U,Pu)O2 material on the scale of the pellet (Small Angle Neutron Diffusion), on the scale of powder granules (X-Ray High Resolution Micro-Tomography) and with CeO2 at the 'Institut de Chimie Separative' in Marcoule on a single crystal scale (Environmental Scanning Electron Microscope). The required microstructure homogeneity for nuclear fuels has led to a campaign of experimental studies about the role of Cr2O3 as a sintering aid. Whole of these studies improve our understanding of fuel sintering and hence leads to an improved mastering of this process. (author)

  10. Coordination polymers: trapping of radionuclides and chemistry of tetravalent actinides (Th, U) carboxylates

    The use of nuclear energy obviously raises the question of the presence of radionuclides in the environment. Currently, their mitigation is a major issue associated with nuclear chemistry. This thesis focuses on both the trapping of radionuclides by porous solids called Metal-Organic Frameworks (MOF) and the crystal chemistry of the carboxylate of tetravalent actinides (AnIV). The academic knowledge of the reactivity of carboxylate of AnIV could help the understanding of actinides speciation in environment. We focused on the sequestration of iodine by aluminum based MOF. The functionalization (electron-donor group) of the MOF drastically enhances the iodine capture capacity. The removal of light actinides (Th and U) from aqueous solution was also investigated as well as the stability of (Al)-MOF under γ radiation. More than twenty coordination polymers based on tetravalent actinides have been synthesized and characterized by single crystal X-ray diffraction. The use of controlled hydrolysis promotes the formation of coordination polymers exhibiting polynuclear cluster ([U4], [Th6], [U6] and [U38]). In order to understand the formation of the largest cluster, the ex-situ study of the solvo-thermal synthesis of compound {U38} has also been investigated. (author)

  11. Actinides-1981

    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.

  12. Actinides-1981

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

  13. Chemistry of neptunium and of other actinides in carbonate medium

    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

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

    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.

  15. Advancing Chemistry with the Lanthanide and Actinide Elements Final Report, September 2013

    Evans, William John [Univ. of California, Irvine, CA (United States)

    2013-09-11

    The objective of this research is to use the unique chemistry available from complexes of the lanthanides and actinides, as well as related heavy metals such as scandium, yttrium, and bismuth to advance chemistry in energy-related areas. The lanthanides and actinides have a combination of properties in terms of size, charge, electropositive character, and f valence orbitals that provides special opportunities to probe reactivity and catalysis in ways not possible with the other metals in the periodic table. We seek to discover reaction pathways and structural types that reveal new options in reaction chemistry related to energy. Identification of new paradigms in structure and reactivity should stimulate efforts to develop new types of catalytic processes that at present are not under consideration because either the transformation or the necessary intermediates are unknown. This project is one half of my laboratory’s DOE research which was split 50:50 between Catalysis and Heavy Element Chemistry programs in 2010. Hence, this report is for a half-project.

  16. Proceedings of the specialists' meeting on the chemistry and technology of actinide elements 2011

    This report contains the Proceedings of the 17th Specialists' Meeting on the Chemistry and Technology of Actinide Elements, which was held at Research Reactor Institute, Kyoto University, on February 15, 2012. This specialists' meeting has been held annually since 1994, and this is the 17th meeting for the fiscal year 2011. The accident of Fukushima Daiich Nuclear Power Plant, which occurred on March 11, 2011, showed the presence of defect in Japanese past approach to keep nuclear system safe. There is the need to improve existing technological and operational problems, as well as regulatory problems, but we should be aware of the significance of recovering social trust and peoples' peace of mind with the nuclear power. It should be noted that public's anxiety on the backend issue of nuclear system is remarkably big, and thus we must try to provide an understandable solution to them. In this meeting, we dealt with actinide chemistry and technology, which are related to the advanced nuclear fuel cycle development and the disposal of the HLW or TRU wastes. This is because, in the backend of the nuclear system, Actinide and TRU elements have substantial importance, because all of reprocessing, geologic disposal, and partitioning and transmutation depend significantly on the chemistry and technology of Actinides. Therefore, we have continued discussion and information exchange on the Actinide issues over 16 years, and this year's 17th meeting had a special meaning as the first one after the accident. In this context in this 17th meeting, we tried to return to the fundamentals of molten salt chemistry, which is the base of the dry reprocessing development. In addition, in order to expand our attitude by crossing over the fence of nuclear society, we tried to explore the potential of the adoption of molten salt chemistry to the general industry. This was a small new attempt in compliance with the recent tendency to nuclear power reduction in

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

    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

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

    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.

  19. Handbook on the physics and chemistry of the actinides. V. 6

    In the last 15 years, actinide research has presented unique challenges both for experimentalists and theorists. The uniqueness stems not only from their nuclear properties, which since the early 1940's has led to their important role in nuclear energy and nuclear technology, but also from their unusual chemical and physical properties which have added new excitement and discoveries to both these disciplines. It is the purpose of this handbook to describe in detail the present understanding of the actinides by means of comprehensive, critical, broad and up-to-date reviews covering both the physics and chemistry of these exotic elements. They are intended to serve as an introduction to the subject for the non-specialist, as a convenient reference work for the specialist, and as a guide for future research. The rapid accelerated pace of research in the last decade continues and carries with it new vigor and excitement to a field in a state of transition. The present sixth volume completes the series. Like volumes 3 and 4, the emphasis is on chemistry, though physical aspects, such as self-radiation effects and electron paramagnetic resonance are also treated. The main body of the volume is devoted to systematic and comprehensive studies of a variety of important actinide compounds. These include relatively simple salts as well as various complexes and organic compounds. The data accumulated on such materials are broadly scattered in the literature, due to the interdisciplinary nature of much of the underlying research. Experts on the various substances have now reviewed this literature and brought it together in this book. refs.; figs.; tabs

  20. Chemistry of tetravalent actinides phosphates. The thorium phosphate-diphosphate as immobilisation matrix of actinides; Chimie des phosphates d'actinides tetravalents. Le phosphate-diphosphate de thorium en tant que matrice d'imobilisation des actinides

    Dacheux, N

    2002-07-01

    The author presents in this document its scientific works from 1992 to 2001, in order to obtain the enabling to manage scientific and chemical researches at the university Paris Sud Orsay. The first part gives an abstract of the thesis on the characterizations, lixiviation and synthesis of uranium and thorium based phosphate matrix in the framework of the search for a ceramic material usable in the radioactive waste storage. The second part presents briefly the researches realized at the CEA, devoted to a reliable, independent and accurate measure of some isotopes activity. The last part presents the abstracts of researches activities from 1996 to 2001 on the tetravalent actinides phosphates chemistry, the sintering of PDT and solid solutions of PDTU and the kinetic and thermodynamical studies of the PDT dissolution. Many references and some publication in full text are provided. (A.L.B.)

  1. Basic actinide and fission products chemistry in the CEC-coordinated project: Migration of radionuclides in the geosphere (MIRAGE)

    The paper reviews the research works performed on the basic actinide (Am, Pu, Np) and fission product (Tc, Sr) chemistry by four CEC member laboratories under the project named 'MIRAGE' for the years 1983 and 1984. Research subjects dealt with are solubility, carbonate complexation, hydrolysis reaction, colloid generation, speciation methods and sorption phenomena. Important achievements are summarized and discussed for each subject separately. (orig.)

  2. Influence of chloride ions on actinide chemistry. Effects of radiolysis and temperature

    This research thesis addresses the chemistry of radionuclides in natural waters, an issue which is related to the management of long life radioactive wastes. Chloride ions are the most concentrated ions but their weak complexing power explains the fact that they are often neglected in speciation calculations. The objective of this research is to identify the influence of chloride ions on transuranium elements (Np, Pu and Am). Their influence is investigated with respect to chemical conditions close to that of underground waters and for concentrated media related to storage conditions in saline media. The author discusses media-related corrections applied to thermodynamic functions, reports a bibliographic study on the stability of actinide chloride complexes, reports a spectrophotometric investigation of complexation by chlorides, and reports the study of the influence of chlorides in a carbonate medium (solubility of americium at different temperatures, and notably at room temperature)

  3. Probing the chemistry, electronic structure and redox energetics in pentavalent organometallic actinide complexes

    Graves, Christopher R [Los Alamos National Laboratory; Vaughn, Anthony E [Los Alamos National Laboratory; Morris, David E [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

    2008-01-01

    Complexes of the early actinides (Th-Pu) have gained considerable prominence in organometallic chemistry as they have been shown to undergo chemistries not observed with their transition- or lanthanide metal counterparts. Further, while bonding in f-element complexes has historically been considered to be ionic, the issue of covalence remains a subject of debate in the area of actinide science, and studies aimed at elucidating key bonding interactions with 5f-orbitals continue to garner attention. Towards this end, our interests have focused on the role that metal oxidation state plays in the structure, reactivity and spectral properties of organouranium complexes. We report our progress in the synthesis of substituted U{sup V}-imido complexes using various routes: (1) Direct oxidation of U{sup IV}-imido complexes with copper(I) salts; (2) Salt metathesis with U{sup V}-imido halides; (3) Protonolysis and insertion of an U{sup V}-imido alkyl or aryl complex with H-N{double_bond}CPh{sub 2} or N{triple_bond}C-Ph, respectively, to form a U{sup V}-imido ketimide complex. Further, we report and compare the crystallographic, electrochemical, spectroscopic and magnetic characterization of the pentavalent uranium (C{sub 5}Me{sub 5}){sub 2}U({double_bond}N-Ar)(Y) series (Y = OTf, SPh, C{triple_bond}C-Ph, NPh{sub 2}, OPh, N{double_bond}CPh{sub 2}) to further interrogate the molecular, electronic, and magnetic structures of this new class of uranium complexes.

  4. Sol gel chemistry applied to the synthesis of actinide-based compounds for the fabrication of advanced fuels

    The chemistry of the sol-gel process is based on hydroxylation and condensation of molecular precursors and can be used for the elaboration of advanced nuclear fuel or transmutation targets. On the one hand, some fundamental studies are conducted, based on complexation reactions to modulate and control the reactivity of the different cations (Zr(IV) and minor actinides) prior to hydrolysis and condensation step. The purpose of this work is to obtain hetero poly-condensation in order to form homogenous compounds with a controlled microstructure. On the other hand, internal gelation process, one of the important sol-gel routes for the preparation of actinides microspheres (the dedicated design for advanced nuclear fuel or transmutation targets) is developed. Investigations are currently carried out to study the gelation behaviour of solutions containing actinides (III) or (IV) in comparison with the more well known behaviour of U(VI) studied during the development of process for beads production (1960 - 1990). (authors)

  5. Combining theoretical chemistry and Xanes multi-edge experiments to probe actinide valence states

    Both structural and electronic properties of the actinide cations are of fundamental interest in order to describe the intramolecular interactions. The 5f and 6d orbitals are the first partially or totally vacant states of these elements and their properties reflect the nature of the actinide-ligand bond. Because of its chemical and orbital selectivities, XANES spectroscopy is useful to probe the actinides' frontier orbitals and then understand the cation reactivity toward chelating ligands. The actinide L3 edge contains structural information on the coordination polyhedron because of important scattering features. But very little electronic information can be extracted, due to the short core-hole lifetime, broadening the edge signal. On the other hand, the actinide M4,5 edges provide a better resolution and allow one to achieve electronic and structural information. Furthermore, coupling simulations of the experimental spectra and quantum chemical calculations lead to quantitative information such as the determination of the actinide coordination sphere and its effective charge. (authors)

  6. Combining theoretical chemistry and Xanes multi-edge experiments to probe actinide valence states

    Fillaux, C.; Guilbaud, Ph.; Guillaumont, D.; Moisy, Ph.; Den Auwer, Ch. [CEA Valrho, Dir. de l' Energie Nucleaire (DEN/DRCP/SCPS), 30 - Marcoule (France); Berthet, J.C. [CEA Saclay, Dept. de Recherche sur l' Etat Condense, les Atomes et les Molecules (DSM/DRECAM/SCM), 91 - Gif sur Yvette (France); Conradsonc, St.D. [Los Alamos National Laboratory, Los Alamos, NM (United States); Hennig, C. [Forschungszentrum Rossendorf, ROBL at ESRF, 38 - Grenoble (France); Roques, J.; Simoni, E. [Institut de Physique Nucleaire, 91 - Orsay (France); Shuh, D.K.; Tyliszczak, T.; Castro-Rodriguez, I. [Lawrence Berkeley National Laboratory, Berkeley, CA (United States)

    2007-10-15

    Both structural and electronic properties of the actinide cations are of fundamental interest in order to describe the intramolecular interactions. The 5f and 6d orbitals are the first partially or totally vacant states of these elements and their properties reflect the nature of the actinide-ligand bond. Because of its chemical and orbital selectivities, XANES spectroscopy is useful to probe the actinides' frontier orbitals and then understand the cation reactivity toward chelating ligands. The actinide L3 edge contains structural information on the coordination polyhedron because of important scattering features. But very little electronic information can be extracted, due to the short core-hole lifetime, broadening the edge signal. On the other hand, the actinide M4,5 edges provide a better resolution and allow one to achieve electronic and structural information. Furthermore, coupling simulations of the experimental spectra and quantum chemical calculations lead to quantitative information such as the determination of the actinide coordination sphere and its effective charge. (authors)

  7. A quantum chemistry study of actinide(III) and lanthanide(III) complexes with tridentate nitrogen ligands

    The structure and bonding in large complexes of actinide(III) and lanthanide(III) with tridentate N-donor ligands and water molecules have been investigated through quantum chemistry calculations in order to characterize the nature of the lanthanide-ligand and actinide-ligand bonds. Calculations have been performed using relativistic density functional theory on [M(L)(H2O)6]3+, [M(L)(H2O)5Cl]2+ and [M(H2O)9]3+ clusters where M = La, Ce, Nd, U, Pu, Am or Cm and L = 2,2':6'2''ter-pyridine (Terpy) or 2,6-bis(5,6-di-methyl-1,2,4-triazine-3-yl)pyridine (MeBtp). The calculated evolution of the M-L bond as a function of the cation shows that lanthanide-ligand distances decrease with the diminution of the ionic radius, whereas the actinide-ligand distances increase from uranium to americium and are shorter than Ln-N distances. These trends are explained by the presence of covalent effects in the metal-ligand decreasing in the order U > Pu > Am ≅ Cm ≅ Ln. (author)

  8. Research in actinide chemistry. Final report, March 1, 1993--February 28, 1996

    The present three-year grant period has been a fruitful one for the laboratory as research entered some new areas while continuing in others in which the group has been successful. As in past grant periods, the principal focus has been on complexation of actinide elements with inorganic and organic ligands. The ligands to study have been chosen for their value (known or potential) in actinide separations or for their potential role in environmental behavior of the actinides. Since the radioactivity of some actinides limits the variety of techniques which can be used in their study, we have used open-quotes oxidation state analogsclose quotes. These analogs have the same oxidation state and very similar chemical behavior but are stable or very long-lived. Also, the analogs are chosen for their redox stability to avoid uncertainties in interpretation of systems in which several oxidations may coexist (e.g., in the case of Pu). Examples of such analogs which we have used are: Nd(III), Eu(III) for Pu(III), Am(III), Cm(III); Th(IV) for U(IV), Pu(IV); NpO2+ for PuO2+; UO22+ for NpO22+, PuO22+. These analogs have allowed use of techniques which can increase significantly our understanding of actinide complexation

  9. Research in actinide chemistry. Final report, March 1, 1993--February 28, 1996

    Choppin, G R

    1997-01-01

    The present three-year grant period has been a fruitful one for the laboratory as research entered some new areas while continuing in others in which the group has been successful. As in past grant periods, the principal focus has been on complexation of actinide elements with inorganic and organic ligands. The ligands to study have been chosen for their value (known or potential) in actinide separations or for their potential role in environmental behavior of the actinides. Since the radioactivity of some actinides limits the variety of techniques which can be used in their study, we have used {open_quotes}oxidation state analogs{close_quotes}. These analogs have the same oxidation state and very similar chemical behavior but are stable or very long-lived. Also, the analogs are chosen for their redox stability to avoid uncertainties in interpretation of systems in which several oxidations may coexist (e.g., in the case of Pu). Examples of such analogs which we have used are: Nd(III), Eu(III) for Pu(III), Am(III), Cm(III); Th(IV) for U(IV), Pu(IV); NpO{sub 2}{sup +} for PuO{sub 2}{sup +}; UO{sub 2}{sup 2+} for NpO{sub 2}{sup 2+}, PuO{sub 2}{sup 2+}. These analogs have allowed use of techniques which can increase significantly our understanding of actinide complexation.

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

    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 (11H, 613C, 57139La) 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 139La for both halate and chloroacetate complexes; interaction of Pu(VI) with carbonates and bicarbonates; Ca+2, UO2+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

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

    Visible spectroscopy, NMR (1H1, 6C13, 57La139) spectroscopy, potentiometry, and calorimetry were used in lanthanide studies which have allowed much more thorough interpretation of actinide tracer studies. In the last several years, the studies were expanded to include actinides in the IV, V and VI oxidation states. Part of the research during this time was directed to investigation of actinide interaction with naturally occurring polyelectrolytes such as humic and fulvic acids. Since redox reactions seemingly occur in some of these interactions, a study of plutonium and neptunium redox behavior in the presence of organic complexing agents was started. Preliminary data are given for reduction of Np(VI) by various organic acids

  12. Chemistry of gaseous lower-valent actinide halides. Technical progress report

    Objective is to provide thermochemical data for key actinide halide and oxyhalide systems. Progress is reported on bond dissociation energies of gaseous ThCl4, ThCl3, ThCl2, and ThCl; bond dissociation energies of ruthenium fluorides; and mass spectroscopy of UF6

  13. Crystallo-chemistry of actinide nitrides (U1-yPuy)N and effect of impurities

    Investigations on actinide nitrides has been done in our Laboratories for Fast Breeder Reactors since the seventies and some properties are reported to show the interest for these fuels. Today, the actinide nitrides are reconsidered as possible fuels for the future fission reactors (GFR and LMFR selected by the international forum Generation IV). The results of new investigations on crystal structure of mixed mono-nitrides (U,Pu)N, and the effects of oxygen and carbon contaminations on this structure are presented. The cubic 'NaCl-fcc' type structure of actinide nitrides AnN with space group O5/h-Fm3m does not respect the 'Vegard law' model for the mixed nitrides (U1-yPuy)N. These nitrides are usually considered with strong metallic character associated with partial ionic bonding, but the ionic contribution in the An-N bonding determined in this work is very important and near 41.6% for UN and PuN. From results published on resistivity of mixed nitrides, the data on bonding must be also modified for partial covalence. This is in good agreement with the experimental lattice parameters which are not compatible with dominant metallic bonding. The numbers of bonding electrons in the nitrides (U1-yPuy)N are reevaluated and the low values proposed comparatively with those previously published confirm the strong ionic character with high concentration of An3+ ions. The solubility of oxygen and carbon in actinide nitrides (U1-yPuy)N are discussed from measurements on volume concentration of actinide oxide phase, total oxygen and carbon contents, and lattice parameter of nitrides. The oxygen solubility limit in UN is near 1000 ppm, with a lightly higher value of 1200 ppm for the mixed nitride (U0.8Pu0.2)N. The effects of oxygen or carbon atoms in the lattice of (U1-yPuy)N are analysed

  14. Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry

    Travis S. Grimes; Richard D. Tillotson; Leigh R. Martin

    2014-05-01

    TALSPEAK is a liquid/liquid extraction process designed to separate trivalent lanthanides (Ln3+) from minor actinides (MAs) Am3+ and Cm3+. Traditional TALSPEAK organic phase is comprised of a monoacidic dialkyl bis(2-ethylhexyl)phosphoric acid extractant (HDEHP) in diisopropyl benzene (DIPB). The aqueous phase contains a soluble aminopolycarboxylate diethylenetriamine-N,N,N’,N”,N”-pentaacetic acid (DTPA) in a concentrated (1.0-2.0 M) lactic acid (HL) buffer with the aqueous acidity typically adjusted to pH 3.0. TALSPEAK balances the selective complexation of the actinides by DTPA against the electrostatic attraction of the lanthanides by the HDEHP extractant to achieve the desired trivalent lanthanide/actinide group separation. Although TALSPEAK is considered a successful separations scheme, recent fundamental studies have highlighted complex chemical interactions occurring in the aqueous and organic phases during the extraction process. Previous attempts to model the system have shown thermodynamic models do not accurately predict the observed extraction trends in the p[H+] range 2.5-4.8. In this study, the aqueous phase is modified by replacing the lactic acid buffer with a variety of simple and longer-chain amino acid buffers. The results show successful trivalent lanthanide/actinide group separation with the aqueous-modified TALSPEAK process at pH 2. The amino acid buffer concentrations were reduced to 0.5 M (at pH 2) and separations were performed without any effect on phase transfer kinetics. Successful modeling of the aqueous-modified TALSPEAK process (p[H+] 1.6-3.1) using a simplified thermodynamic model and an internally consistent set of thermodynamic data is presented.

  15. Einsteinium chemistry in the gas phase: exploring the divalent character of heavy actinides

    The first chemical studies of the monopositive einsteinium ion, Es+, in the gas phase have been carried out, and its behavior compared to those for other actinide ions, with a particular focus on Bk+. The yield of laser-ablated EsO+ indicates that the Es+-O bond energy is significantly smaller than that of Bk+-O. Fluorination of Es+ and Bk+ through F-abstraction from hexafluoropropene demonstrated clearly the stability of the divalent state of Es: whereas by this process both BkF+ and BkF2+ are produced, only the ''divalent'' EsF+ product is formed. The reaction of Es+ with several different alkenes produced only small yields of adducts (e.g., EsC4H8+). These adducts are the first organoeinsteinium complexes to be identified. Whereas Es+ was inert towards 1,5-cyclooctadiene, in contrast Bk+ dehydrogenated this substrate to give BkC8H8+, demonstrating the greater activation activity of Bk+ than Es+ towards alkenes. The chemical behaviors observed in these studies are consistent with the predicted electronic structure and energetics of Es+, and the results obtained are discussed in the context of systematic trends across the actinide series. (orig.)

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

    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 250C. Results indicate that three different coordination modes, one tridentate and two bidentate are in evidence. Tracer level 241Am - 155Eu 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 241Am, 155Eu, and 160Tb 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

  17. Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals

    Garza, Alejandro J; Scuseria, Gustavo E

    2015-01-01

    Singlet-paired coupled cluster doubles (CCD0) is a simplification of CCD that relinquishes a fraction of dynamic correlation in order to be able to describe static correlation. Combinations of CCD0 with density functionals that recover specifically the dynamic correlation missing in the former have also been developed recently. Here, we assess the accuracy of CCD0 and CCD0+DFT (and variants of these using Brueckner orbitals) as compared to well-established quantum chemical methods for describing ground-state properties of singlet actinide molecules. The $f^0$ actinyl series (UO$_2^{2+}$, NpO$_2^{2+}$, PuO$_2^{2+}$), the isoelectronic NUN, and Thorium (ThO, ThO$^{2+}$) and Nobelium (NoO, NoO$_2$) oxides are studied.

  18. Synthesis, growth, and studies (crystal chemistry, magnetic chemistry) of actinide-based intermetallic compounds and alloys with a 1.1.1 stoichiometry

    The first part of this research thesis reports the study of the synthesis and reactivity of intermetallic compounds with a 1.1.1 stoichiometry. It presents the thermal properties of 1.1.1 compounds: general presentation of physical transitions, and of solid solutions and formation heat, application to actinides (reactivity analysis from phase diagrams, techniques of crystal synthesis and crystal growth. It describes experimental techniques: synthesis, determination of fusion temperature by dilatometry, methods used for crystal growth, characterisation techniques (metallography, X ray diffraction on powders, dilatometry). It discusses the obtained results in terms of characterisation of synthesised samples, of crystal growth, and of measurements of fusion temperature. The second part addresses crystal chemistry studies: structure of compounds with a 1.1.1 stoichiometry (Laves structures, Zr, Ti and Pu compounds), techniques of analysis by X-ray diffraction (on powders and on single crystals), result interpretation (UNiX compounds, AnTAl compounds with T being a metal from group VIII, AnTGa compounds, AnNiGe compounds, distance comparison, structure modifications under pressure). The third part concerns physical issues. The author addresses the following topics: physical properties of intermetallic 1.1.1 compounds (magnetism of yttrium phases, behaviour of uranium-based Laves phases, analysis of pseudo-binary diagrams, physical characteristics of uranium-based 1.1.1 compounds, predictions of physical measurements), analysis techniques (Moessbauer spectroscopy, SQUID for Superconducting Quantum Interference Device), and result interpretation

  19. Chemistry and migration behaviour of the actinides and fission products in natural aquatic systems

    The 66th PTB seminar was held on April 24th and 25th, 1986, at the Munich Technical University (TUM) in Garching in cooperation with the Institute for Radiochemistry of the Munich Technical University, the 'Nuclear Chemistry' special group of the Society of German Chemists, and UB/SN responsible for the BMFT project. The seminar was organized by the TUM's Institute for Radiochemistry. The seminar dealt with the following main topics: primary geochemical reactions and colloid formation; sorption mechamisms and migration behaviour in Konrad/Gorleben aquifer systems; sampling and experimental investigations; evaluation and interpretation of the data obtained by experiments. The seminar was to achieve the following objectives: information and exchange of experience with regard to the work carried out up to the present; if necessary, formulation of new issues to be discussed; improvement of the interdisciplinary cooperation (chemistry, geosciences, modelling). The following topics and individual aspects were of particular interest and were given special attention: complementary basic research in order to interpret, support and model the results obtained by experiments (sorption mechanisms and thermodynamic data for natural systems); comparability of batch, column and diffusion tests; transferability of laboratory data to natural systems (e.g. Gorleben, Konrad); redox transitions for Np, Tc at Eh values of the natural systems; dependence of the sorption/desorption data on different influencing factors, importance of the influencing factors and selection of data for model calculations. Subject analyses of the individual contributions have been made for the Energy data base. (orig./RB)

  20. Concentration of actinides in the food chain

    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)

  1. The seventh international conference on the chemistry and migration behavior of actinides and fission products in the Geosphere MIGRATION'99 abstracts

    The Migration conferences focus on recent developments in the fundamental chemistry of actinides and fission products in natural aquifer systems, their interactions and migration in the geosphere, and the processes involved in modeling their geochemical behavior. The primary mode dissemination of technical information will be early evening poster sessions designed to encourage intensive communication between the authors and participants. Daily oral sessions will be opened with invited lectures followed by contributed papers within the scope of each session. Sessions cover: (A) Chemistry of actinides and fission products in natural aquatic systems: (1) Solubilities and dissolution reactions; (2) Complexation with inorganic and organic ligands; (3) Redox reactions; (4) Colloid formation; and (5) Experimental methods. (B) Geochemical interactions and transport phenomena: (1) Diffusion and migration in geologic media; (2) Sorption/desorption phenomena; (3) Natural analog studies; (4) Effects of biological activities and organic materials; (5) Colloid transport; (6) Radionuclides in soils; and (7) Soil-remediation chemistries. (C) Data base development and modeling: (1) Data selection and evaluation; (2) Data base management; (3) Geochemical models and modeling; (4) Application of models; and (5) Validation of modeling results

  2. The seventh international conference on the chemistry and migration behavior of actinides and fission products in the Geosphere MIGRATION'99 abstracts

    Palmer, C

    1999-09-01

    The Migration conferences focus on recent developments in the fundamental chemistry of actinides and fission products in natural aquifer systems, their interactions and migration in the geosphere, and the processes involved in modeling their geochemical behavior. The primary mode dissemination of technical information will be early evening poster sessions designed to encourage intensive communication between the authors and participants. Daily oral sessions will be opened with invited lectures followed by contributed papers within the scope of each session. Sessions cover: (A) Chemistry of actinides and fission products in natural aquatic systems: (1) Solubilities and dissolution reactions; (2) Complexation with inorganic and organic ligands; (3) Redox reactions; (4) Colloid formation; and (5) Experimental methods. (B) Geochemical interactions and transport phenomena: (1) Diffusion and migration in geologic media; (2) Sorption/desorption phenomena; (3) Natural analog studies; (4) Effects of biological activities and organic materials; (5) Colloid transport; (6) Radionuclides in soils; and (7) Soil-remediation chemistries. (C) Data base development and modeling: (1) Data selection and evaluation; (2) Data base management; (3) Geochemical models and modeling; (4) Application of models; and (5) Validation of modeling results.

  3. Subsurface Biogeochemistry of Actinides

    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).

  4. Proceedings of the seminar on the joint research project between JAERI and Universities. 'Actinide researches for 21st century - fusion between chemistry and engineering'. August 20-21, 1999, Japan Atomic Energy Research Inst., Tokai, Japan

    NONE

    2000-06-01

    The Seminar on the Joint Research Project between JAERI and Universities was held in Tokai, August 20-21, 1999, to discuss future perspectives of the actinide researches for the nuclear fuel cycle. The papers related to the Joint Research Project on the Backend Chemistry were presented and discussed. The present report complies the papers contributed to the Seminar. (author)

  5. Proceedings of the seminar on the joint research project between JAERI and Universities. 'Actinide researches for 21st century - fusion between chemistry and engineering'. August 20-21, 1999, Japan Atomic Energy Research Inst., Tokai, Japan

    The Seminar on the Joint Research Project between JAERI and Universities was held in Tokai, August 20-21, 1999, to discuss future perspectives of the actinide researches for the nuclear fuel cycle. The papers related to the Joint Research Project on the Backend Chemistry were presented and discussed. The present report complies the papers contributed to the Seminar. (author)

  6. Extraction chemistry of actinide cations by N,N,N',N'-tetraalkyl-2 alkyl propane-1,3 diamides

    N, N, N', N'-tetraalkyl 2-alkyl propane 1,3-diamides (RR'NCO)2 CHR were investigated in view to separate the actinides contained in nuclear wastes. These extractants can be considered as an alternative to CMPO (octyl(phenyl)-N, N-diisobutylcarbamoyl methyl phosphine oxide) used in the TRUEX process [1]. Unlike organophosphorus molecules, amides and their degradation products are completely incinerable. These facts implicate minimum production of secondary wastes after the degraded solvent incineration. N, N'-dimethyl N, N'-dibutyl tetradecyl malonamide (DMDBTDMA) was selected. This molecule is usable in aliphatic diluents, is able to extract trivalent actinides. Americium extraction is faster than iron extraction, this phenomenon increases the interest of these solvents in nuclear industry. We will present extraction equilibria of UO22+, Pu4+, and Am3+ from nitrate solutions. Researches are performed to point out the main features of complexes (amidecation) providing extraction (different species, stoechiometries, part of acidity). Technics used are spectrophotometry (IR, UV-visible), distribution ratios measurements and saturation of the organic phase. (author). 6 figs

  7. Specific sequestering agents for the actinides. VI. Synthetic and structural chemistry of tetrakis(N-alkylalkanehydroxamato)thorium(IV) complexes

    Hydroxamate complexes of the actinides have been investigated as structural archetypes in the design of actinide-specific sequestering agents. The complexes Th[(CH3)2CHN(O)O(O)R]4 have been prepared (R = C(CH3)3 (1) or CH2C(CH3)3 (2) The uranium(IV) analogue of 1 was also prepared. The tert-butyl groups of 1 dominate the stereochemistry of the complex by assuming a tetrahedral disposition around the metal. The coordination polyhedron of 1, which has 4 (S4) crystallographic symmetry, is nearly cubic. The localization of charge on the nitrogen oxygen of the hydroxamate group makes this ligand unsymmetrical, and this gives rise to a 0.14-A difference in R(Th-O/sub N/) [2.357(3) A] and R(Th-O/sub C/) [2.492 (3) A]. The sterically less constrained neopentyl derivative 2 shows a more typical eight-coordinate geometry - the D/sub 2d/ trigonal-faced (mmmm) dodecahedron. The average R(Th-O/sub N/) [2.36 (1) A] is again shorter than R(Th-O/sub C/) [2.46 (2) A]. There is apparently no sorting of sites by ligand charge, since the O/sub N/ and O/sub C/ atoms are equally distributed between the A and B sites of the dodecahedron. Crystals of 1 conform to space group I41/a with a = 17.338 (4) A and c = 12.706 (4) A. For 4 formula units per cell the calculated density d/sub calcd/ is 1.50 g cm-3 and d/sub obsd/ is 1.50 (1) g cm-3. Crystals of 2 conform to space group P1 with a = 9.777 (2) A, b = 14.633 (2) A, c = 18.515 (1) A, α = 74.0610 (8), β = 88.41 (1)0, and γ = 74.71 (2)0. For 2 formula units per cell d/sub calcd/ = 1.30 g cm-3 and d/sub obsd/ = 1.19 g cm-3. Full-matrix least-squares refinement of both structures using all averaged, independent data with F2 > 3sigma(F)2 gave for 1 with 1798 data and 117 variables R = 0.027 and R/sub w/ = 0.032 and for 2 with 6978 data and 467 variables R = 0.034, R/sub w/ = 0.042. 10 figures, 11 tables

  8. Synthesis, chemistry, and catalytic activity of complexes of lanthanide and actinide metals in unusual oxidation states and coordination environments. Progress report, February 1, 1981-January 31, 1982

    The objectives of this research project are: (1) to demonstrate experimentally that the lanthanide and actinide metals have a more extensive chemistry than is presently known; (2) to develop a better understanding of the special features of the f orbital elements which will allow the design of f orbital complexes possessing unique chemical and physical properties; (3) to provide a basis for seeking unusual catalytic transformations involving these elements; and (4) to synthesize and explore the chemical and physical properties of mixed metal complexes which contain both lanthanide and transition metals. During the past year progress was made in each area. Some of the specific results are: (1) the first activation of CO by an organolanthanide complex was demonstrated; (2) the first, crystallograhically characterized, molecular lanthanide hydride complexes, the bridged dimers, [(C5H4R)2LnH(THF)]2 (R=H, CH3; Ln=Lu, Er, Y), were synthesized by hydrogenolysis of the appropriate (C5H4R)2Ln(C(CH3)3)(THF) complex; (3) [(C5H5)2(THF)ErH]2 was found to catalyze the homogeneous hydrogenation of alkynes; (4) the first trimetallic organolanthanide complex was synthesized; (5) the first polyhydridic organolanthanide complex was synthesized; (6) U(III) hydride was found to catalytically activate molecular hydrogen in alkene and alkyne hydrogenation reactions

  9. Research on the chemical speciation of actinides

    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

  10. Photochemistry of the actinides

    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

  11. Endohedral Fullerenes with Actinide-Actinide Bonds: Unwilling Bonding in U2@C80

    Foroutan-Nejad, C.; Patzschke, M.; Straka, Michal

    Opole: -, 2014. [MMNB 2014. Polish-Taiwanese Conference. From Molecular Modeling to Nano- and Biotechnology . 04.09.2014-06.09.2014, Opole] R&D Projects: GA ČR(CZ) GA14-03564S Grant ostatní: European Social Fund(XE) CZ.1.07/2.3.00/30.009 Institutional support: RVO:61388963 Keywords : endohedral actinide fullerene * U-U bonding * actinide-actinide bonding Subject RIV: CF - Physical ; Theoretical Chemistry

  12. Actinide recycle

    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

  13. Equilibrium constants in aqueous lanthanide and actinide chemistry from time-resolved fluorescence spectroscopy: The role of ground and excited state reactions

    Equilibrium constants for aqueous reactions between lanthanide or actinide ions and (in-) organic ligands contain important information for various radiochemical problems, such as nuclear reprocessing or the migration of radioelements in the geosphere. We study the conditions required to determine equilibrium constants by time-resolved fluorescence spectroscopy measurements. Based on a simulation study it is shown that the possibility to determine equilibrium constants depends upon the reaction rates in the photoexcited states of the lanthanide or actinide ions. (orig.)

  14. Research on the chemical speciation of actinides

    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

  15. Kinetics of actinide complexation reactions

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

  16. 33rd Actinide Separations Conference

    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.

  17. Advanced Aqueous Separation Systems for Actinide Partitioning

    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.

  18. Successive change regularity of actinide properties with atomic number

    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 f7n-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

  19. Actinides and the environment

    The book combines in one volume the opinions of experts regarding the interaction of radionuclides with the environment and possible ways to immobilize and dispose of nuclear waste. The relevant areas span the spectrum from pure science, such as the fundamental physics and chemistry of the actinides, geology, environmental transport mechanisms, to engineering issues such as reactor operation and the design of nuclear waste repositories. The cross-fertilization between these various areas means that the material in the book will be accessible to seasoned scientists who may wish to obtain an overview of the current state of the art in the field of environmental remediation of radionuclides, as well as to beginning scientists embarking on a career in this field. refs

  20. ACTINET-I3 Summer School on Analytical Innovation in the field of actinide recycling - Slides of the presentations

    This conference dealt with 3 main topics: analytical innovation in separation processes (hyphenated techniques, analytical chips,...), actinide recycling (extraction, interfaces, processes,...) and chemistry and thermodynamics of actinides. This document is composed of the slides of the presentations

  1. Ventilation system of actinides handling facility in Oarai-branch of Tohoku University

    We have reported the development of the facility for handling actinides in Tohoku University at the second KAERI-JAERI joint seminar on PIE technology. Actinide isotopes have most hazardous α-radioactivity. Therefore, a specially designed facility is necessary to carry out experimental study for actinide physics and chemistry. In this paper, we will describe the ventilation system and monitoring system for actinide handling facility. (author)

  2. Actinide co-ordination and discrimination by human transferrin

    The design and evaluation of synthetic chelating agents which are specific for the actinide(IV) ions are described. The initial approach has been based on the biological and chemical similarities of Pu(IV) and Fe(III). In particular, using a philosophy influenced by naturally occurring ferric ion chelating agents, tetracatechoylamide ligands have been developed for the actinides. The test of the degree to which there was an actinide-specific complexing agent has been based on studies using Pu4+ as a biological contaminant. For a chelating agent to be able to sequester actinides effectively, it must remove actinides from actinide(IV)-protein complexes. The complexation chemistry of Th(IV)-transferrin system is described. The evidence suggests that, based on a size criterion, Th(IV) may be a poor biological model for Pu(IV) in some cases, with U(IV) being a somewhat better model. (author)

  3. The lanthanides and actinides

    This paper relates the chemical properties of the actinides to their position in the Mendeleev periodic system. The changes in the oxidation states of the actinides with increasing atomic number are similar to those of the 3d elements. Monovalent and divalent actinides are very similar to alkaline and alkaline earth elements; in the 3+ and 4+ oxidation states they resemble d elements in the respective oxidation states. However, in their highest oxidation states the actinides display their individual properties with only a slight resemblance to d elements. Finally, there is a profound similarity between the second half of the actinides and the first half of the lanthanides

  4. Actinide and fission product partitioning and transmutation

    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.)

  5. Actinide and fission product partitioning and transmutation

    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.)

  6. Chemistry

    The chemical research and development efforts related to the design and ultimate operation of molten-salt breeder reactor systems are concentrated on fuel- and coolant-salt chemistry, including the development of analytical methods for use in these systems. The chemistry of tellurium in fuel salt is being studied to help elucidate the role of this element in the intergranular cracking of Hastelloy N. Studies were continued of the effect of oxygen-containing species on the equilibrium between dissolved UF3 and dissolved UF4, and, in some cases, between the dissolved uranium fluorides and graphite, and the UC2. Several aspects of coolant-salt chemistry are under investigation. Hydroxy and oxy compounds that could be formed in molten NaBF4 are being synthesized and characterized. Studies of the chemistry of chromium (III) compounds in fluoroborate melts were continued as part of a systematic investigation of the corrosion of structural alloys by coolant salt. An in-line voltammetric method for determining U4+/U3+ ratios in fuel salt was tested in a forced-convection loop over a six-month period. (LK)

  7. Actinide phosphonate complexes in aqueous solutions

    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 (-PO3H2) 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

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

    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 (AmIII YII Zriv)Orx 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)

  9. Chemistry

    Research progress is reported in programs on fuel-salt chemistry, properties of compounds in the Li--Te system, Te spectroscopy UF4--H equilibria, porous electrode studies of molten salts, fuel salt-coolant salt reactions, thermodynamic properties of transition-metal fluorides, and properties of sodium fluoroborate. Developmental work on analytical methods is summarized including in-line analysis of molten MSBR fuel, analysis of coolant-salts for tritium, analysis of molten LiF--BeF2--ThF4 for Fe and analysis of LiF--BeF--ThF4 for Te

  10. Speciation of actinides by the mean of synchrotron radiation; Speciation des actinides au moyen du rayonnement synchrotron

    Simoni, E. [Institut de Physique Nucleaire, (IN2P3/CNRS) 91 - Orsay (France); Den Auwer, Ch. [CEA Marcoule, Dept. Radiochimie et Procedes (DRCP/SCPS), 30 (France)

    2005-09-01

    After having recalled the principle of the X absorption spectroscopy, the authors give examples illustrating the analytical possibilities of this technique and the different application fields concerning the actinides physico-chemistry (coordination chemistry, interface, solid state, solution). (O.M.)

  11. The Actinide User Laboratory at ITU-Karlsruhe

    The interest in actinide materials arises mainly from their fundamental physics and chemistry and the complexity of their behaviour as illustrated through numerous papers of this conference. Such research also impacts on nuclear fuel technology and the problem of nuclear waste and long-term storage. Despite the great interest in the actinides the number of Laboratories equipped to handle these materials is steadily decreasing due to heavy and costly security requirements. The Institute for Transuranium Elements (ITU) is a Laboratory of the Joint Research Centre of the European Commission which addresses a large number of questions related to actinides, both basic and applied, and is the only non-classified Laboratory in Europe where research on appreciable quantities of transuranium materials is conducted across a wide range of chemistry and physics. In order to keep alive an essential and exciting field of research in physic and chemistry, we have decided to offer access to our facilities to external users through an Actinide User Laboratory. Materials preparation facilities and a suite of instruments, together with expert technical assistance, are available for conducting basic or applied research studies. The Actinide User Laboratory is selected as a user facility to participate in the European Community - Access to Research Infrastructures action of the Improving Human Potential Programme (IHP) which supports access to our actinide facility for the selected users teams, travel and subsistence fees of visiting scientists. The programme is open to EC users and to scientists of the associated states. (author)

  12. Chemistry

    Research and development activities dealing with the chemical problems related to design and ultimate operation of molten-salt reactor systems are described. An experimental test stand was constructed to expose metallurgical test specimens to Te2 vapor at defined temperatures and deposition rates. To better define the chemistry of fluoroborate coolant, several aspects are being investigated. The behavior of hydroxy and oxy compounds in molten NaBF4 is being investigated to define reactions and compounds that may be involved in corrosion and/or could be involved in methods for trapping tritium. Two corrosion products of Hastelloy N, Na3CrF6 and Na5Cr3F14, were identified from fluoroborate systems. The evaluation of fluoroborate and alternate coolants continued. Research on the behavior of hydrogen and its isotopes is summarized. The solubilities of hydrogen, deuterium, and helium in Li2BeF4 are very low. The sorption of tritium on graphite was found to be significant (a few milligrams of tritium per kilogram of graphite), possibly providing a means of sequestering a portion of the tritium produced. Development of analytical methods continued with emphasis on voltammetric and spectrophotometric techniques for the in-line analysis of corrosion products such as Fe2+ and Cr3+ and the determination of the U3+/U4+ ratio in MSBR fuel salt. Similar studies were conducted with the NaBF4--NaF coolant salt. Information developed during the previous operation of the CSTF has been assessed and used to formulate plans for evaluation of in-line analytical methods in future CSTF operations. Electroanalytical and spectrophotometric research suggests that an electroactive protonic species is present in molten NaBF4--NaF, and that this species rapidly equilibrates with a volatile proton-containing species. Data obtained from the CSTF indicated that tritium was concentrated in the volatile species. (JGB)

  13. Adaptation of ICP-AES in lead cell facility in Chemistry Group, IGCAR and analysis of simulated high level waste as a part of the studies on minor actinide partitioning

    The spent fuel discharged from the nuclear reactor contains unused uranium and plutonium, and Np, Am, Cm called as minor actinides and fission products. Spent fuel is dissolved in nitric acid. U and Pu are recovered by a solvent extraction process known as PUREX process using 1.1 M TBP as extractant. The raffinate rejected is known as High Level Liquid Waste which is a complex mixture of minor actinides, corrosion products, and fission products. Partitioning of minor actinides (MA) and its transmutation is a viable strategy for the safe management of high level liquid waste (HLLW)

  14. Actinide and fission product partitioning and transmutation

    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.)

  15. Actinide and fission product partitioning and transmutation

    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.)

  16. Characterization of actinides in simulated alkaline tank waste sludges and leach solutions

    Current plans call for an alkaline scrub of actinide-bearing sludges in the Hanford Waste tanks prior to their incorporation in glass waste forms. Though it is assumed that actinides will remain in the sludge phase during this procedure, this assumption is based on insufficient supporting thermodynamic and kinetic data. In this project the authors will investigate the fundamental chemistry of actinides in strongly alkaline solution and solid phases to strengthen the foundation and identify potential limitations of this approach. They will focus on the characterization of the leaching of actinides from simulated BiPO4, REDOX, and PUREX sludges, the identification of actinide mineral phases in the sludge simulants, and the possible solubilization of actinides by complexation and radiolysis effects. This program will provide new fundamental information on the chemical behavior and speciation of uranium, neptunium, plutonium, and americium in simulated alkaline tank waste sludges and alkaline scrub liquors. Sludge simulants will be prepared from the appropriate matrix components using published data for guidance. Actinide ions will be introduced in the oxidation states pertinent to process conditions. The authors will characterize the speciation of the actinides in the sludges using a variety of techniques. In parallel studies, they will address the chemistry of actinide ions in alkaline solutions, principally those containing chelating agents. The third critical element of this research will be to assess the impact of radiolysis on actinide behavior. By correlating actinide speciation in the solid and solution phases with sludge composition, it will be possible to predict conditions favoring mobilization (or immobilization) of actinide ions during sludge washing. The new information will increase predictability of actinide behavior during tank sludge washing, and so contribute to minimization of the volume of high level waste created

  17. Actinide isotopic analysis systems

    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

  18. Chemical properties of the trans-actinide elements studied in liquid phase with SISAK

    This article starts with a review of the current SISAK liquid-liquid extraction system, as used after the physical pre-separator BGS (Berkeley Gas-filled Separator) at Lawrence Berkeley National Laboratory (LBNL) for chemical studies of trans-actinide elements. Emphasis will be on new additions and developments. Then the possibilities offered by the new TASCA (Trans-Actinide Separator and Chemistry Apparatus) separator at GSI (Darmstadt, Germany) and the use of actinide targets at both GSI and LBNL are discussed with respect to future SISAK trans-actinide experiments. Finally, current and future liquid-liquid extraction systems for studying elements Rutherfordium up to Hassium are discussed. (authors)

  19. Chemical properties of the trans-actinide elements studied in liquid phase with SISAK

    Omtvedt, J.P.; Alstad, J.; Bjornstad, T.; Opel, K.; Polakova, D.; Samadani, F.; Schulz, F.; Stavsetra, L.; Zheng, L. [Oslo Univ., Centre for Accelerator based Research and Energy Physics (SAFE) (Norway); Dullmann, Ch.E; Gregorich, K.E.; Hoffman, D.C.; Nitsche, H.; Sudowe, R. [Lawrence Berkeley National Laboratory (LBNL), Nuclear Science Div., One Cyclotron Road, Berkeley, CA (United States); Dullmann, Ch.E.; Hoffman, D.C.; Nitsche, H. [California Univ., Dept. of Chemistry, Berkeley, CA (United States); Skarnemark, G. [Chalmers Univ. of Technology, Nuclear Chemistry, Dept. of Chemical and Biological Engineering (Sweden)

    2007-10-15

    This article starts with a review of the current SISAK liquid-liquid extraction system, as used after the physical pre-separator BGS (Berkeley Gas-filled Separator) at Lawrence Berkeley National Laboratory (LBNL) for chemical studies of trans-actinide elements. Emphasis will be on new additions and developments. Then the possibilities offered by the new TASCA (Trans-Actinide Separator and Chemistry Apparatus) separator at GSI (Darmstadt, Germany) and the use of actinide targets at both GSI and LBNL are discussed with respect to future SISAK trans-actinide experiments. Finally, current and future liquid-liquid extraction systems for studying elements Rutherfordium up to Hassium are discussed. (authors)

  20. ACTINET: a European Network for Actinide Sciences

    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

  1. Actinide behavior under final repository relevant conditions

    Experiments on the solubility behavior and the redox chemistry of actinides and long-living fission products under different geochemical boundary conditions, here on the Np(V) solubility in alkaline CaCl2 systems, provide basic information on processes that can occur in a nuclear final repository in case of water ingress. The thermodynamic constants derived from these experiments allow the geochemical modeling of these processes and a rough estimation of radionuclide solubility limits for different scenarios. Scientific research projects on this issue will reduce the uncertainties of long-term safety analyses for final repositories for high-level radioactive wastes significantly.

  2. Actinide behavior in a freshwater pond

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

  3. Recovering actinide values

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

  4. X-Ray Absorption Spectroscopy of the Actinides

    Antonio, Mark R.; Soderholm, Lynda

    The recent availability of synchrotron radiation has revolutionized actinide chemistry. This is particularly true in environmental studies, where heterogeneous samples add to the already multifaceted chemistry exhibited by these ions. Environmental samples are often inhomogeneous, chemically diverse, and amorphous or poorly crystalline. Even surrogates prepared in the laboratory to simplify the natural complexity are plagued by multiple oxidation state and varied coordination polyhedra that are a reflection of inherent 5f chemistry. For example, plutonium can be found as Pu3+ Pu4+ Pu(V)O2 +, and Pu(VI)O2 2 + within naturally occurring pH-Eh conditions, consequently complex equilibria are found between these oxidation states in one solution. In addition, dissolved actinides have significant affinities for various mineral surfaces, to which they can adsorb with or without concomitant reduction-oxidation (redox) activity, depending on details of the solution and surface conditions.

  5. Actinides: why are they important biologically

    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

  6. Photoelectron spectra of actinide compounds

    A brief overview of the application of photoelectron spectroscopy is presented for the study of actinide materials. Phenomenology as well as specific materials are discussed with illustrative examples

  7. Radioecology of the actinide elements

    Research progress is reported in sections entitled: scope of studies supported by the Department of Energy; oxidation state diagrams are a potential tool for studying the redox chemistry of Pu in natural waters; studies are initiated to investigate the effect of pH and organic matter on the distribution coefficients of Cm with natural sediments; the relative distributions of resuspended and direct deposited Pu in a corn canopy are quantified; the retention of Pu surface contamination by corn plants is being studied; Pu concentrations in tobacco are being determined; concentrations of Pu per unit mass and per unit surface area are compared for subterranean crops; models of Pu behavior in agricultural crops are being validated; distribution of aerially released Pu in loblolly pine plantations is independent of deposition rate; investigation of the effects of chelate and redox potential of the uptake of Pu and Cm by rice is underway; studies of Cm cycling in a floodplain forest have been initiated; the effects of unusually large Pu deposition onto a wheat ecosystem are being studied using computer simulations; long-term kinetic models of Pu behavior in plant-soil systems are being developed; scope of studies supported by the Nuclear Regulatory Commission; growth form of broadleaf crop may affect Pu contents; root uptake of Pu and Cm measured for rice root uptake of Pu and Cm measured for rice; long-term actinide uptake study is continuing at SREL; and uranium cycling in major southeastern agricultural crops being studied

  8. The selective extraction of oxidized minor actinides: a possible route for the Actinex program

    In the SPIN programme, defined by CEA to improve the management of high level nuclear waste, a part called ACTINEX is specially devoted to the extraction of long-lived alpha emitters and fission products from high level liquid waste issuing from the PUREX process. Concerning the actinides elements, as U and Pu are already recovered, the main objective to reach is now the quantitative extraction of Np and Am. The transmutation of these recovered actinides into short-lived radionuclides is then forecast. This paper deals with the possibilities to define a minor actinides partitioning process based on the selective extraction of actinides oxidized to their oxidation states higher than three. It essentially focuses on americium chemistry. Finally, two general separation scheme for minor actinide partitioning are proposed and discussed. (authors). 5 figs., 13 refs

  9. Advanced Aqueous Separation Systems for Actinide Partitioning

    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

  10. 44th Journées des Actinides and 10th SPCA. Scientific Programme and Abstracts

    In the opening Session for the 10th SPCA the program of the school will be presented.The sessions of the 10th SPCA are: Physics, Chemistry,Theory, electronic structure,Nuclear forensics, Measuring systems. While the 10th SPCA lectures on crystallography, Physics, Chemistry and basics of actinides research

  11. An introduction to the Advanced Testing Line for Actinide Separations (ATLAS)

    Pope, N.G.; Yarbro, S.L.; Schreiber, S.B.; Day, R.S.

    1992-03-01

    The Advanced Testing Line for Actinide Separations (ATLAS) will evaluate promising plutonium recovery process modifications and new technologies. It combines advances in process chemistry, process control, process analytical chemistry, and process engineering. ATLAS has a processing capability equal to other recovery systems but without the pressure to achieve predetermined recovery quotas.

  12. An introduction to the Advanced Testing Line for Actinide Separations (ATLAS)

    The Advanced Testing Line for Actinide Separations (ATLAS) will evaluate promising plutonium recovery process modifications and new technologies. It combines advances in process chemistry, process control, process analytical chemistry, and process engineering. ATLAS has a processing capability equal to other recovery systems but without the pressure to achieve predetermined recovery quotas

  13. Optical techniques for actinide research

    In recent years, substantial gains have been made in the development of spectroscopic techniques for electronic properties studies. These techniques have seen relatively small, but growing, application in the field of actinide research. Photoemission spectroscopies, reflectivity and absorption studies, and x-ray techniques will be discussed and illustrative examples of studies on actinide materials will be presented

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

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

    2009-12-01

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

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

    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.

  16. Actinides in molecules: exotic properties probed by X-ray Absorption Spectroscopy

    Dealing with actinide elements in molecular chemistry may result in particularly attractive and exotic physico-chemical properties. In solution, one of the spectroscopic tools able to selectively probe the structural or electronic properties of these molecules is the X-ray absorption process. Different aspects of absorption edge or EXAFS analysis related to actinide studies are presented, including phenomenological and semi-quantitative approaches. (authors)

  17. Recycling of actinides and fission products, the Dutch RAS research programme

    An ECN, a research programme has been started to contribute to current international research efforts in the field of P and T. The name of this programme is RAS, which is the dutch acronym for recycling of actinides and fission products. This multidisciplinary programme consists of the following components: - Nuclear data ('cross-section libraries') - Reactor physics and scenario studies - Chemical studies ('actinide chemistry') - Technological studies and irradiations. (orig./HP)

  18. Emergence of californium as the second transitional element in the actinide series

    Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E.; Stritzinger, Jared T.; GREEN, THOMAS D.; Diefenbach, Kariem; Cross, Justin N.; Knappenberger, Kenneth L.; Liu, Guokui; Silver, Mark A.; DePrince, A. Eugene; Polinski, Matthew J.; Van Cleve, Shelley M.; House, Jane H.; Kikugawa, Naoki

    2015-01-01

    A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resu...

  19. Actinides in molecules: exotic properties probed by X-ray Absorption Spectroscopy

    Den Auwer, C.; Moisy, P.; Guilbaud, P.; Guillaumont, D.; Simoni, E.; Conradson, S.D

    2004-07-01

    Dealing with actinide elements in molecular chemistry may result in particularly attractive and exotic physico-chemical properties. In solution, one of the spectroscopic tools able to selectively probe the structural or electronic properties of these molecules is the X-ray absorption process. Different aspects of absorption edge or EXAFS analysis related to actinide studies are presented, including phenomenological and semi-quantitative approaches. (authors)

  20. Mathematical modelling of the effects of aerobic and anaerobic chelate biodegradation on actinide speciation

    Biodegradation of natural and anthropogenic chelating agents directly and indirectly affects the speciation, and hence, the mobility of actinides in subsurface environments. We combined mathematical modelling with laboratory experimentation to investigate the effects of aerobic and anaerobic chelate biodegradation on actinide [Np(IV/V), Pu(IV)] speciation. Under aerobic conditions, nitrilotriacetic acid (NTA) biodegradation rates were strongly influenced by the actinide concentration. Actinide-chelate complexation reduced the relative abundance of available growth substrate in solution and actinide species present or released during chelate degradation were toxic to the organisms. Aerobic bioutilization of the chelates as electron-donor substrates directly affected actinide speciation by releasing the radionuclides from complexed form into solution, where their fate was controlled by inorganic ligands in the system. Actinide speciation was also indirectly affected by pH changes caused by organic biodegradation. The two concurrent processes of organic biodegradation and actinide aqueous chemistry were accurately linked and described using CCBATCH, a computer model developed at Northwestern University to investigate the dynamics of coupled biological and chemical reactions in mixed waste subsurface environments. CCBATCH was then used to simulate the fate of Np during anaerobic citrate biodegradation. The modelling studies suggested that, under some conditions, chelate degradation can increase Np(IV) solubility due to carbonate complexation in closed aqueous systems. (orig.)

  1. Mathematical modeling of the effects of aerobic and anaerobic chelate biodegradation on actinide speciation

    Biodegradation of natural and anthropogenic chelating agents directly and indirectly affects the speciation, and, hence, the mobility of actinides in subsurface environments. We combined mathematical modeling with laboratory experimentation to investigate the effects of aerobic and anaerobic chelate biodegradation on actinide [Np(IV/V), Pu(IV)] speciation. Under aerobic conditions, nitrilotriacetic acid (NTA) biodegradation rates were strongly influenced by the actinide concentration. Actinide-chelate complexation reduced the relative abundance of available growth substrate in solution and actinide species present or released during chelate degradation were toxic to the organisms. Aerobic bio-utilization of the chelates as electron-donor substrates directly affected actinide speciation by releasing the radionuclides from complexed form into solution, where their fate was controlled by inorganic ligands in the system. Actinide speciation was also indirectly affected by pH changes caused by organic biodegradation. The two concurrent processes of organic biodegradation and actinide aqueous chemistry were accurately linked and described using CCBATCH, a computer model developed at Northwestern University to investigate the dynamics of coupled biological and chemical reactions in mixed waste subsurface environments. CCBATCH was then used to simulate the fate of Np during anaerobic citrate biodegradation. The modeling studies suggested that, under some conditions, chelate degradation can increase Np(IV) solubility due to carbonate complexation in closed aqueous systems

  2. Biological pathways and chemical behavior of plutonium and other actinides in the environment

    The principal long-lived actinide elements that may enter the environment from either U or Pu fuel cycles are Pu, Am, Cm, and Np. Approximately 25% of the alpha activity estimated to be released to the atmosphere from the LMFBR fuel cycle will be contributed by 241Am, 242Cm, and 244Cm. The balance of the alpha activity will come from Pu isotopes. Activities of 242Cm, 244Cm, 241Am, 243Am, and 237Np in waste may exceed concentrations of Pu isotopes in waste after various periods of decay. Thorium and uranium isotopes may also be released by operations of the thorium fuel cycle. Environmental actinides are discussed under the following headings: sources of man-made actinide elements; pathways of exposure; environmental chemistry of actinides; uptake of actinides by plants; distribution of actinides in components of White Oak Lake; entry of actinides into terrestrial food chains; relationship between chemical behavior and uptake of actinides by organisms; and behavior of Pu in freshwater and marine food chains

  3. Managing Inventories of Heavy Actinides

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

  4. Calorimetric assay of minor actinides

    Rudy, C.; Bracken, D.; Cremers, T.; Foster, L.A.; Ensslin, N.

    1996-12-31

    This paper reviews the principles of calorimetric assay and evaluates its potential application to the minor actinides (U-232-4, Am-241, Am- 243, Cm-245, Np-237). We conclude that calorimetry and high- resolution gamma-ray isotopic analysis can be used for the assay of minor actinides by adapting existing methodologies for Pu/Am-241 mixtures. In some cases, mixtures of special nuclear materials and minor actinides may require the development of new methodologies that involve a combination of destructive and nondestructive assay techniques.

  5. Calorimetric assay of minor actinides

    This paper reviews the principles of calorimetric assay and evaluates its potential application to the minor actinides (U-232-4, Am-241, Am- 243, Cm-245, Np-237). We conclude that calorimetry and high- resolution gamma-ray isotopic analysis can be used for the assay of minor actinides by adapting existing methodologies for Pu/Am-241 mixtures. In some cases, mixtures of special nuclear materials and minor actinides may require the development of new methodologies that involve a combination of destructive and nondestructive assay techniques

  6. Environmental research on actinide elements

    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

  7. Properties of minor actinide nitrides

    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)

  8. Actinide elements in aquatic and terrestrial environments

    Progress is reported in terrestrial ecology studies with regard to plutonium in biota from the White Oak Creek forest; comparative distribution of plutonium in two forest ecosystems; an ecosystem model of plutonium dynamics; actinide element metabolism in cotton rats; and crayfish studies. Progress is reported in aquatic studies with regard to transuranics in surface waters, frogs, benthic algae, and invertebrates from pond 3513; and radioecology of transuranic elements in cotton rats bordering waste pond 3513. Progress is also reported in stability of trivalent plutonium in White Oak Lake water; chemistry of plutonium, americium, curium, and uranium in pond water; uranium, thorium, and plutonium in small mammals; and effect of soil pretreatment on the distribution of plutonium

  9. Isotope and Nuclear Chemistry Division annual report, FY 1990, October 1, 1989--September 30, 1990

    This report describes some of the major research and development programs of the Isotope and Nuclear Chemistry Division during FY 1990. The report includes articles on weapons chemistry, environmental chemistry, actinide and transition metal chemistry, geochemistry, nuclear structure and reactions, biochemistry and nuclear medicine, materials chemistry, and INC Division facilities and laboratories

  10. Synthesis and structural characterization of actinide oxalate compounds

    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)

  11. Molecular solids of actinide hexacyanoferrate: Structure and bonding

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

  12. Experimental Evaluation of Actinide Transport in a Fractured Granodiorite

    Dittrich, Timothy M. [Los Alamos National Laboratory; Reimus, Paul W. [Los Alamos National Laboratory

    2015-03-16

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

  13. Molecular and electronic structure of actinide hexa-cyanoferrates

    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: AnIV[FeII(CN)6].xH2O (An = Th, U, Np, Pu); AmIII[FeIII(CN)6].xH2O; Pu III[CoIII(CN)6].xH2O and K(H?)AnIII[FeII(CN)6].xH2O (An = Pu, Am). The metal oxidation states have been obtained thanks to the νCN, stretching vibration and to the actinide LIII absorption edge studies. As Prussian Blue, the AnIV[FeII(CN)6].xH2O (An = Np, Pu) are class II of Robin and Day compounds. X-ray Diffraction has shown besides that these complexes crystallize in the P63/m space group, as the isomorphic LaKFe(CN)6.4H2O complex used as structural model. The EXAFS oscillations at the iron K edge and at the An LIII 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 AnIV versus LnIII 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)

  14. On the crystal structures of USe2, UTe2, ThOTe, and Er2Se3 - a contribution to the crystal chemistry of rare earth and actinide chalcogenides

    The dichalcogenides of rare earth metals and actinides were classified into isostructural compounds without considering their composition. The structures of of α-USe2, β-USe2, UTe2, and HoSe2 as well as of ThOTe, Er2Se3, and UTe3 were determined by X-ray diffraction of their crystals. The results demonstrate that α-USe2 has a SrBr2-analog structure and a stoichiometric composition. The atomic parameters derived from powder data of ThOTe and UTe2 could be confirmed by X-ray analysis of the crystalline compounds. ThOTe crystallizes into a PbFCl-analog structure. The order of atoms in UTe2 is similar to that of the ZrSe3 type. The crystals of ErSe3, UTe3, HoSe2, and β-USe2 were investigated only by camera methods. As in the case of Er2Se3 or UTe3 twin formation could be observed in β-USe3. (orig./RB)

  15. THERMODYNAMICS OF THE ACTINIDES

    Cunningham, Burris B.

    1962-04-01

    Recent work on the thermodynamic properties of the transplutonium elements is presented and discussed in relation to trends in thermodynamic properties of the actinide series. Accurate values are given for room temperature lattice parameters of two crystallographic forms, (facecentred cubic) fcc and dhcp (double-hexagonal closepacked), of americium metal and for the coefficients of thermal expansion between 157 and 878 deg K (dhcp) and 295 to 633 deg K (fcc). The meiting point of the metal, and its magnetic susceptibility between 77 and 823 deg K are reported and the latter compared with theoretical values for the tripositive ion calculated from spectroscopic data. Similar data (crystallography, meiting point and magnetic susceptibility) are given for metallic curium. A value for the heat of formation of americium monoxide is reported in conjunction with crystallographic data on the monoxide and mononitride. A revision is made in the current value for the heat of formation of Am/O/sub 2/ and for the potential of the Am(III)-Am(IV) couple. The crystal structures and lattice parameters are reported for the trichloride, oxychloride and oxides of californium. (auth)

  16. SACSESS – the EURATOM FP7 project on actinide separation from spent nuclear fuels

    Bourg Stéphane

    2015-12-01

    Full Text Available Recycling of actinides by their separation from spent nuclear fuel, followed by transmutation in fast neutron reactors of Generation IV, is considered the most promising strategy for nuclear waste management. Closing the fuel cycle and burning long-lived actinides allows optimizing the use of natural resources and minimizing the long-term hazard of high-level nuclear waste. Moreover, improving the safety and sustainability of nuclear power worldwide. This paper presents the activities striving to meet these challenges, carried out under the Euratom FP7 collaborative project SACSESS (Safety of Actinide Separation Processes. Emphasis is put on the safety issues of fuel reprocessing and waste storage. Two types of actinide separation processes, hydrometallurgical and pyrometallurgical, are considered, as well as related aspects of material studies, process modeling and the radiolytic stability of solvent extraction systems. Education and training of young researchers in nuclear chemistry is of particular importance for further development of this field.

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

    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)

  18. 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

    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)

  19. Frontiers in nuclear chemistry

    This book contains articles on the landmarks in nuclear and radiochemistry which takes through scientific history spanning over five decades from the times of Roentgen to the middle of this century. Articles on nuclear fission and back end of the nuclear fuel cycle give an insight into the current status of this subject. Reviews on frontier areas like lanthanides, actinides, muonium chemistry, accelerator based nuclear chemistry, fast radiochemical separations and nuclear medicine bring out the multidisciplinary nature of nuclear sciences. This book also includes an article on environmental radiochemistry and safety. Chapters relevant to INIS are indexed separately

  20. Extraction chemistry of some bidentate organophosphorus compounds

    Martella, L.L.; Navratil, J.D.; Santiago, W.F.

    1978-01-01

    The extraction chemistry of methylenediphosphonates, carbamoylphosphonates, and carbamoylmethylenephosphonates has been investigated. The bidentate organophosphorus compounds extract actinides strongly, extract lanthanides, iron, gallium, molybdenum, titanium, vanadium, and zirconium partially, and do not extract most other elements from 5 to 7 M nitric acid. The properties of the extractants and extraction mechanisms are discussed. The effect of complexing agents on the extraction of actinides and lanthanides is also presented.

  1. Actinide burning and waste disposal

    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. Thermal-hydraulics of actinide burner reactors

    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)

  3. Actinides and Life's Origins.

    Adam, Zachary

    2007-12-01

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

  4. ALMR potential for actinide consumption

    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)

  5. Actinides in earth materials: the importance of natural analogues

    Predictions of the stability of waste forms designed for long-term storage of actinides require an accurate knowledge of the long-term properties of these actinides in their host matrix. One useful approach to address this issue involves comparison of structural and thermodynamic information derived from short time-scale experiments on synthetic samples with similar information from natural samples, including natural glasses and metamict minerals. These natural analogues of synthetic waste forms, although significantly different in structure, properties and composition from the synthetic samples, offer a number of examples of earth materials that have received large doses of radioactivity (mainly α events) over very long time periods (106-109 years). In this paper, we present a review of the co-ordination chemistry of actinides in natural deep-seated earth systems and their analogues (mostly glasses, melts and radiation-damaged minerals). Special emphasis is given to data analysis methods that are important in determining accurate XAFS-derived interatomic distances and co-ordination numbers for actinides in these complex materials, including anharmonicity, multi-electronic transitions, deconvolution procedures, and ab initio calculations of near-edge structure. The effects of anharmonicity and multi-electronic transitions are best studied using high-energy resolution spectrometers on third-generation synchrotron sources. Application of these methods to selected natural minerals (crystalline and radiation-damaged) is presented, together with a comprehensive list of unusual mineral structures that are known to incorporate relatively large amounts of actinides over long periods of geologic time in a stable manner. (authors)

  6. Using Correlations to Understand Changes in Actinide Bonding

    An important issue in actinide science is the changing role of the 5f electrons, both when progressing across the series, as well as how experimental variables affect these roles in a particular element's chemistries and physics. The function of these 5f electrons can be changed by experimental conditions: temperature and pressure being two of many such variables. The 5f electrons of several actinide metals, their alloys and compounds are affected greatly by pressure, due to the very large decreases in interatomic distances encountered under pressure. The latter bring about significant changes in the total energy of the system and in the electronic energy levels, which in turn affect the potential for overlap/hybridization) of their orbitals, promotion of electrons to other orbitals, etc. The physical state, temperature, pressure, specific structures, magnetic interactions and spin polarization effects are all critical parameters for bonding. Often correlations of behavior with these parameters can provide unique insights and understanding into the bonding and the changes that occur in it. With the advancement of modern computation approaches using FPMTO, or other approaches, theory has enlightened greatly the understanding of not only the bonding behavior of these elements but also the understanding of changes observed experimentally. But these computational efforts have some complications and limitations, and at times experimental findings and theory are not always in full agreement. In contrast to the behaviors of the elements, changes observed with compounds often are not be linked directly to the involvement of 5f electrons, due in part to the presence and bonding role of non-actinide atoms. The latter affect both the actinide interatomic distances and the type of electronic orbitals that interact. Presented here is an overview of the pressure behavior several actinide elements, some insights into the bonding behavior of compounds under pressure and selected

  7. Investigating Actinide Molecular Adducts From Absorption Edge Spectroscopy

    Den Auwer, C.; Conradson, S.D.; Guilbaud, P.; Moisy, P.; Mustre de Leon, J.; Simoni, E.; /SLAC, SSRL

    2006-10-27

    Although Absorption Edge Spectroscopy has been widely applied to the speciation of actinide elements, specifically at the L{sub III} edge, understanding and interpretation of actinide edge spectra are not complete. In that sense, semi-quantitative analysis is scarce. In this paper, different aspects of edge simulation are presented, including semi-quantitative approaches. Comparison is made between various actinyl (U, Np) aquo or hydroxy compounds. An excursion into transition metal osmium chemistry allows us to compare the structurally related osmyl and uranyl hydroxides. The edge shape and characteristic features are discussed within the multiple scattering picture and the role of the first coordination sphere as well as contributions from the water solvent are described.

  8. Actinide cation-cation complexes

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO2+) 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 AnO2+; therefore, cation-cation complexes indicate something unique about AnO2+ cations compared to actinide cations in general. The first cation-cation complex, NpO2+·UO22+, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO2+ species, the cation-cation complexes of NpO2+ have been studied most extensively while the other actinides have not. The only PuO2+ cation-cation complexes that have been studied are with Fe3+ and Cr3+ 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 NpO2+·UO22+, NpO2+·Th4+, PuO2+·UO22+, and PuO2+·Th4+ 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

  9. Orbital effects in actinide systems

    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

  10. Fabrication of actinide mononitride fuel

    Fabrication of actinide mononitride fuel in JAERI is summarized. Actinide mononitride and their solid solutions were fabricated by carbothermic reduction of the oxides in N2 or N2-H2 mixed gas stream. Sintering study was also performed for the preparation of pellets for the property measurements and irradiation tests. The products were characterized to be high-purity mononitride with a single phase of NaCl-type structure. Moreover, fuel pins containing uranium-plutonium mixed nitride pellets were fabricated for the irradiation tests in JMTR and JOYO. (author)

  11. Computational Study of Covalency and Complexation in Actinides using Static and Dynamic Simulation and Topological Density Analysis

    Kirker, I. D. J.

    2013-01-01

    The separation of minor actinides such as americium and curium from other actinide and lanthanide-bearing components of used nuclear fuel is a necessary part of post-processing and recycling this fuel into storable components and new fuel material. Separation ratios can be optimised using a comprehensive understanding of the differences between these elements and their aqueous chemistry. This work uses computational simulation to investigate bonding behaviour and covalency differences between...

  12. Molecular structure of actinides in biochemistry

    In case of internal contamination, drugs used for decorporation are scarce and do not act very specifically. For instance the sole de-corporating drug recommended for plutonium decontamination is a water-soluble ligand named DTPA (Diethylene-Triamino-Pentaacetate). The transport of DTPA to its organ-target and its bio-availability on the spot are not satisfactorily understood. The conventional method to develop new ligands is based on molecular approaches but it is not sufficient. A new method that combines methods from structural biochemistry with methods of bio-inorganic chemistry and with methods from physico-chemistry (particularly X-ray absorption spectroscopy) is so far the best way to understand molecular speciation and to detail the local arrangement of atoms around a cation for instance, which are valuable information to understand the behaviour of a ligand. EXAFS (Extended X-ray Absorption Fine structure Spectroscopy) measurements suggest that during the formation of a complex involving an actinide (An) and a ligand, the inter-atomic distance An-O decreases when the atomic number of the cation increases while it is the reverse in the case of An-N

  13. Progress in molecular uranium-nitride chemistry

    King, David M.; Liddle, Stephen T

    2014-01-01

    The coordination, organometallic, and materials chemistry of uranium nitride has long been an important facet of actinide chemistry. Following matrix isolation experiments and computational characterisation, molecular, solution-based uranium chemistry has developed significantly in the last decade or so culminating most recently in the isolation of the first examples of long-sought terminal uranium nitride linkages. Herein, the field is reviewed with an emphasis on well-defined molecular spec...

  14. Fuel Chemistry Division: progress report for 1987

    The progress of research and development activities of the Fuel Chemistry Division of the Bhabha Atomic Research Centre, Bombay, during 1987 is reported in the form of summaries which are arranged under the headings: Fuel Development Chemistry, Chemistry of Actinides, Chemical Quality Control of Fuel, and Studies related to Nuclear Material Accounting. A list of publications by the members of the Division during the report period is given at the end of the report. (M.G.B.). refs., 15 figs., 85 tabs

  15. Study of kinetics of extraction of actinides in processes of reprocessing of nuclear fuels

    This research thesis reports a bibliographical study on extraction kinetics. After some generalities on solvent-based extraction, and on the chemistry of actinides in solution, on the methods of kinetics study which are generally used and their mathematical treatments, the author compares the published results for the extraction kinetics of nitric acid, uranium VI, uranium IV, neptunium IV and plutonium IV

  16. Archetypes for actinide-specific chelating agents

    The complexes of uranium and thorium with monomeric hydroxamic acids can serve as archetypes for an optimized macrochelate designed for tetravalent actinides. The eight-coordinate complexes, Th(i-PrN(O)C(O)R)4, where R = tert-butyl or R = neopentyl, have been synthesized and their structures have been determined by x-ray diffraction. The bulky alkyl substituents impart remarkable volatility and hydrocarbon solubility to these complexes, and the steric interactions of these substituents largely determine the structures. When R = tert-butyl, the substituents occupy the corners of a tetrahedron and force the complex into a distorted cubic geometry with crystallographic S4 symmetry. Insertion of a methylene group between the carbonyl carbon and the tert-butyl group relaxes the steric requirements, and the coordination polyhedron of the neopentyl derivative is close to the mmmm isomer of the trigonal-faced dodecahedron. Uranium tetrachloride was quantitatively oxidized via an oxygen transfer reaction with two equivalents of N-phenylbenzohydroxamic acid anion (PBHA) in tetrahydrofuran (THF) to form UO2 Cl(PBHA)(THF)2 and benzanilide. The structure of the uranyl complex has been determined from x-ray diffraction data; the linear uranyl ion is surrounded by a planar pentagonal array composed of two hydroxamate oxygen atoms, a chloride ion and two THF oxygens, such that the chloride ion is opposite the hydroxamate group. That the THF and phenyl rings are twisted from this equatorial plane limits the molecular geometry to that of the C1 point group. Some aspects of the chemistry of hydroxamic acids and of their incorporation into molecules that may serve as precursors of tetravalent actinide specific sequestering agents have also been investigated

  17. The JAERI and Universities joint project research reports on the 4th joint research project between JAERI and Universities on backend chemistry

    NONE

    2003-02-01

    In the Joint Research Project between JAERI and Universities on Backend Chemistry, the 4th-term researches of it were performed on sixteen themes from April of 1999 to March of 2001 under the four categories, i.e. Nuclear-chemistry and physical-chemistry properties of actinides', 'Solid state chemistry and nuclear fuel engineering of actinides', 'Solution chemistry and technologies for separation and analysis of actinides' and Treatment of radioactive waste and environmental chemistry'. The present report compiled the papers contributed to the Joint Research Project. (author)

  18. Environmental research on actinide elements

    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)

  19. ENDF/B-V actinides

    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)

  20. Electrochemistry of actinides in molten fluoride media: application to the actinides - lanthanides separation

    This study is part of a R and D program to assess the potentialities of high temperature molten salt technology for the reprocessing of spent nuclear fuel. The main objective is to acquire greater basic knowledge of actinides and lanthanides in molten salts. This paper deals with uranium and plutonium chemistry in molten fluorides. This work is focused on the electrochemical study of these two elements. The reduction process of uranium(IV) takes place in two steps whereas plutonium(III) is reduced in one step in the studied molten fluoride. A prospect on An-Ln separation is presented with the neodymium which has been previously studied. From a thermodynamic point of view the uranium and plutonium would be extracted at 99.99% without neodymium from an AnF3-NdF3-LiF-CaF2 mixture at 810 deg. C. (authors)

  1. Characterization Of Actinides In Simulated Alkaline Tank Waste Sludges And Leachates

    In this project, both the fundamental chemistry of actinides in alkaline solutions (relevant to those present in Hanford-style waste storage tanks), and their dissolution from sludge simulants (and interactions with supernatants) have been investigated under representative sludge leaching procedures. The leaching protocols were designed to go beyond conventional alkaline sludge leaching limits, including the application of acidic leachants, oxidants and complexing agents. The simulant leaching studies confirm in most cases the basic premise that actinides will remain in the sludge during leaching with 2-3 M NaOH caustic leach solutions. However, they also confirm significant chances for increased mobility of actinides under oxidative leaching conditions. Thermodynamic data generated improves the general level of experiemental information available to predict actinide speciation in leach solutions. Additional information indicates that improved Al removal can be achieved with even dilute acid leaching and that acidic Al(NO3)3 solutions can be decontaminated of co-mobilized actinides using conventional separations methods. Both complexing agents and acidic leaching solutions have significant potential to improve the effectiveness of conventional alkaline leaching protocols. The prime objective of this program was to provide adequate insight into actinide behavior under these conditions to enable prudent decision making as tank waste treatment protocols develop.

  2. CHARACTERIZATION OF ACTINIDES IN SIMULATED ALKALINE TANK WASTE SLUDGES AND LEACHATES

    Nash, Kenneth L.

    2008-11-20

    In this project, both the fundamental chemistry of actinides in alkaline solutions (relevant to those present in Hanford-style waste storage tanks), and their dissolution from sludge simulants (and interactions with supernatants) have been investigated under representative sludge leaching procedures. The leaching protocols were designed to go beyond conventional alkaline sludge leaching limits, including the application of acidic leachants, oxidants and complexing agents. The simulant leaching studies confirm in most cases the basic premise that actinides will remain in the sludge during leaching with 2-3 M NaOH caustic leach solutions. However, they also confirm significant chances for increased mobility of actinides under oxidative leaching conditions. Thermodynamic data generated improves the general level of experiemental information available to predict actinide speciation in leach solutions. Additional information indicates that improved Al removal can be achieved with even dilute acid leaching and that acidic Al(NO3)3 solutions can be decontaminated of co-mobilized actinides using conventional separations methods. Both complexing agents and acidic leaching solutions have significant potential to improve the effectiveness of conventional alkaline leaching protocols. The prime objective of this program was to provide adequate insight into actinide behavior under these conditions to enable prudent decision making as tank waste treatment protocols develop.

  3. Fundamental experimental determinations of thermal and radiolytic gas generation over actinide oxides

    In the areas of actinide waste disposition and storage and medium- to long-term retrievable U and Pu materials storage, the issue of water and other small molecule interactions with pure or impure actinide oxide materials and metal has become a major concern. Small molecule reactions in these systems have led to changes in materials stoichiometry, containment corrosion and breaches, dispersal of material resulting from pressurization, and the collapse of sealed containers due to the formation of partial vacuum. The exact nature of these reactions and the resulting implications for medium- to long-term storage are not well understood, although some studies have attempted to explain them from a large body of observations and experiments. The interaction of water with actinide and actinide oxide surfaces constitutes the fundamental technical basis for understanding and predicting long-term actinide material storage behavior. In this paper some of the studies that pertain to these efforts are summarized with particular emphasis on gas generation and/or consumption events relevant to actinide materials storage. These studies include fundamental surface studies of actinide and actinide oxide materials with water vapor using a wide variety of physical chemical and surface-specific techniques. In addition, radical surface chemistry arising from radiolytic decomposition of adsorbed water molecules is experimentally examined using unique gas exposure techniques. Preliminary studies are described and compared with conventional molecular gas-solid chemical model systems. Where possible, the relevant results from the surface science studies are utilized in understanding the back reaction of H2 and O2 to form H2O at relevant pressures in actual storage scenarios (described by Morales)

  4. Actinides recycling assessment in a thermal reactor

    Highlights: • Actinides recycling is assessed using BWR fuel assemblies. • Four fuel rods are substituted by minor actinides rods in a UO2 and in a MOX fuel assembly. • Performance of standard fuel assemblies and the ones with the substitution is compared. • Reduction of actinides is measured for the fuel assemblies containing minor actinides rods. • Thermal reactors can be used for actinides recycling. - Abstract: Actinides recycling have the potential to reduce the geological repository burden of the high-level radioactive waste that is produced in a nuclear power reactor. The core of a standard light water reactor is composed only by fuel assemblies and there are no specific positions to allocate any actinides blanket, in this assessment it is proposed to replace several fuel rods by actinides blankets inside some of the reactor core fuel assemblies. In the first part of this study, a single uranium standard fuel assembly is modeled and the amount of actinides generated during irradiation is quantified for use it as reference. Later, in the same fuel assembly four rods containing 6 w/o of minor actinides and using depleted uranium as matrix were replaced and depletion was simulated to obtain the net reduction of minor actinides. Other calculations were performed using MOX fuel lattices instead of uranium standard fuel to find out how much reduction is possible to obtain. Results show that a reduction of minor actinides is possible using thermal reactors and a higher reduction is obtained when the minor actinides are embedded in uranium fuel assemblies instead of MOX fuel assemblies

  5. Synergistic extraction of actinides : Part II. Tetra-and trivalent actinides

    A detailed discussion on the synergistic solvent extraction behaviour of tetra- and trivalent actinide ions is presented. Structural aspects of the natural donor adducts of the tetravalent actinide ion chelates involved in synergism are also discussed. (author)

  6. Spin Hamiltonians for actinide ions

    The breakdown of Russel Saunders coupling for correlated f-levels of actinide ions is due to both spin orbit coupling and the crystalline electric field (CEF). Experiments on curium, an S-state ion in the metal for which the CEF is weak indicate a g-factor close to the Russel-Saunders value. Spin-orbit coupling is therefore too weak to produce jj coupling. This suggests a model for magnetic actinide ions in which the CEF ground multiplet is well separated from higher levels, completely determining thermodynamic magnetic properties. On this basis simplified spin Hamiltonians are derived for GAMMA1-GAMMA5 ground states in order to interpret thermodynamic measurements and ordering phenomena. (author)

  7. Actinide recovery techniques utilizing electromechanical processes

    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

  8. Actinide Waste Forms and Radiation Effects

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

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

  9. Anthropogenic Actinides in the Environment

    The use of nuclear energy and the testing of nuclear weapons have led to significant releases of anthropogenic isotopes, in particular a number of actinide isotopes generally not abundant in nature. Most prominent amongst these are 239Pu, 240Pu, and 236U. The study of these actinides in nature has been an active field of study ever since. Measurements of actinides are applied to nuclear safeguards, investigating the sources of contamination, and as a tracer for a number of erosion and hydrology studies. Accelerator Mass Spectrometry (AMS) is ideally suited for these studies and generally offers higher sensitivities than competing techniques, like ICP-MS or decay counting. Recent advances in AMS allow the study of “minor” plutonium isotopes (241Pu, 242Pu, and 244Pu). Furthermore, 236U can now be measured at the levels expected from the global stratospheric fall-out of the atmospheric nuclear weapon tests in the 1950s and 1960s. Even the pre-anthropogenic isotope ratios could be within reach. However, the distribution and abundance levels of these isotopes are not well known yet. I will present an overview of the field, and in detail two recent studies on minor plutonium isotopes and 236U, respectively.(author)

  10. AERE Harwell Applied Chemistry Division unclassified progress report and bibliography for the period 1st April 1975 to 31st March 1976

    The Progress Report is under the headings: Analytical Chemistry Group, Actinide Analysis Group, Applied Electrochemistry Group, Nuclear Fuels Group, Solid State Chemistry Group, Separation Processes Group, list of unclassified publications. (U.K.)

  11. PWRs potentialities for minor actinides burning

    In the frame of the SPIN program at CEA, the impacts of the minor actinides (MA) incineration in PWRs are analysed. The aim is to reduce the mass, the potential radiotoxicity level. The recycling of all actinide elements is evaluated in a PWR nuclear yard. A sensitivity study is done to evaluate the incineration for each minor actinide element. This gives the most efficient way of incineration for each MA elements in a PWR and helps to design a PWR burner. This burner is disposed in a PWR nuclear system in which the actinides are recycled until equilibrium. (author)

  12. Long-term plant availability of actinides

    Environmental releases of actinide elements raise issues about which data are very limited. Quantitative information is required to assess the long-term behavior of actinides and their potential hazards resulting from the transport through food chains leading to man. Of special interest is the effect of time on the changes in the availability of actinide elements for uptake by plants from soil. This study provides valuable information on the effects of weathering and aging on the uptake of actinides from soil by range and crop plants grown under realistic field conditions

  13. Separation of actinides and fission products using solvent extraction, extraction chromatography, supported liquid membrane and biosorption techniques

    The actinide elements play an important role in the development of nuclear energy. The elements, 90Th to 103Lw, occupy a unique position in the periodic table. Seaborg has classified these elements as f-group elements(l) similar to the lanthanides where electrons get filled in the 4f shell. In the case of actinides, electrons get filled in the 5f shell. Some of the properties of the 4f- and 5f-elements are quite similar, such as complex formation, lanthanide/actinide contraction, multiple valency etc. Hence specially the chemistry of actinides has aroused much interest among the scientists, to carry out different types of investigations. (author)

  14. Emergence of californium as the second transitional element in the actinide series.

    Cary, Samantha K; Vasiliu, Monica; Baumbach, Ryan E; Stritzinger, Jared T; Green, Thomas D; Diefenbach, Kariem; Cross, Justin N; Knappenberger, Kenneth L; Liu, Guokui; Silver, Mark A; DePrince, A Eugene; Polinski, Matthew J; Van Cleve, Shelley M; House, Jane H; Kikugawa, Naoki; Gallagher, Andrew; Arico, Alexandra A; Dixon, David A; Albrecht-Schmitt, Thomas E

    2015-01-01

    A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. The metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence. PMID:25880116

  15. Actinide sequestration using self-assembled monolayers on mesoporous supports.

    Fryxell, Glen E; Lin, Yuehe; Fiskum, Sandy; Birnbaum, Jerome C; Wu, Hong; Kemner, Ken; Kelly, Shelley

    2005-03-01

    Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometalate anions, and radionuclides. Details addressing the design, synthesis, and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental cleanup necessary after 40 years of weapons-grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented. PMID:15787373

  16. Fuel Chemistry Division annual progress report for 1986

    The research and development activities of the Fuel Chemistry Division during 1986 are reported in the form of summaries. These activities mainly deal with nuclear fuel development, the chemistry of actinides and solid and solution state, analytical methods for chemical quality control of fuels and other related materials. (M.G.B.)

  17. Heavy element nuclear chemistry research in JAERI

    Heavy element nuclear chemistry research in JAERI is reviewed. Recent experimental results on decay studies of neutron deficient actinide nuclei using the gas-jet coupled JAERI-ISOL are presented. Successful production of the transactinide nuclei, 261Rf and 262Db, and the present status of studies of chemical properties on the transactinide elements are introduced. (author)

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

    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, P63/m group). Here, extended X-ray Absorption Fine Structure (EXAFS) at the iron K-edge and actinide L3-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 L2,3 edge, nitrogen and carbon K-edge and also actinides N4,5 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

  19. Calculated Atomic Volumes of the Actinide Metals

    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....

  20. PIE analysis for minor actinide

    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)

  1. Actinide co-conversion by internal gelation

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

  2. Actinides analysis by accelerator mass spectrometry

    At the ANTARES accelerator at ANSTO a new beamline has been commissioned, incorporating new magnetic and electrostatic analysers, to optimise the efficiency for Actinides detection by Accelerator Mass Spectrometry (AMS). The detection of Actinides, particularly the isotopic ratios of uranium and plutonium, provide unique signatures for nuclear safeguards purposes. We are currently engaged in a project to evaluate the application of AMS to the measurement of Actinides in environmental samples for nuclear safeguards. Levels of certain fission products, Actinides and other radioactive species can be used as indicators of undeclared nuclear facilities or activities, either on-going or in the past Other applications of ultra-sensitive detection of Actinides are also under consideration. neutron-attenuation images of a porous reservoir rock

  3. Actinide ion sensor for pyroprocess monitoring

    Jue, Jan-fong; Li, Shelly X.

    2014-06-03

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

  4. EUROPART: an European integrated project on actinide partitioning

    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

  5. Liquid scintillation counting techniques for the determination of some alpha emitting actinides: a review

    The present report is a review of the work on liquid scintillation counting techniques, for the determination of alpha emitting actinides like uranium, plutonium, americium etc; for the last three decades (1970-1999). It covers the progress that has taken place in conventional liquid scintillation counting employing various solvents, scintillators and extractants. There is gradual development in instrumentation from integral counting of alpha emitters to alpha liquid scintillation spectrometry to resolve and identify different alpha emitters. These advancements have led to Pulse Shape Analysis (PSA) and Photon Electron Rejecting Alpha Liquid Scintillation Spectrometry (PERALS) techniques for the determination of the alpha emitters in the presence of beta and gamma activity. These techniques allow the determination of actinides at very low levels which has increased their applications to almost all the fields of chemistry; be it biomedical, environmental, geological or process chemistry of nuclear fuels. The development of biphasic technique using various extractants to separate different elements and counting in presence of one another has been made possible. Inorganic scintillators have been recently developed which have the advantage of eliminating effects of quenching and presence of beta/gamma emitting actinides. This review will serve as a reference to those who want to carry out work in the field of determination of actinides using liquid scintillation counting techniques. (author)

  6. Rare-earth metal π-complexes of reduced arenes, alkenes, and alkynes: Bonding, electronic structure, and comparison with actinides and other electropositive metals

    Huang, W.; Diaconescu, PL

    2015-01-01

    © 2015 The Royal Society of Chemistry. Rare-earth metal complexes of reduced π ligands are reviewed with an emphasis on their electronic structure and bonding interactions. This perspective discusses reduced carbocyclic and acyclic π ligands; in certain categories, when no example of a rare-earth metal complex is available, a closely related actinide analogue is discussed. In general, rare-earth metals have a lower tendency to form covalent interactions with π ligands compared to actinides, m...

  7. The ALMR actinide burning system

    The advanced liquid-metal reactor (ALMR) actinide burning system is being developed under the sponsorship of the US Department of Energy to bring its unique capabilities to fruition for deployment in the early 21st century. The system consists of four major parts: the reactor plant, the metal fuel and its recycle, the processing of light water reactor (LWR) spent fuel to extract the actinides, and the development of a residual waste package. This paper addresses the status and outlook for each of these four major elements. The ALMR is being developed by an industrial group under the leadership of General Electric (GE) in a cost-sharing arrangement with the US Department of Energy. This effort is nearing completion of the advanced conceptual design phase and will enter the preliminary design phase in 1994. The innovative modular reactor design stresses simplicity, economics, reliability, and availability. The design has evolved from GE's PRISM design initiative and has progressed to the final stages of a prelicensing review by the US Nuclear Regulatory Commission (NRC); a safety evaluation report is expected by the end of 1993. All the major issues identified during this review process have been technically resolved. The next design phases will focus on implementation of the basic safety philosophy of passive shutdown to a safe, stable condition, even without scram, and passive decay heat removal. Economic projections to date show that it will be competitive with non- nuclear and advanced LWR nuclear alternatives

  8. Lanthanide and actinide extractions with cobalt bis(dicarbollide) ion derivatives covalently bonded to diglycolyl diamide platform

    Lučaníková, M.; Selucký, P.; Rais, J.; Grüner, Bohumír; Kvíčalová, Magdalena

    2011-01-01

    Roč. 1, č. 1 (2011), s. 89-95. ISSN 2193-2875 R&D Projects: GA ČR GA104/09/0668; GA MŠk LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : Dicarbollides derivatives * TODGA * Liquid-liquid extraction * Lanthanides * Actinides Subject RIV: CA - Inorganic Chemistry

  9. Chemistry of heavy- and trans-actinide elements. Experiments

    Experimental results on the chemical properties of the transactinide element, Rf (Z=104), on an atom-at-a-time base are reviewed. Status and future plans for the study of chemical behavior of transactinide elements with the JAERI tandem accelerator are reported. (author)

  10. Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes.

    Carter, Tyler J; Wilson, Richard E

    2015-10-26

    The synthesis, X-ray crystal structure, vibrational and optical spectroscopy for the eight-coordinate thiocyanate compounds, [Et4 N]4 [Pu(IV) (NCS)8 ], [Et4 N]4 [Th(IV) (NCS)8 ], and [Et4 N]4 [Ce(III) (NCS)7 (H2 O)] are reported. Thiocyanate was found to rapidly reduce plutonium to Pu(III) in acidic solutions (pHthiocyanate complex [Et4 N]4 [Pu(IV) (NCS)8 ] was crystallized when a large excess of [Et4 N][NCS] was present. This compound, along with its U(IV) analogue, maintains inner-sphere thiocyanate coordination in acetonitrile based on the observation of intense ligand-to-metal charge-transfer bands. Spectroscopic and crystallographic data do not support the interaction of the metal orbitals with the ligand π system, but support an enhanced An(IV) -NCS interaction, as the Lewis acidity of the metal ion increases from Th to Pu. PMID:26493880

  11. Relativistic DV-DS MO method for actinide chemistry

    After a brief description of the relativistic discrete-variational Dirac-Slater (DV-DS) method, the electronic structure calculation of uranyl nitrate dihydrate cluster is performed. The charge distribution and bond overlap population between the central uranium atom and the closest oxygens are investigated by the Mulliken's population analysis. The orbital components and chemical bonding nature at the valence levels are also elucidated. (author)

  12. Experimental studies of actinides in molten salts

    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

  13. Experimental studies of actinides in molten salts

    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.

  14. Spin and orbital moments in actinide compounds

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

    1991-01-01

    -electron band-structure calculations, is that the orbital moments of the actinide 5f electrons are considerably reduced from the values anticipated by a simple application of Hund's rules. To test these ideas, and thus to obtain a measure of the hybridization, we have performed a series of neutron scattering...... 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 as...

  15. Electronic structure and magnetic properties of actinides

    The study of the actinide series shows the change between transition metal behavior and lanthanide behavior, between constant weak paramagnetism for thorium and strong Curie-Weiss paramagnetism for curium. Curium is shown to be the first metal of the actinide series to be magnetically ordered, its Neel temperature being 52K. The magnetic properties of the actinides depending on all the peripheral electrons, their electronic structure was studied and an attempt was made to determine it by means of a phenomenological model. Attempts were also made to interrelate the different physical properties which depend on the outer electronic structure

  16. Fuel Chemistry Division annual progress report for 1990

    The progress report gives brief descriptions of the various activities of the Fuel Chemistry Division of Bhabha Atomic Research Centre, Bombay for the year 1990. The descriptions of activities are arranged under the headings: Fuel Development Chemistry, Chemistry of Actinides, Quality Control of Nuclear Fuels, and studies related to Nuclear Materials Accounting. At the end of the report, a list of papers published in journals and presented at various conferences/symposia is also given. (author). 7 figs., 52 tabs

  17. Actinide recovery from pyrochemical residues

    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 62- from high-chloride low-acid solution. Americium and other metals are washed from the ion exchange column with lN HNO3-4.8M NaCl. After elution, plutonium is recovered by hydroxide precipitation, and americium is recovered by NaHCO3 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

  18. PF-4 actinide disposition strategy

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

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

    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)

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

    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.

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

    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

  2. PWRs potentialities for minor actinides burning

    In the frame of the SPIN program at CEA, the impacts of the Minor Actinides (MA) incineration in PWRs are analysed. The aim is to reduce the mass and the potential radiotoxicity level. This study is done separately one on the Plutonium recycling. But the plutonium is essential. Thus, the recycling of all Actinide elements is evaluated in a PWR nuclear yard. A sensitivity study is done to evaluate the incineration for each Minor Actinide element. This gives us the most efficient way of incineration for each MA element in a PWR and help us to design a PWR burner. This burner is disposed in a PWR nuclear system in which the Actinides are recycled until equilibrium. (authors). 2 refs

  3. Electronic structure and correlation effects in actinides

    Albers, R.C.

    1998-12-01

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

  4. Preparation of actinide targets by electrodeposition

    Trautmann, N.; Folger, H.

    1989-10-01

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

  5. Actinide research to solve some practical problems

    The following topics are discussed: generation of plutonium inventories by nuclear power plants; resettlement of the Marshallese Islanders into an actinide contaminated environment; high radiation background areas of the world; and radiation hazards to uranium miners

  6. BWR Assembly Optimization for Minor Actinide Recycling

    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).

  7. Superconductivity in rare earth and actinide compounds

    Rare earth and actinide compounds and the extraordinary superconducting and magnetic phenomena they exhibit are surveyed. The rare earth and actinide compounds described belong to three classes of novel superconducting materials: high temperature, high field superconductors (intermetallics and layered cuprates); superconductors containing localized magnetic moments; heavy fermion superconductors. Recent experiments on the resistive upper critical field of high Tc cuprate superconductors and the peak effect in the critical current density of the f-electron superconductor CeRu2 are discussed. (orig.)

  8. Lanthanides and actinides in ionic liquids

    Binnemans, Koen

    2007-01-01

    This lecture gives an overview of the research possibilities offered by combining f-elements (lanthanides and actinides) with ionic liquids [1] Many ionic liquids are solvents with weakly coordinating anions. Solvation of lanthanide and actinide ions in these solvents is different from what is observed in conventional organic solvents and water. The poorly solvating behavior can also lead to the formation of coordination compounds with low coordination numbers. The solvation of f-elements can...

  9. New molecules to separate actinides: the picolinamides

    The reprocessing of spent fuel is made with the Purex process, funded on liquid-liquid extraction of uranium nitrates(VI) and plutonium nitrates(IV) by the BTP (tributyl phosphate). To improve this proceeding, we look for extractants which allow, beyond U and Pu extractions, these of actinides (II) and allow separation of the whole actinides from the fission products, which have an important fraction of lanthanides. A new family seems to give good results: the picolinamides

  10. Lattice effects in the light actinides

    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

  11. Evaluation of actinide partitioning and transmutation

    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

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

    (IV). Further studies showed that the [NpVO2]+ analogue (which is stable with respect to disproportionation) was not reduced by G. sulfurreducens. These results suggest that the reductive mechanism shows a surprising degree of selectivity for hexavalent actinides and illustrates the need for mechanistic understanding and care in devising in situ bio-remediation strategies for complex wastes containing other redox-active actinides. Our current studies are investigating the effect of G.sulfurreducens on the redox chemistry of plutonium. (authors)

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

    Renshaw, J.C.; Livens, F.R. [Williamson Research Centre for Molecular Environmental Science, School of Earth, Atmospheric and Environmental Science, The University of Manchester, Manchester, M13 9PL (United Kingdom)]|[Centre for Radiochemistry Research, School of Chemistry, The University of Manchester, Manchester, M13 9PL (United Kingdom); May, I. [Centre for Radiochemistry Research, School of Chemistry, The University of Manchester, Manchester, M13 9PL (United Kingdom); Lloyd, J.R. [Williamson Research Centre for Molecular Environmental Science, School of Earth, Atmospheric and Environmental Science, The University of Manchester, Manchester, M13 9PL (United Kingdom)

    2005-07-01

    , forming an unstable [UO{sub 2}]{sup +} species which subsequently disproportionates to give insoluble U(IV). Further studies showed that the [Np{sup V}O{sub 2}]{sup +} analogue (which is stable with respect to disproportionation) was not reduced by G. sulfurreducens. These results suggest that the reductive mechanism shows a surprising degree of selectivity for hexavalent actinides and illustrates the need for mechanistic understanding and care in devising in situ bio-remediation strategies for complex wastes containing other redox-active actinides. Our current studies are investigating the effect of G.sulfurreducens on the redox chemistry of plutonium. (authors)

  14. Actinides in Solution: Disproportionation, Strong Correlations, and Emergence

    Marston, Brad; Horowitz, Steven

    2010-03-01

    Plutonium in acid solutions can be found in oxidation states III through VI. There is a striking near perfect degeneracy of the reduction-oxidation (redox) potentials, each being about 1 volt. Neptunium is the only other element that approaches this degree of degeneracy. One consequence of the redox degeneracy is a marked tendency of plutonium ions to disproportionate; up to four different oxidation states can coexist simultaneously in the same solution, greatly complicating the environmental chemistry of the element. While the degeneracy could simply be a coincidence, it could also be the manifestation of a higher-level organizing principle at work. Other systems that exhibit disproportionation raise the possibility of an emergent negative-U attractive interaction. The hypothesis is tested by combining first-principles relativistic density-functional calculations using the Amsterdam Density Functional (ADF) package with exact diagonalizations of Hubbard-like models of the strong correlations between the actinide 5f electrons.

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

    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.

  16. Actinide transmutation in nuclear reactors

    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)

  17. Isotope and nuclear chemistry division. Annual report, FY 1987. Progress report, October 1986-September 1987

    This report describes progress in the major research and development programs carried out in FY 1987 by the Isotope and Nuclear Chemistry Division. The report includes articles on radiochemical weapons diagnostics and research and development; other unclassified weapons research; stable and radioactive isotope production and separation; chemical biology and nuclear medicine; element and isotope transport and fixation; actinide and transition metal chemistry; structural chemistry, spectroscopy, and applications; nuclear structure and reactions; irradiation facilities; advanced concepts and technology; and atmospheric chemistry

  18. Assessment of photochemical applications to specific stages in Savannah River Plant actinide reprocessing streams

    The application of photochemical redox methods has been evaluated as a means of separating actinides in Purex reprocessing streams. This chemistry promises to eliminate many of the chemical reagents which are otherwise necessary to effect valence control of such actinides as plutonium and neptunium. The most promising processing stages of the Savannah River Plant reprocessing facility for feasibility testing of the photochemical method appear to be those in which the concentrations of the actinides in question are the lowest, thus minimizing the required amount of absorbed light. Although neptunium valence control appears to be feasible through the photochemical generation of nitrite ion, the urgency for its control is secondary to that of plutonium. Therefore, the Purex ''2nd-U-cycle feed'' stage has been selected as the top priority for testing the photochemical technique. The chemistry initially involves the photoreduction of U(VI) to U(IV), which in turn reduces Pu(IV) to Pu(III). The results of preliminary experiments on nitrate ion and uranyl ion photoreduction are also given. With less than 100 W of absorbed power, the rates of NO2- and U4+ generation, respectively, appear ample to handle process requirements. 14 refs., 3 figs., 5 tabs

  19. Use of fast reactors for actinide transmutation

    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

  20. Waste disposal aspects of actinide separation

    Two recent NRPB reports are summarized (Camplin, W.C., Grimwood, P.D. and White, I.F., The effects of actinide separation on the radiological consequences of disposal of high-level radioactive waste on the ocean bed, Harwell, National Radiological Protection Board, NRPB-R94 (1980), London, HMSO; Hill, M.D., White, I.F. and Fleishman, A.B., The effects of actinide separation on the radiological consequences of geologic disposal of high-level waste. Harwell, National Radiological Protection Board, NRPB-R95 (1980), London, HMSO). They describe preliminary environmental assessments relevant to waste arising from the reprocessing of PWR fuel. Details are given of the modelling of transport of radionuclides to man, and of the methodology for calculating effective dose equivalents in man. Emphasis has been placed on the interaction between actinide separation and the disposal options rather than comparison of disposal options. The reports show that the effects of actinide separation do depend on the disposal method. Conditions are outlined where the required substantial further research and development work on actinide separation and recycle would be justified. Toxicity indices or 'toxic potentials' can be misleading and should not be used to guide research and development. (U.K.)

  1. Solubility of actinide surrogates in nuclear glasses

    This paper discusses the results of a study of actinide surrogates in a nuclear borosilicate glass to understand the effect of processing conditions (temperature and oxidizing versus reducing conditions) on the solubility limits of these elements. The incorporation of cerium oxide, hafnium oxide, and neodymium oxide in this borosilicate glass was investigated. Cerium is a possible surrogate for tetravalent and trivalent actinides, hafnium for tetravalent actinides, and neodymium for trivalent actinides. The material homogeneity was studied by optical, scanning electron microscopy. Cerium LIII XANES spectroscopy showed that the Ce3+/Cetotal ratio increased from about 0.5 to 0.9 as the processing temperature increased from 1100 to 1400 deg. C. Cerium LIII XANES spectroscopy also confirmed that the increased Ce solubility in glasses melted under reducing conditions was due to complete reduction of all the cerium in the glass. The most significant results pointed out in the current study are that the solubility limits of the actinide surrogates increases with the processing temperature and that Ce3+ is shown to be more soluble than Ce4+ in this borosilicate glass

  2. TUCS/phosphate mineralization of actinides

    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.

  3. New reagents for actinide-lanthanide group separations

    Organic extractants which possess nitrogen or sulfur donor atoms preferentially complex the trivalent actinide. They are potential reagents for actinide lanthanide group separations, which can be performed at low pH without the addition of inorganic salts

  4. Bad chemistry

    Petsko, Gregory A

    2004-01-01

    General chemistry courses haven't changed significantly in forty years. Because most basic chemistry students are premedical students, medical schools have enormous influence and could help us start all over again to create undergraduate chemistry education that works.

  5. Sorption of actinides onto nanodiamonds

    Buchatskaya, Yulia; Romanchuk, Anna; Yakovlev, Ruslan; Kulakova, Inna [Lomonosov Moscow State Univ., Moscow (Russian Federation). Dept. of Chemistry; Shiryaev, Andrei [Russian Academy of Sciences, Moscow (Russian Federation). Frumkin Institute of Physical Chemistry and Electrochemistry; Russian Academy of Sciences, Moscow (Russian Federation). Inst. of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry; Kalmykov, Stepan [Lomonosov Moscow State Univ., Moscow (Russian Federation). Dept. of Chemistry; Russian Academy of Sciences, Moscow (Russian Federation). Frumkin Institute of Physical Chemistry and Electrochemistry; Russian Academy of Sciences, Moscow (Russian Federation). Vernadsky Institute of Geochemistry and Analytical Chemistry

    2015-06-01

    Detonation nanodiamonds (ND) present a significant part of nanocarbons group, which could be produced on commercial scale by detonation of explosives in a closed chamber. Their unique properties of high surface area, low weight and radiation resistance make ND a prospective candidate for applications in sorption processes in radiochemistry. To study the influence of surface chemistry on sorption properties, apristine sample of ND was treated with acids and hydrogen. The surface chemistry of the samples was characterised by infrared spectroscopy, X-ray photoelectron spectroscopy and Boehm titration. The sorption properties of ND were tested fordifferent radionuclides. The sorption capacity of ND was shown to be higher than those of commonly used radionuclide sorbents like activated carbon and compariable to other members of nanocarbon group like graphene oxide and carbon nanotubes. The sorption properties were shown to be influenced by the presence of oxygen-containing groups on the surface of ND. This represents an opportunity to increase the sorption capacity of ND.

  6. Separation of actinides with alkylpyridinium salts

    Various f-elements are separated as anionic complexes from both acidic and alkaline solutions by precipitation with alkylpyridinium salts. The precipitates are also cationic surfactants where the simple counter-ion (e.g. nitrate or chloride) is replaced by the negatively charged complex anion of an actinide or lanthanide. The low solubility of these precipitates is explained by a strong affinity of divalent complex counter-ions of f-elements to the quaternary nitrogen. Precipitations in solutions of nitric acid allow to separate tetravalent f-elements from other metals, in alkaline carbonate solutions tetravalent and hexavalent actinides are precipitated simultaneously. The last procedure yields precipitates, which are very intimate mixtures of hexavalent and tetravalent actinides. This allows to prepare mixed oxides in a simple way. (author) 6 refs.; 3 figs.; 3 tabs

  7. Minior Actinide Doppler Coefficient Measurement Assessment

    Nolan E. Hertel; Dwayne Blaylock

    2008-04-10

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

  8. Research on Actinides in Nuclear Fuel Cycles

    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

  9. Neutron scattering studies of the actinides

    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 UO2, 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

  10. Homogeneous recycling of minor actinides in an EFR type fast reactor

    The capability of the European Fast Reactor (EFR) as a typical large fast reactor to incinerate the minor actinides Np and Am, produced in LWRs, has been investigated for the case of homogeneous recycling of Np, Am and Pu. Detailed account is taken for a three-region reload scheme in which every two years 1/3 of the core is refuelled. The fraction of admixed minor actinides is varied from 2.8 to 7.5%. Results are given in terms of the number of clean-up LWRs by one burner, the nuclide inventories during recycling, and the risk potential of the waste from the incineration system compared to the non-incineration case. It is concluded that an enforced research should be done in chemistry to prove that a satisfactory separation especially of Am and also of Cm from the rare earths in the waste is possible on large scale. (author). 4 refs, 7 figs, 1 tab

  11. Spin-Orbit Coupling in Actinide Cations

    Bagus, Paul S.; Ilton, Eugene S.; Martin, Richard L.; Jensen, Hans Jorgen A.; Knecht, Stefan

    2012-09-01

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

  12. Spin-orbit coupling in actinide cations

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

    2012-09-01

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

  13. Actinide and fission product separation and transmutation

    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.)

  14. Actinide elements in aquatic and terrestrial environments

    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 239Np 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

  15. Sequential analysis of selected actinides in urine

    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)

  16. Actinide and fission product separation and transmutation

    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.)

  17. Isotope and Nuclear Chemistry Division annual report, FY 1983

    Heiken, J.H.; Lindberg, H.A. (eds.)

    1984-05-01

    This report describes progress in the major research and development programs carried out in FY 1983 by the Isotope and Nuclear Chemistry Division. It covers radiochemical diagnostics of weapons tests; weapons radiochemical diagnostics research and development; other unclassified weapons research; stable and radioactive isotope production, separation, and applications (including biomedical applications); element and isotope transport and fixation; actinide and transition metal chemistry; structural chemistry, spectroscopy, and applications; nuclear structure and reactions; irradiation facilities; advanced analytical techniques; development and applications; atmospheric chemistry and transport; and earth and planetary processes.

  18. Isotope and Nuclear Chemistry Division annual report, FY 1984

    This report describes progress in the major research and development programs carried out in FY 1984 by the Isotope and Nuclear Chemistry Division. It covers radiochemical diagnostics of weapons tests; weapons radiochemical diagnostics research and development; other unclassified weapons research; stable and radioactive isotope production, separation, and applications (including biomedical applications); element and isotope transport and fixation; actinide and transition metal chemistry; structural chemistry, spectroscopy, and applications; nuclear structure and reactions; irradiation facilities; advanced analytical techniques: development and applications; atmospheric chemistry and transport; and earth and planetary processes. 287 refs

  19. Isotope and Nuclear Chemistry Division annual report, FY 1983

    This report describes progress in the major research and development programs carried out in FY 1983 by the Isotope and Nuclear Chemistry Division. It covers radiochemical diagnostics of weapons tests; weapons radiochemical diagnostics research and development; other unclassified weapons research; stable and radioactive isotope production, separation, and applications (including biomedical applications); element and isotope transport and fixation; actinide and transition metal chemistry; structural chemistry, spectroscopy, and applications; nuclear structure and reactions; irradiation facilities; advanced analytical techniques; development and applications; atmospheric chemistry and transport; and earth and planetary processes

  20. Fuel Chemistry Division: annual progress report for 1988

    The progress report gives the brief descriptions of various activites of the Fuel Chemistry Division of Bhabha Atomic Research Centre, Bombay for the year 1988. The descriptions of activities are arranged under the headings: Fuel Development Chemistry of Actinides, Quality Control of Fuel, and Studies related to Nuclear Material Accounting. At the end of report, a list of publications published in journals and papers presented at various conferences/symposia during 1988 is given. (author). 13 figs., 61 tabs

  1. Actinide recycle in LMFBRs as a waste management alternative

    Beaman, S.L.

    1979-08-21

    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.

  2. Chemical compatibility of HLW borosilicate glasses with actinides

    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 230C and 1150C. (orig.)

  3. Actinide recycle in LMFBRs as a waste management alternative

    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

  4. Halogen protected cobalt bis(dicarbollide) ions with covalently bonded CMPO functions as anionic extractants for trivalent lanthanide/actinide partitioning

    Grüner, Bohumír; Švec, Petr; Selucký, P.; Bubeníková, M.

    2012-01-01

    Roč. 38, č. 1 (2012), s. 103-112. ISSN 0277-5387 R&D Projects: GA ČR GA104/09/0668 Institutional research plan: CEZ:AV0Z40320502 Keywords : carboranes * metallaboranes * dicarbollides * CMPR * liquid-liquid extraction * lanthanides * actinides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.813, year: 2012

  5. Separation of trivalent actinides and lanthanides from simulated high-level waste using cobalt bis(dicarbollide) ion derivate substituted with diphenyl-N-tert.octyl-carbamoylmethylphosphine oxide

    Selucký, P.; Lučaníková, M.; Grüner, Bohumír

    2012-01-01

    Roč. 100, č. 3 (2012), s. 179-183. ISSN 0033-8230 R&D Projects: GA MŠk LC523; GA ČR GA104/09/0668 Institutional research plan: CEZ:AV0Z40320502 Keywords : dicarbollide * CMPO * liquid-liquid extraction * actinides * lanthanides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.373, year: 2012

  6. Complex chemistry

    Kim, Bong Gon; Kim, Jae Sang; Kim, Jin Eun; Lee, Boo Yeon

    2006-06-15

    This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

  7. Complex chemistry

    This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

  8. Chemistry for fast reactor fuel cycle

    The fuel cycle for the fast reactors poses several challenging chemistry issues. The use of fuels with high plutonium content, the variety of fuel matrices (oxides, carbides, metal alloys), the high burn-up to which the fuel is driven and the need to close the fuel cycle with minimum out-of-pile inventory are examples of special features of fast reactors. The need to reduce waste generation and the need to identify matrices for safe long term disposal of waste are additional issues that need a chemist's attention. As a chemist, the subject of actinide separations has been very stimulating to me, with a myriad of interesting possibilities and at the same time, demanding careful attention to the unique chemistry of the actinides including multiplicity of oxidation states. The presence of high concentrations of plutonium in the reprocessing streams introduces issues such as third phase formation, which provides an incentive for the development of candidates for solvent extraction as alternatives to tri-n-butyl phosphate, currently used for the Purex reprocessing scheme. With the advent of supercritical fluid extraction as a tool for actinide recovery from a variety of matrices, and the potential of room temperature ionic liquids to offer significant advantages in actinide processing, actinide separations is an element of fast reactor fuel cycle that is full of opportunities and challenges. The need to process metallic alloy fuels using molten salt electrorefining as the route, adds further to the challenges. The presentation will highlight some of the recent progress achieved in this area at IGCAR. (author)

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

    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

  10. Geochemistry of actinides. Application to the storage of high level radioactive wastes. Under the supervision of Mr Michel Treuil

    This collective research report first addresses the chemistry of actinides with a description of their atomic orbitals and the study of their behaviour in solution. The author addresses several aspects: historical overview on actinides, radioactivity, chemical reactions in aqueous solution, redox chemistry, speciation in solution with respect to water characteristics in deep storage conditions. The second part gathers several studies performed on a natural laboratory (the Oklo site in which nuclear reactions occurred about 2 billions years ago) and reports the modelling of radionuclide transfer within a geological system (the model is applied to the Oklo site). The third part addresses issues related to the nuclear fuel cycle, and the storage modes and materials envisaged and involved regarding the storage of high level radioactive wastes, notably in France