Impact of Including Higher Actinides in Fast Reactor Transmutation Analyses

DOE Office of Scientific and Technical Information (OSTI.GOV)

B. Forget; M. Asgari; R. Ferrer

2007-09-01

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

Testing actinide fission yield treatment in CINDER90 for use in MCNP6 burnup calculations

DOE PAGES

Fensin, Michael Lorne; Umbel, Marissa

2015-09-18

Most of the development of the MCNPX/6 burnup capability focused on features that were applied to the Boltzman transport or used to prepare coefficients for use in CINDER90, with little change to CINDER90 or the CINDER90 data. Though a scheme exists for best solving the coupled Boltzman and Bateman equations, the most significant approximation is that the employed nuclear data are correct and complete. Thus, the CINDER90 library file contains 60 different actinide fission yields encompassing 36 fissionable actinides (thermal, fast, high energy and spontaneous fission). Fission reaction data exists for more than 60 actinides and as a result, fissionmore » yield data must be approximated for actinides that do not possess fission yield information. Several types of approximations are used for estimating fission yields for actinides which do not possess explicit fission yield data. The objective of this study is to test whether or not certain approximations of fission yield selection have any impact on predictability of major actinides and fission products. Further we assess which other fission products, available in MCNP6 Tier 3, result in the largest difference in production. Because the CINDER90 library file is in ASCII format and therefore easily amendable, we assess reasons for choosing, as well as compare actinide and major fission product prediction for the H. B. Robinson benchmark for, three separate fission yield selection methods: (1) the current CINDER90 library file method (Base); (2) the element method (Element); and (3) the isobar method (Isobar). Results show that the three methods tested result in similar prediction of major actinides, Tc-99 and Cs-137; however, certain fission products resulted in significantly different production depending on the method of choice.« less

The Efficacy of Denaturing Actinide Elements as a Means of Decreasing Materials Attractiveness

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hase, Kevin R.; Ebbinghaus, Bartley B.; Sleaford, Brad W.

2013-07-01

This paper is an extension to earlier studies that examined the attractiveness of materials mixtures containing special nuclear materials (SNM) and alternate nuclear materials (ANM). This study considers the concept of denaturing as applied to the actinide elements present in spent fuel as a means to reduce materials attractiveness. Highly attractive materials generally have low values of bare critical mass, heat content, and dose.

Synthesis of actinide nitrides, phosphides, sulfides and oxides

DOEpatents

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

1992-01-01

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

Incorporation mechanisms of actinide elements into the structures of U 6+ phases formed during the oxidation of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Burns, Peter C.; Ewing, Rodney C.; Miller, Mark L.

1997-05-01

Uranyl oxide hydrate and uranyl silicate phases will form due to the corrosion and alteration of spent nuclear fuel under oxidizing conditions in silica-bearing solution. The actinide elements in the spent fuel may be incorporated into the structures of these secondary U6+ phases during the long-term corrosion of the UO 2 in spent fuel. The incorporation of actinide elements into the crystal structures of the alteration products may decrease actinide mobility. The crystal chemistry of the various oxidation states of the actinide elements of environmental concern is examined to identify possible incorporation mechanisms. The substitutions Pu 6+U 6+ and (Pu 5+, Np 5+)U 6+ should readily occur in many U 6+ structures, although structural modification may be required to satisfy local bond-valence requirements. Crystal-chemical characteristics of the U 6+ phases indicate that An 4+ (An: actinide)U 6+ substitution is likely to occur in the sheets of uranyl polyhedra that occur in the structures of the minerals schoepite, [(UO 2) 8O 2(OH) 12](H 2O) 12, ianthinite, [U 24+ (UO 2) 4O 6(OH) 4(H 2O) 4](H 2O) 5, becquerelite, Ca[(UO 2) 3O 2(OH) 3] 2(H 2O) 8, compreignacite, K 2[(UO 2) 3O 2(OH) 3] 2(H 2O) 8, α-uranophane, Ca[(UO 2)(SiO 3OH)] 2(H 2O) 5, and boltwoodite, K(H 2O)[(UO 2)(SiO 4)], all of which are likely to form due to the oxidation and alteration of the UO 2 in spent fuel. The incorporation of An 3+ into the sheets of the structures of α-uranophane and boltwoodite, as well as interlayer sites of various uranyl phases, may occur.

Final Technical Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dr. Asok K. Ray

2012-05-22

During the past decades, considerable theoretical efforts have been devoted to studying the electronic and geometric structures and related properties of surfaces. Such efforts are particularly important for systems like the actinides for which experimental work is relatively difficult to perform due to material problems and toxicity. The actinides are characterized by a gradual filling of the 5f-electron shell with the degree of localization increasing with the atomic number Z along the last series of the periodic table. The open shell of the 5f electrons determines the atomic, molecular, and solid state properties of the actinide elements and their compoundsmore » and understanding the quantum mechanics of the 5f electrons is the defining issue in the chemistry and physics of actinide elements. These elements are also characterized by the increasing prominence of relativistic effects and their studies can, in fact, help us understand the role of relativity throughout the periodic table. However, the electronic and geometric structures of the actinides, specifically the trans-uranium actinides and the roles of the 5f electrons in chemical bonding are still not well understood. This is crucial not only for our understanding of the actinides but also for the fact that the actinides constitute 'the missing link' between the d transition elements and the lanthanides. The 5f orbitals have properties intermediate between those of localized 4f and delocalized 3d orbitals. Thus, a proper understanding of the actinides will help us understand the behavior of the lanthanides and transition metals as well. In fact, there is an urgent need for continued extensive and detailed theoretical research in this area to provide significant and deep understandings of the electronic and geometric structures of the actinides. In this work, we have performed electronic structure studies for plutonium (Pu), americium (Am), and curium (Cm) surfaces, and molecular adsorptions on Pu and Am surfaces. In particular, the region at the boundary of Pu and Am, is widely believed to be the crossover region between d-like itinerant and f-like localized behavior The eventual goal is a complete understanding of the surface chemistry and physics processes of all actinide surfaces, defining the chemistry and physics of such heavy elements. Among the actinides, plutonium, with five 5f electrons in the solid state, is arguably the most complex, fascinating, and enigmatic element known to mankind and has attracted extraordinary scientific and technological interests because of its unique properties, generating a significant body of research in diverse areas, including superconductivity. Pu has, at least, six stable allotropes between room temperature and melting at atmospheric pressure, indicating that the valence electrons can hybridize into a number of complex bonding arrangements. Central and critical questions relate to the electronic structure, localization of the 5f electrons and the magnetism of Pu. For the light-actinides, from Th to Pu, the 5f electrons are believed to be delocalized, hybridizing with the 6d and 7s electrons. For the heavier actinides, Am and beyond, the 5f electrons are localized with the 5f orbitals progressively lower in energy relative to the 6d configuration. Hence, Pu is in a position where the 5f electronic behavior changes from itinerant to localized. As far as magnetism is concerned, a majority of the theoretical calculations continues to claim the existence of magnetism while almost all the experimental results do not find any support for such claims. The second element of interest to us, namely americium, occupies a central position in the actinide series with respect to the involvement of 5f electrons in metallic bonding. It is widely believed that the 5f electrons in Am are localized and that Am undergoes a series of crystallographic phase changes with pressure. Fully-relativistic all electron surface studies of the different phases of Am, initially for the dhcp and the fcc surfaces, can and have provided us with valuable information about chemical bonding in Am and the transitions from f-electron delocalization to f-electron localization in trans-uranium compounds. In particular, a comparative study of the electronic structures of the Pu and Am surfaces using the techniques of all-electron modern density functional theory and beyond can provide significant information about the role of 5f electrons in bond formation as also the localization of the 5f electrons, matters of considerable controversies. The change from metallic 5f bonding into local-moment nonbonding configurations that takes place between Pu and Am is rather unique in the periodic table and is at the very heart of our understanding of electronic structure. We believe that, considering the narrow bandwidth of surface states, any transition from itinerant to localized behavior first takes place at the actinide surfaces with possible reconstructions.« less

Yttrium and rare earth stabilized fast reactor metal fuel

DOEpatents

Guon, Jerold; Grantham, LeRoy F.; Specht, Eugene R.

1992-01-01

To increase the operating temperature of a reactor, the melting point and mechanical properties of the fuel must be increased. For an actinide-rich fuel, yttrium, lanthanum and/or rare earth elements can be added, as stabilizers, to uranium and plutonium and/or a mixture of other actinides to raise the melting point of the fuel and improve its mechanical properties. Since only about 1% of the actinide fuel may be yttrium, lanthanum, or a rare earth element, the neutron penalty is low, the reactor core size can be reduced, the fuel can be burned efficiently, reprocessing requirements are reduced, and the nuclear waste disposal volumes reduced. A further advantage occurs when yttrium, lanthanum, and/or other rare earth elements are exposed to radiation in a reactor, they produce only short half life radioisotopes, which reduce nuclear waste disposal problems through much shorter assured-isolation requirements.

The discovery of plutonium reorganized the periodic table and aided the discovery of new elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, David L

2009-01-01

The modern Periodic Table derives principally from the work of the great Russian scientist Dimitri Mendeleev, who in 1869 enunciated a 'periodic law' that the properties of the elements are a periodic function of their atomic weights, and arranged the 65 known elements in a 'periodic table'. Fundamentally, every column in the main body of the Periodic Table is a grouping of elements that display similar chemical and physical behavior. Similar properties are therefore exhibited by elements with widely different mass. Chemical periodicity is central to the study of chemistry, and no other generalization comes close to its ability tomore » systematize and rationalize known chemical facts. With the development of atomic theory, and an understanding of the electronic structure of atoms, chemical periodicity and the periodic table now find their natural explanation in the electronic structure of atoms. Moving from left to right along any row, the elements are arranged sequentially according to nuclear charge (the atomic number). Electrons counter balance that nuclear charge, hence each successive element has one more electron in its configuration. The electron configuration, or distribution of electrons among atomic orbitals, may be determined by application of the Pauli principle (paired spin in the same orbital) and the aufbau principle (which outlines the order of filling of electrons into shells of orbitals - s, p, d, f, etc.) such that in a given atom, no two electrons may have all four quantum numbers identical. In 1939, only three elements were known to be heavier than actinium: thorium, protactinium, and uranium. All three exhibited variable oxidation states and a complex chemistry. Thorium, protactinium and uranium were assumed to be d-transition metals and were placed in the Periodic Table under hafnium, tantalum, and tungsten, respectively. By 1940, McMillan and Abelson bombarded uranium atoms with slow neutrons and successfully identified atoms of element 93, which they named neptunium after the planet Neptune. This rapidly set the stage for the discovery of the next succeeding element, plutonium (Seaborg, McMillan, Kennedy, and Wahl, 1940), named after the next planet away from the Sun, Pluto. The newly discovered elements were presumed to fit comfortably in the Periodic Table under rhenium and osmium, respectively. However, subsequent tracer chemical experiments showed that neptunium and plutonium were closer in their chemical properties to uranium than their presumed homologues, rhenium and osmium. Spectroscopic evidence also indicated that the new elements were not typical transition elements, but had f-electrons in their valence shell. Thus, several researchers, including McMillan and Wahl, and Zachariasen at Los Alamos, suggested that these elements might be part of a second inner-transition series in which the 5f-electron subshell was being filled. It was not clear, however, where the new series would begin. McMillian had proposed a 'uraninide series' that started with neptunium, but attempts to isolate elements with atomic numbers 95 and 96 based on assumed similarities to uranium were unsuccessful. Both Wahl and Zacharias en had proposed a thoride series that started with protactinium. In 1944, Seaborg proposed that the series started with thorium, and that all of the elements heavier than actinium constituted an 'actinide' series similar to the lanthanides. Because the 5f-shell began filling in the same relative position as the 4f-shell, the electronic configuration of elements in the two series would be similar. Guided by the hypothesis that elements 95 and 96 were homologues of europium and gadolinium, new experiments were designed and the elements were uniquely synthesized and separated from all others. The new elements were subsequently named americium and curium. Seaborg's 'Actinide Concept' thus played a major role in the discovery of the transplutonium elements. It provided the framework that supported synthesis, isolation, and identification of the succeeding actinide elements berkelium through lawrencium and beyond to the element with Atomic Number 118. But as research has progressed in the study of the actinide elements, it has become clear that the 5f series has a unique chemistry that is distinct from the lanthanides. One of the focal points of study in actinide research has been to better define the scope and limitations of the actinide concept. Seaborg's actinide concept of heavy element electronic structure, prediction that the actinides form a transition series analogous to the rare earth series of lanthanide elements, is now well accepted in the scientific community and included in all standard configurations of the Periodic Table.« less

PuS: Reflectivity

NASA Astrophysics Data System (ADS)

Troć, R.

This document is part of subvolume B6bβ`Actinide Monochalcogenides' of Volume 27 `Magnetic properties of non-metallic inorganic compounds based on transition elements' of Landolt-Börnstein - Group III `Condensed Matter'. The volume presents magnetic and related properties of monochalcogenides based on actinides and their solid solutions.

Molecular orbital studies of the bonding in heavy element organometallics: Progress report

NASA Astrophysics Data System (ADS)

Bursten, B. E.

1988-03-01

Over the past two years we have made considerable progress in the understanding of the bonding in heavy element mononuclear and binuclear complexes. For mononuclear complexes, our strategy has been to study the orbital interactions between the actinide metal center and the surrounding ligands. One particular system which has been studied extensively is X sub 3 AnL (where X = Cp, Cl, NH sub 2 ; An = actinide; and L = neutral or anionic ligand). We are interested not only in the mechanics of the An-X orbital interactions, but also how the relative donor characteristics of X may influence coordination of the fourth ligand L to the actinide. For binuclear systems, we are interested not only in homobimetallic complexes, but also in heterobimetallic complexes containing actinides and transition metals. In order to make the calculations of such large systems tractable, we have transferred the X-alpha-SW codes to the newly acquired Cray XMP24 at the Ohio Supercomputer Center. This has resulted in significant savings of money and time.

A Multireference Density Functional Approach to the Calculation of the Excited States of Uranium Ions

DTIC Science & Technology

2007-03-01

approach. xiv A MULTIREFERENCE DENSITY FUNCTIONAL APPROACH TO THE CALCULATION OF THE EXCITED STATES OF URANIUM IONS I. Introduction Actinide chemistry, in...oxidation state of the uranium atom. Uranium, like most early actinides , can possess a wide range of oxidation states, ranging from +3 to +6, due in part...in predicting the electronic spectra for heavy element compounds. The first difficulty is that relativistic effects for actinides are significant

PuS: Thermoelectric Power

NASA Astrophysics Data System (ADS)

Troć, R.

This document is part of subvolume B6bβ`Actinide Monochalcogenides' of Volume 27 `Magnetic properties of non-metallic inorganic compounds based on transition elements' of Landolt-Börnstein - Group III `Condensed Matter'. The volume presents magnetic and related properties of monochalcogenides based on actinides and their solid solutions.

Protactinium and the intersection of actinide and transition metal chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, Richard E.; De Sio, Stephanie; Vallet, Valérie

The role of the 5f and 6d orbitals in the chemistry of the actinide elements has been of considerable interest since their discovery and synthesis. Relativistic effects cause the energetics of the 5f and 6d orbitals to change as the actinide series is traversed left to right imparting a rich and complex chemistry. The 5f and 6d atomic states cross in energy at protactinium (Pa), making it a potential intersection between transition metal and actinide chemistries. Herein, we report the synthesis of a Pa-peroxo cluster, A(6)(Pa4O(O-2)(6)F-12) [A = Rb, Cs, (CH3)(4)N], formed in pursuit of an actinide polyoxometalate. Quantum chemicalmore » calculations at the density functional theory level demonstrate equal 5f and 6d orbital participation in the chemistry of Pa and increasing 5f orbital participation for the heavier actinides. Periodic changes in orbital character to the bonding in the early actinides highlights the influence of the 5f orbitals in their reactivity and chemical structure.« less

Support for Students and Young Scientists to Participate in the 2009 Actinides Conference to be held in San Francisco, CA, Sunday, 12 July 2009 -- Friday, 17 July 2009

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raymond, Kenneth N.

2011-04-08

Early career scientist were provided support to attend and participate in the Actinides 2009 (AN2009) International Conference held in San Francisco, California from 12-17 July 2011. This is the premier conference in the field of actinide chemistry, physics, and materials science of the actinide elements. Participation in the preeminent scientific meeting in actinide science keeps the U.S at the forefront of developments in this key field. The specific involvement of early career scientists combats the loss of expertise in the aforementioned critical areas related to f-element chemistry such as energy, homeland, and environmental security. Without these trained scientists, the U.S.more » will not be able to properly exploit nuclear technology to its fullest and will not be able to address its energy needs in either an environmentally safe or cost–effective manner nor will it be able to provide for its national defense. Furthermore, the early career scientists added greatly to the scientific content of the meeting and stimulates early career scientists to remain in the filed of actinide science. Providing support for participation in the AN2009 Conference via registration fee waivers, hotel cost support, and travel cost support, was extremely effective in securing the participation of early career scientists that would have not otherwise been able to attend.« less

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

PubMed

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

2016-01-28

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

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

DOE PAGES

Dumas, Thomas; Guillaumont, Dominique; Fillaux, Clara; ...

2016-01-01

The electronic properties of actinide cations are of fundamental interest to describe intramolecular interactions and chemical bonding in the context of nuclear waste reprocessing or direct storage. The 5f and 6d orbitals are the first partially or totally vacant states in these elements, and the nature of the actinide ligand bonds is related to their ability to overlap with ligand orbitals. Because of its chemical and orbital selectivities, X-ray absorption spectroscopy (XAS) is an effective probe of actinide species frontier orbitals and for understanding actinide cation reactivity toward chelating ligands. The soft X-ray probes of the light elements provide bettermore » resolution than actinide L 3 -edges to obtain electronic information from the ligand. Thus coupling simulations to experimental soft X-ray spectral measurements and complementary quantum chemical calculations yields quantitative information on chemical bonding. In this study, soft X-ray XAS at the K-edges of C and N, and the L 2,3 -edges of Fe was used to investigate the electronic structures of the well-known ferrocyanide complexes K 4 Fe II (CN) 6 , thorium hexacyanoferrate Th IV Fe II (CN) 6 , and neodymium hexacyanoferrate KNd III Fe II (CN) 6 . The soft X-ray spectra were simulated based on quantum chemical calculations. Our results highlight the orbital overlapping effects and atomic effective charges in the Fe II (CN) 6 building block. In addition to providing a detailed description of the electronic structure of the ferrocyanide complex (K 4 Fe II (CN) 6 ), the results strongly contribute to confirming the actinide 5f and 6d orbital oddity in comparison to lanthanide 4f and 5d.« less

New Perspectives on the Essential Trace Elements.

ERIC Educational Resources Information Center

Frieden, Earl

1985-01-01

Provides a comprehensive overview of the 19 essential trace elements, examining: the concept of essentiality; evolution of these elements; possible future essential elements; the lanthanides and actinides; how essential trace elements work; the metalloenzymes; the nonmetals; iodine and the thyroid hormones; and antagonism among these elements. (JN)

Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States

DOE PAGES

Evans, William J.

2016-09-15

A fundamental aspect of any element is the range of oxidation states accessible for useful chemistry. This tutorial describes the recent expansion of the number of oxidation states available to the rare-earth and actinide metals in molecular complexes that has resulted through organometallic chemistry involving the cyclopentadienyl ligand. These discoveries demonstrate that the cyclopentadienyl ligand, which has been a key component in the development of organometallic chemistry since the seminal discovery of ferrocene in the 1950s, continues to contribute to the advancement of science. Lastly, we present background information on the rare-earth and actinide elements, as well as the sequencemore » of events that led to these unexpected developments in the oxidation state chemistry of these metals.« less

Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States

DOE Office of Scientific and Technical Information (OSTI.GOV)

Evans, William J.

A fundamental aspect of any element is the range of oxidation states accessible for useful chemistry. This tutorial describes the recent expansion of the number of oxidation states available to the rare-earth and actinide metals in molecular complexes that has resulted through organometallic chemistry involving the cyclopentadienyl ligand. These discoveries demonstrate that the cyclopentadienyl ligand, which has been a key component in the development of organometallic chemistry since the seminal discovery of ferrocene in the 1950s, continues to contribute to the advancement of science. Lastly, we present background information on the rare-earth and actinide elements, as well as the sequencemore » of events that led to these unexpected developments in the oxidation state chemistry of these metals.« less

Systematization of actinides using cluster analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

1994-11-01

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

Extraction processes and solvents for recovery of cesium, strontium, rare earth elements, technetium and actinides from liquid radioactive waste

DOEpatents

Zaitsev, Boris N.; Esimantovskiy, Vyacheslav M.; Lazarev, Leonard N.; Dzekun, Evgeniy G.; Romanovskiy, Valeriy N.; Todd, Terry A.; Brewer, Ken N.; Herbst, Ronald S.; Law, Jack D.

2001-01-01

Cesium and strontium are extracted from aqueous acidic radioactive waste containing rare earth elements, technetium and actinides, by contacting the waste with a composition of a complex organoboron compound and polyethylene glycol in an organofluorine diluent mixture. In a preferred embodiment the complex organoboron compound is chlorinated cobalt dicarbollide, the polyethylene glycol has the formula RC.sub.6 H.sub.4 (OCH.sub.2 CH.sub.2).sub.n OH, and the organofluorine diluent is a mixture of bis-tetrafluoropropyl ether of diethylene glycol with at least one of bis-tetrafluoropropyl ether of ethylene glycol and bis-tetrafluoropropyl formal. The rare earths, technetium and the actinides (especially uranium, plutonium and americium), are extracted from the aqueous phase using a phosphine oxide in a hydrocarbon diluent, and reextracted from the resulting organic phase into an aqueous phase by using a suitable strip reagent.

Abundance of live 244Pu in deep-sea reservoirs on Earth points to rarity of actinide nucleosynthesis

PubMed Central

Wallner, A.; Faestermann, T.; Feige, J.; Feldstein, C.; Knie, K.; Korschinek, G.; Kutschera, W.; Ofan, A.; Paul, M.; Quinto, F.; Rugel, G.; Steier, P.

2015-01-01

Half of the heavy elements including all actinides are produced in r-process nucleosynthesis, whose sites and history remain a mystery. If continuously produced, the Interstellar Medium is expected to build-up a quasi-steady state of abundances of short-lived nuclides (with half-lives ≤100 My), including actinides produced in r-process nucleosynthesis. Their existence in today’s interstellar medium would serve as a radioactive clock and would establish that their production was recent. In particular 244Pu, a radioactive actinide nuclide (half-life=81 My), can place strong constraints on recent r-process frequency and production yield. Here we report the detection of live interstellar 244Pu, archived in Earth’s deep-sea floor during the last 25 My, at abundances lower than expected from continuous production in the Galaxy by about 2 orders of magnitude. This large discrepancy may signal a rarity of actinide r-process nucleosynthesis sites, compatible with neutron-star mergers or with a small subset of actinide-producing supernovae. PMID:25601158

The role of the 5f valence orbitals of early actinides in chemical bonding

PubMed Central

Vitova, T.; Pidchenko, I.; Fellhauer, D.; Bagus, P. S.; Joly, Y.; Pruessmann, T.; Bahl, S.; Gonzalez-Robles, E.; Rothe, J.; Altmaier, M.; Denecke, M. A.; Geckeis, H.

2017-01-01

One of the long standing debates in actinide chemistry is the level of localization and participation of the actinide 5f valence orbitals in covalent bonds across the actinide series. Here we illuminate the role of the 5f valence orbitals of uranium, neptunium and plutonium in chemical bonding using advanced spectroscopies: actinide M4,5 HR-XANES and 3d4f RIXS. Results reveal that the 5f orbitals are active in the chemical bonding for uranium and neptunium, shown by significant variations in the level of their localization evidenced in the spectra. In contrast, the 5f orbitals of plutonium appear localized and surprisingly insensitive to different bonding environments. We envisage that this report of using relative energy differences between the 5fδ/ϕ and 5fπ*/5fσ* orbitals as a qualitative measure of overlap-driven actinyl bond covalency will spark activity, and extend to numerous applications of RIXS and HR-XANES to gain new insights into the electronic structures of the actinide elements. PMID:28681848

The role of the 5f valence orbitals of early actinides in chemical bonding

NASA Astrophysics Data System (ADS)

Vitova, T.; Pidchenko, I.; Fellhauer, D.; Bagus, P. S.; Joly, Y.; Pruessmann, T.; Bahl, S.; Gonzalez-Robles, E.; Rothe, J.; Altmaier, M.; Denecke, M. A.; Geckeis, H.

2017-07-01

One of the long standing debates in actinide chemistry is the level of localization and participation of the actinide 5f valence orbitals in covalent bonds across the actinide series. Here we illuminate the role of the 5f valence orbitals of uranium, neptunium and plutonium in chemical bonding using advanced spectroscopies: actinide M4,5 HR-XANES and 3d4f RIXS. Results reveal that the 5f orbitals are active in the chemical bonding for uranium and neptunium, shown by significant variations in the level of their localization evidenced in the spectra. In contrast, the 5f orbitals of plutonium appear localized and surprisingly insensitive to different bonding environments. We envisage that this report of using relative energy differences between the 5fδ/φ and 5fπ*/5fσ* orbitals as a qualitative measure of overlap-driven actinyl bond covalency will spark activity, and extend to numerous applications of RIXS and HR-XANES to gain new insights into the electronic structures of the actinide elements.

METHOD FOR THE PREPARATION OF STABLE ACTINIDE METAL OXIDE-CONTAINING SLURRIES AND OF THE OXIDES THEREFOR

DOEpatents

Hansen, R.S.; Minturn, R.E.

1958-02-25

This patent deals with a method of preparing actinide metal oxides of a very fine particle size and of forming stable suspensions therefrom. The process consists of dissolving the nitrate of the actinide element in a combustible organic solvent, converting the solution obtained into a spray, and igniting the spray whereby an oxide powder is obtained. The oxide powder is then slurried in an aqueous soiution of a substance which is adsorbable by said oxides, dspersed in a colloid mill whereby a suspension is obtained, and electrodialyzed until a low spectiic conductance is reached.

FIIDOS--A Computer Code for the Computation of Fallout Inhalation and Ingestion Dose to Organs Computer User’s Guide (Revision 4)

DTIC Science & Technology

2007-05-01

35 5 Actinide product radionuclides... actinides , and fission products in fallout. Doses from low-linear energy transfer (LET) radiation (beta particles and gamma rays) are reported separately...assumptions about the critical parameters used in calculating internal doses – resuspension factor, breathing rate, fractionation, and scenario elements – to

Protected Nuclear Fuel Element

DOEpatents

Kittel, J. H.; Schumar, J. F.

1962-12-01

A stainless steel-clad actinide metal fuel rod for use in fast reactors is reported. In order to prevert cladding failures due to alloy formation between the actinide metal and the stainless steel, a mesh-like sleeve of expanded metal is interposed between them, the sleeve metal being of niobium, tantalum, molybdenum, tungsten, zirconium, or vanadium. Liquid alkali metal is added as a heat transfer agent. (AEC)

Thermally Activated Driver

NASA Technical Reports Server (NTRS)

Kinard, William H.; Murray, Robert C.; Walsh, Robert F.

1987-01-01

Space-qualified, precise, large-force, thermally activated driver (TAD) developed for use in space on astro-physics experiment to measure abundance of rare actinide-group elements in cosmic rays. Actinide cosmic rays detected using thermally activated driver as heart of event-thermometer (ET) system. Thermal expansion and contraction of silicone oil activates driver. Potential applications in fluid-control systems where precise valve controls are needed.

Separation of actinides from lanthanides

DOEpatents

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

1988-03-31

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

Separation of actinides from lanthanides

DOEpatents

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

1989-01-01

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

Removal of actinide elements from liquid scintillation cocktail wastes using liquid-liquid extraction and demulsification techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foltz, K.; Landsberger, S.; Srinivasan, B.

1994-12-31

A method for the separation of radionuclides with Z greater than 88, from lower-level radioactive wastes (liquid scintillation cocktail or LSC wastes), is described. The method is liquid-liquid extraction (LLX) and demulsification. The actinide elements are removed from the LSC wastes by extraction into an aqueous phase after the cocktail has been demulsified. The aqueous and organic phases are separated, then the wastes type remaining may be incinerated. Future experiments will be performed to study the effects of pH and temperature and to extend the study to wastes containing americium.

2017 Report for New LANL Physical Vapor Deposition Capability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roman, Audrey Rae; Zhao, Xinxin; Bond, Evelyn M.

There is an urgent need at LANL to achieve uniform, thin film actinide targets that are essential for nuclear physics experiments. The target preparation work is currently performed externally by Professor Walter Loveland at Oregon State University, who has made various evaporated actinide targets such as Th and U for use on several nuclear physics measurements at LANSCE. We are developing a vapor deposition capability, with the goal of evaporating Th and U in the Actinide Research Facility (ARF) at TA-48. In the future we plan to expand this work to evaporating transuranic elements, such as Pu. The ARF ismore » the optimal location for evaporating actinides because this lab is specifically dedicated to actinide research. There are numerous instruments in the ARF that can be used to provide detailed characterization of the evaporated thin films such as: Table top Scanning Electron Microscope, In-situ X-Ray Diffraction, and 3D Raman spectroscopy. These techniques have the ability to determine the uniformity, surface characterization, and composition of the deposits.« less

Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules

PubMed Central

Lyon, Jonathan T.; Hu, Han-Shi; Andrews, Lester; Li, Jun

2007-01-01

Chemistry of the actinide elements represents a challenging yet vital scientific frontier. Development of actinide chemistry requires fundamental understanding of the relative roles of actinide valence-region orbitals and the nature of their chemical bonding. We report here an experimental and theoretical investigation of the uranium methylidyne molecules X3UCH (X = F, Cl, Br), F2ClUCH, and F3UCF formed through reactions of laser-ablated uranium atoms and trihalomethanes or carbon tetrafluoride in excess argon. By using matrix infrared spectroscopy and relativistic quantum chemistry calculations, we have shown that these actinide complexes possess relatively strong UC triple bonds between the U 6d-5f hybrid orbitals and carbon 2s-2p orbitals. Electron-withdrawing ligands are critical in stabilizing the U(VI) oxidation state and sustaining the formation of uranium multiple bonds. These unique UC-bearing molecules are examples of the long-sought actinide-alkylidynes. This discovery opens the door to the rational synthesis of triple-bonded actinidecarbon compounds. PMID:18024591

Method of loading organic materials with group III plus lanthanide and actinide elements

DOEpatents

Bell, Zane W [Oak Ridge, TN; Huei-Ho, Chuen [Oak Ridge, TN; Brown, Gilbert M [Knoxville, TN; Hurlbut, Charles [Sweetwater, TX

2003-04-08

Disclosed is a composition of matter comprising a tributyl phosphate complex of a group 3, lanthanide, actinide, or group 13 salt in an organic carrier and a method of making the complex. These materials are suitable for use in solid or liquid organic scintillators, as in x-ray absorption standards, x-ray fluorescence standards, and neutron detector calibration standards.

Crystal growth methods dedicated to low solubility actinide oxalates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tamain, C., E-mail: christelle.tamain@cea.fr; Arab-Chapelet, B.; Rivenet, M.

Two novel crystal growth syntheses dedicated to low solubility actinide-oxalate systems and adapted to glove box handling are described. These methods based on the use of precursors of either actinide metal or oxalic acid have been optimized on lanthanide systems (analogue of actinides(III)) and then assessed on real actinide systems. They allow the synthesis of several actinide oxalate single crystals, Am{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 3}·xH{sub 2}O, Th(C{sub 2}O{sub 4}){sub 2}·6H{sub 2}O, M{sub 2+x}[Pu{sup IV}{sub 2−x}Pu{sup III}{sub x}(C{sub 2}O{sub 4}){sub 5}]·nH{sub 2}O and M{sub 1−x}[Pu{sup III}{sub 1−x}Pu{sup IV}{sub x}(C{sub 2}O{sub 4}){sub 2}·H{sub 2}O]·nH{sub 2}O. It is the first timemore » that these well-known compounds are formed by crystal growth methods, thus enabling direct structural studies on transuranic element systems and acquisition of basic data beyond deductions from isomorphic (or not) lanthanide compounds. Characterizations by X-ray diffraction, UV–visible solid spectroscopy, demonstrate the potentialities of these two crystal growth methods to obtain oxalate compounds. - Graphical abstract: Two new single crystal growth methods dedicated to actinide oxalate compounds. - Highlights: • Use of diester as oxalate precursor for crystal growth of actinide oxalates. • Use of actinide oxide as precursor for crystal growth of actinide oxalates. • Crystal growth of Pu(III) and Am(III) oxalates. • Crystal growth of mixed Pu(III)/Pu(IV) oxalates.« less

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

PubMed

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

2015-08-18

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

Crystal growth methods dedicated to low solubility actinide oxalates

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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

PubMed Central

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

2015-01-01

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

Chemical bonds and vibrational properties of ordered (U, Np, Pu) mixed oxides

NASA Astrophysics Data System (ADS)

Yang, Yu; Zhang, Ping

2013-01-01

We use density functional theory +U to investigate the chemical bonding characters and vibrational properties of the ordered (U, Np, Pu) mixed oxides (MOXs), UNpO4,NpPuO4, and UPuO4. It is found that the 5f electronic states of different actinide elements keep their localized characters in all three MOXs. The occupied 5f electronic states of different actinide elements do not overlap with each other and tend to distribute over the energy band gap of the other actinide element's 5f states. As a result, the three ordered MOXs all show smaller band gaps than those of the component dioxides, with values of 0.91, 1.47, and 0.19 eV for UNpO4,NpPuO4, and UPuO4, respectively. Through careful charge density analysis, we further show that the U-O and Pu-O bonds in MOXs show more ionic character than in UO2 and PuO2, while the Np-O bonds show more covalent character than in NpO2. The change in covalencies in the chemical bonds leads to vibrational frequencies of oxygen atoms that are different in MOXs.

Implications of human tissue studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kathren, R.L.

1986-10-01

Through radiochemical analysis of voluntary tissue donations, the United States Transuranium and Uranium Registries are gaining improved understanding of the distribution and biokinetics of actinide elements in occupationally exposed persons. Evaluation of the first two whole body contributions to the Transuranium Registry revealed an inverse proportionality between actinide concentration and bone ash fraction. The analysis of a whole body with a documented /sup 241/Am deposition indicated a significantly shorter half-time in liver and a greater fraction resident in the skeleton than predicted by existing models. Other studies of the Registries are designed to evaluate in vivo estimates of actinide depositionmore » with those derived from postmortem tissue analysis, compare results of animal experiments with human data, and reviw histopathologic slides for tissue toxicity that might be attributable to exposure to uranium and the transuranic elements. The implications of these recent findings and other work of the Registries are discussed from the standpoint of their potential impact on biokinetic modeling, internal dose assessment, safety standards, and operational health physics practices.« less

Soil Sample Dissolution Development by Ultrawave Digester, Followed by Isotopic Separation and Analysis

DTIC Science & Technology

2017-01-09

uranium, americium, and thorium were analyzed, along with other transition and rare earth metals, utilizing inductively coupled plasma- mass spectrometry...inductively coupled plasma- mass spectrometry and/or alpha spectrometry, following digestion. For validation of the microwave protocol, radioactive... actinide elements. HF is a hazardous acid to work with and it is highly toxic. In this evaluation and validation, the actinides are of particular

Directed evolution of the periodic table: probing the electronic structure of late actinides.

PubMed

Marsh, M L; Albrecht-Schmitt, T E

2017-07-25

Recent investigations of the coordination chemistry and physical properties of berkelium (Z = 97) and californium (Z = 98) have revealed fundamental differences between post-curium elements and lighter members of the actinide series. This review highlights these developments and chronicles key findings and concepts from the last half-century that have helped usher in a new understanding of the evolution of electronic structure in the periodic table.

REGENERATION OF REACTOR FUEL ELEMENTS

DOEpatents

Roake, W.E.; Lyon, W.L.

1960-03-29

A process of concentrating by electrolysis the uraatum and/or plutonium of an aluminum alloy containing these actinides after the actinide has been partially consumed by neutron bombardment in a reactor is given. The alloy is made the anode in a system having an aluminum cathode and a cryolite electrolyte. Electrolysis from 22 to 28 ampere-hours removes a sufficient quantity of aluminum from the alloy to make it suitable for reuse.

Sub-barrier quasifission in heavy element formation reactions with deformed actinide target nuclei

NASA Astrophysics Data System (ADS)

Hinde, D. J.; Jeung, D. Y.; Prasad, E.; Wakhle, A.; Dasgupta, M.; Evers, M.; Luong, D. H.; du Rietz, R.; Simenel, C.; Simpson, E. C.; Williams, E.

2018-02-01

Background: The formation of superheavy elements (SHEs) by fusion of two massive nuclei is severely inhibited by the competing quasifission process. Low excitation energies favor SHE survival against fusion-fission competition. In "cold" fusion with spherical target nuclei near 208Pb, SHE yields are largest at beam energies significantly below the average capture barrier. In "hot" fusion with statically deformed actinide nuclei, this is not the case. Here the elongated deformation-aligned configurations in sub-barrier capture reactions inhibits fusion (formation of a compact compound nucleus), instead favoring rapid reseparation through quasifission. Purpose: To determine the probabilities of fast and slow quasifission in reactions with prolate statically deformed actinide nuclei, through measurement and quantitative analysis of the dependence of quasifission characteristics at beam energies spanning the average capture barrier energy. Methods: The Australian National University Heavy Ion Accelerator Facility and CUBE fission spectrometer have been used to measure fission and quasifission mass and angle distributions for reactions with projectiles from C to S, bombarding Th and U target nuclei. Results: Mass-asymmetric quasifission occurring on a fast time scale, associated with collisions with the tips of the prolate actinide nuclei, shows a rapid increase in probability with increasing projectile charge, the transition being centered around projectile atomic number ZP=14 . For mass-symmetric fission events, deviations of angular anisotropies from expectations for fusion fission, indicating a component of slower quasifission, suggest a similar transition, but centered around ZP˜8 . Conclusions: Collisions with the tips of statically deformed prolate actinide nuclei show evidence for two distinct quasifission processes of different time scales. Their probabilities both increase rapidly with the projectile charge. The probability of fusion can be severely suppressed by these two quasifission processes, since the sub-barrier heavy element yield is likely to be determined by the product of the probabilities of surviving each quasifission process.

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

PubMed Central

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

SEPARATION OF TRANSURANIC ELEMENTS FROM RARE EARTH COMPOUNDS

DOEpatents

Kohman, T.P.

1961-11-21

A process of separating neptunium and plutonium values from rare earths and alkaline earth fission products present on a solid mixed actinide carrier (Th or U(IV) oxalate or fluoride) --fission product carrier (LaF/sub 3/, CeF/sub 3/, SrF/sub 2/, CaF/sub 2/, YF/sub 3/, La oxalate, cerous oxalate, Sr oxalate, Ca oxalate or Y oxalate) by extraction of the actinides at elevated temperature with a solution of ammonium fluoride and/or ammonium oxalate is described. Separation of the fission-product-containing carriers from the actinide solution formed and precipitation of the neptunium and plutonium from the solution with mineral acid are also accomplished. (AEC)

Minor actinide transmutation in thorium and uranium matrices in heavy water moderated reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhatti, Zaki; Hyland, B.; Edwards, G.W.R.

2013-07-01

The irradiation of Th{sup 232} breeds fewer of the problematic minor actinides (Np, Am, Cm) than the irradiation of U{sup 238}. This characteristic makes thorium an attractive potential matrix for the transmutation of these minor actinides, as these species can be transmuted without the creation of new actinides as is the case with a uranium fuel matrix. Minor actinides are the main contributors to long term decay heat and radiotoxicity of spent fuel, so reducing their concentration can greatly increase the capacity of a long term deep geological repository. Mixing minor actinides with thorium, three times more common in themore » Earth's crust than natural uranium, has the additional advantage of improving the sustainability of the fuel cycle. In this work, lattice cell calculations have been performed to determine the results of transmuting minor actinides from light water reactor spent fuel in a thorium matrix. 15-year-cooled group-extracted transuranic elements (Np, Pu, Am, Cm) from light water reactor (LWR) spent fuel were used as the fissile component in a thorium-based fuel in a heavy water moderated reactor (HWR). The minor actinide (MA) transmutation rates, spent fuel activity, decay heat and radiotoxicity, are compared with those obtained when the MA were mixed instead with natural uranium and taken to the same burnup. Each bundle contained a central pin containing a burnable neutron absorber whose initial concentration was adjusted to have the same reactivity response (in units of the delayed neutron fraction β) for coolant voiding as standard NU fuel. (authors)« less

Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics

PubMed Central

Booth, C.H.; Jiang, Yu; Wang, D.L.; Mitchell, J.N.; Tobash, P.H.; Bauer, E.D.; Wall, M.A.; Allen, P.G.; Sokaras, D.; Nordlund, D.; Weng, T.-C.; Torrez, M.A.; Sarrao, J.L.

2012-01-01

Uranium and plutonium’s 5f electrons are tenuously poised between strongly bonding with ligand spd-states and residing close to the nucleus. The unusual properties of these elements and their compounds (e.g., the six different allotropes of elemental plutonium) are widely believed to depend on the related attributes of f-orbital occupancy and delocalization for which a quantitative measure is lacking. By employing resonant X-ray emission spectroscopy (RXES) and X-ray absorption near-edge structure (XANES) spectroscopy and making comparisons to specific heat measurements, we demonstrate the presence of multiconfigurational f-orbital states in the actinide elements U and Pu and in a wide range of uranium and plutonium intermetallic compounds. These results provide a robust experimental basis for a new framework toward understanding the strongly-correlated behavior of actinide materials. PMID:22706643

Modeling of Plutonium Ionization Probabilities for Use in Nuclear Forensic Analysis by Resonance Ionization Mass Spectrometry

DTIC Science & Technology

2016-12-01

masses collide, they form a supercritical mass . Criticality refers to the neutron population within the system. A critical system is one that can...Spectrometry, no. 242, pp. 161–168, 2005. [9] S. Raeder, “Trace analysis of actinides in the environment by means of resonance ionization mass ...first ionization potential of actinide elements by resonance ionization mass spectrometry.” Spectrochimica Acta part B: Atomic Spectroscopy. vol. 52

Structural properties of lanthanide and actinide compounds within the plane wave pseudopotential approach

PubMed

Pickard; Winkler; Chen; Payne; Lee; Lin; White; Milman; Vanderbilt

2000-12-11

We show that plane wave ultrasoft pseudopotential methods readily extend to the calculation of the structural properties of lanthanide and actinide containing compounds. This is demonstrated through a series of calculations performed on UO, UO2, UO3, U3O8, UC2, alpha-CeC2, CeB6, CeSe, CeO2, NdB6, TmOI, LaBi, LaTiO3, YbO, and elemental Lu.

Separation of Californium from other Actinides

DOEpatents

Mailen, J C; Ferris, L M

1973-09-25

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

Detection of the actinides and cesium from environmental samples

NASA Astrophysics Data System (ADS)

Snow, Mathew Spencer

Detection of the actinides and cesium in the environment is important for a variety of applications ranging from environmental remediation to safeguards and nuclear forensics. The utilization of multiple different elemental concentrations and isotopic ratios together can significantly improve the ability to attribute contamination to a unique source term and/or generation process; however, the utilization of multiple elemental "signatures" together from environmental samples requires knowledge of the impact of chemical fractionation for various elements under a variety of environmental conditions (including predominantly aqueous versus arid conditions). The research reported in this dissertation focuses on three major areas: 1. Improving the understanding of actinide-mineral interactions at ultra-low concentrations. Chapter 2 reports a batch sorption and modeling study of Np(V) sorption to the mineral goethite from attomolar to micromolar concentrations. 2. Improving the detection capabilities for Thermal Ionization Mass Spectrometry (TIMS) analyses of ultra-trace cesium from environmental samples. Chapter 4 reports a new method which significantly improves the chemical yields, purification, sample processing time, and ultimately, the detection limits for TIMS analyses of femtogram quantities of cesium from a variety of environmental sample matrices. 3. Demonstrating how actinide and cesium concentrations and isotopic ratios from environmental samples can be utilized together to determine a wealth of information including environmental transport mechanisms (e.g. aqueous versus arid transport) and information on the processes which generated the original material. Chapters1, 3 and 5 demonstrate these principles using Pu, Am, Np, and Cs concentrations and isotopic ratios from contaminated soils taken near the Subsurface Disposal Area (SDA) of Idaho National Laboratory (INL) (a low level radioactive waste disposal site in southeastern Idaho).

Thermal Stability of Acetohydroxamic Acid/Nitric Acid Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudisill, T.S.

2002-03-13

The transmutation of transuranic actinides and long-lived fission products in spent commercial nuclear reactor fuel has been proposed as one element of the Advanced Accelerator Applications Program. Preparation of targets for irradiation in an accelerator-driven subcritical reactor would involve dissolution of the fuel and separation of uranium, technetium, and iodine from the transuranic actinides and other fission products. The UREX solvent extraction process is being developed to reject and isolate the transuranic actinides in the acid waste stream by scrubbing with acetohydroxamic acid (AHA). To ensure that a runaway reaction will not occur between nitric acid and AHA, an analoguemore » of hydroxyl amine, thermal stability tests were performed to identify if any processing conditions could lead to a runaway reaction.« less

ADS Model in the TIRELIRE-STRATEGIE Fuel Cycle Simulation Code Application to Minor Actinides Transmutation Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garzenne, Claude; Massara, Simone; Tetart, Philippe

2006-07-01

Accelerator Driven Systems offer the advantage, thanks to the core sub-criticality, to burn highly radioactive elements such as americium and curium in a dedicated stratum, and then to avoid polluting with these elements the main part of the nuclear fleet, which is optimized for electricity production. This paper presents firstly the ADS model implemented in the fuel cycle simulation code TIRELIRE-STRATEGIE that we developed at EDF R and D Division for nuclear power scenario studies. Then we show and comment the results of TIRELIRE-STRATEGIE calculation of a transition scenario between the current French nuclear fleet, and a fast reactor fleetmore » entirely deployed towards the end of the 21. century, consistently with the EDF prospective view, with 3 options for the minor actinides management:1) vitrified with fission products to be sent to the final disposal; 2) extracted together with plutonium from the spent fuel to be transmuted in Generation IV fast reactors; 3) eventually extracted separately from plutonium to be incinerated in a ADSs double stratum. The comparison of nuclear fuel cycle material fluxes and inventories between these options shows that ADSs are not more efficient than critical fast reactors for reducing the high level waste radio-toxicity; that minor actinides inventory and fluxes in the fuel cycle are more than twice as high in case of a double ADSs stratum than in case of minor actinides transmutation in Generation IV FBRs; and that about fourteen 400 MWth ADS are necessary to incinerate minor actinides issued from a 60 GWe Generation IV fast reactor fleet, corresponding to the current French nuclear fleet installed power. (authors)« less

Analysis of the Gas Core Actinide Transmutation Reactor (GCATR)

NASA Technical Reports Server (NTRS)

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

1977-01-01

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

Measuring the Cosmic Particle Radiation from electrons to actinides - HNX/TIGERISS

NASA Astrophysics Data System (ADS)

Mitchell, John

2017-01-01

The Heavy Nuclei eXplorer (HNX) mission will measure the abundances of nuclei from Carbon (Z =6) to Curium (Z =96) in the cosmic radiation with the resolution to identify the atomic number of each detected nucleus. HNX will measure a significant number of actinides. HNX utilizes two high-precision instruments, the Extremely-heavy Cosmic-ray Composition Observer (ECCO) and the Cosmic-Ray Trans-Iron Galactic Element Recorder (CosmicTIGER), located in a SpaceX DragonLab capsule orbiting the Earth. This talk will discuss the motivating science, the HNX mission, the design and performance of the HNX instruments, and another new instrument, TIGERISS (Trans-Iron Galactic Element Recorder on the ISS), that will be proposed as an intermediate between SuperTIGER and HNX.

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

DOE PAGES

Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E.; ...

2015-04-16

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, andmore » 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. As a result, the metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence.« less

Actinide and lanthanide separation process (ALSEP)

DOEpatents

Guelis, Artem V.

2013-01-15

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

On the use of X-ray absorption spectroscopy to elucidate the structure of lutetium adenosine mono- and triphosphate complexes.

PubMed

Mostapha, S; Berthon, C; Fontaine-Vive, F; Gaysinski, M; Guérin, L; Guillaumont, D; Massi, L; Monfardini, I; Solari, P L; Thomas, O P; Charbonnel, M C; Den Auwer, C

2014-02-01

Although the physiological impact of the actinide elements as nuclear toxicants has been widely investigated for half a century, a description of their interactions with biological molecules remains limited. It is however of primary importance to better assess the determinants of actinide speciation in cells and more generally in living organisms to unravel the molecular processes underlying actinide transport and deposition in tissues. The biological pathways of this family of elements in case of accidental contamination or chronic natural exposure (in the case of uranium rich soils for instance) are therefore a crucial issue of public health and of societal impact. Because of the high chemical affinity of those actinide elements for phosphate groups and the ubiquity of such chemical functions in biochemistry, phosphate derivatives are considered as probable targets of these cations. Among them, nucleotides and in particular adenosine mono- (AMP) and triphosphate (ATP) nucleotides occur in more chemical reactions than any other compounds on the earth's surface, except water, and are therefore critical target molecules. In the present study, we are interested in trans-plutonium actinide elements, in particular americium and curium that are more rarely considered in environmental and bioaccumulation studies than early actinides like uranium, neptunium and plutonium. A first step in this strategy is to work with chemical analogues like lanthanides that are not radioactive and therefore allow extended physical chemical characterization to be conducted that are difficult to perform with radioactive materials. We describe herein the interaction of lutetium(III) with adenosine AMP and ATP. With AMP and ATP, insoluble amorphous compounds have been obtained with molar ratios of 1:2 and 1:1, respectively. With an excess of ATP, with 1:2 molar ratio, a soluble complex has been obtained. A combination of spectroscopic techniques (IR, NMR, ESI-MS, EXAFS) together with quantum chemical calculations has been implemented in order to assess the lutetium coordination arrangement for the two nucleotides. In all the complexes described in the article, the lutetium cation is coordinated by the phosphate groups of the nucleotide plus additional putative water molecules with various tridimensional arrangements. With AMP 1:2 and ATP 1:1 solid-state compounds, polynuclear complexes are assumed to be obtained. In contrast, with ATP 1:2 soluble compound, the Lu coordination sphere is saturated by two ATP ligands, and this favors the formation of a mononuclear complex. In order to further interpret the EXAFS data obtained at the Lu LIII edge, model structures have been calculated for the 1:1 and 1:2 ATP complexes. They are discussed and compared to the EXAFS best fit metrical parameters.

Science and Technology Review June 2000

DOE Office of Scientific and Technical Information (OSTI.GOV)

de Pruneda, J.H.

2000-06-01

This issue contains the following articles: (1) ''Accelerating on the ASCI Challenge''. (2) ''New Day Daws in Supercomputing'' When the ASCI White supercomputer comes online this summer, DOE's Stockpile Stewardship Program will make another significant advanced toward helping to ensure the safety, reliability, and performance of the nation's nuclear weapons. (3) ''Uncovering the Secrets of Actinides'' Researchers are obtaining fundamental information about the actinides, a group of elements with a key role in nuclear weapons and fuels. (4) ''A Predictable Structure for Aerogels''. (5) ''Tibet--Where Continents Collide''.

Development of a universal solvent for the decontamination of acidic liquid radioactive wastes

NASA Astrophysics Data System (ADS)

Todd, T. A.; Brewer, K. N.; Law, J. D.; Wood, D. J.; Herbest, R. S.; Romanovskiy, V. N.; Esimantovskiy, V. M.; Smirnov, I. V.; Babain, V. A.

1999-01-01

A teritiary solvent containing chlorinated cobalt dicarbollide, polyethylene glycol and diphenylcarbamoylmethylphosphine oxide was evaluated in different non-nitroaromatic diluents for the separation of cesium, strontium, actinides and rare earth elements from acidic liquid radioactive waste. Decontamination factors of >95% for Cs, 99.7% for Sr, and 99.99% for actinides were achieved in four successive batch contacts using actual radioactive waste. Pilot plant testing in centrifugal contactors using simulated wastes, has demonstrated removal of >99% of all targeted ions.

Overview of actinide chemistry in the WIPP

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borkowski, Marian; Lucchini, Jean - Francois; Richmann, Michael K

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 partmore » 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 inorganic complexants are expected to be carbonate/bicarbonate and hydroxide. There are also organic complexants in TRU waste with the potential to strongly influence actinide solubility. (3) Intrinsic and pseudo-actinide colloid formation - Many actinide species in their expected oxidation states tend to form colloids or strongly associate with non actinide colloids present (e.g., microbial, humic and organic). In this context, the relative importance of actinides, based on the TRU waste inventory, with respect to the potential release of actinides from the WIPP, is greater for plutonium and americium, and to less extent for uranium and thorium. The most important oxidation states for WIPP-relevant conditions are III and IV. We will present an update of the literature on WIPP-specific data, and a summary of the ongoing research related to actinide chemistry in the WIPP performed by the Los Alamos National Laboratory (LANL) Actinide Chemistry and Repository Science (ACRSP) team located in Carlsbad, NM [Reed 2007, Lucchini 2007, and Reed 2006].« less

Survey of glass plutonium contents and poison selection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Plodinec, M.J.; Ramsey, W.G.; Ellison, A.J.G.

1996-05-01

If plutonium and other actinides are to be immobilized in glass, then achieving high concentrations in the glass is desirable. This will lead to reduced costs and more rapid immobilization. However, glasses with high actinide concentrations also bring with them undersirable characteristics, especially a greater concern about nuclear criticality, particularly in a geologic repository. The key to achieving a high concentration of actinide elements in a glass is to formulate the glass so that the solubility of actinides is high. At the same time, the glass must be formulated so that the glass also contains neutron poisons, which will preventmore » criticality during processing and in a geologic repository. In this paper, the solubility of actinides, particularly plutonium, in three types of glasses are discussed. Plutonium solubilities are in the 2-4 wt% range for borosilicate high-level waste (HLW) glasses of the type which will be produced in the US. This type of glass is generally melted at relatively low temperatures, ca. 1150{degrees}C. For this melting temperature, the glass can be reformulated to achieve plutonium solubilities of at least 7 wt%. This low melting temperature is desirable if one must retain volatile cesium-137 in the glass. If one is not concerned about cesium volatility, then glasses can be formulated which can contain much larger amounts of plutonium and other actinides. Plutonium concentrations of at least 15 wt% have been achieved. Thus, there is confidence that high ({ge}5 wt%) concentrations of actinides can be achieved under a variety of conditions.« less

Prospects of heavy and superheavy element production via inelastic nucleus-nucleus collisions - from 238U+238U to18O+254Es

NASA Astrophysics Data System (ADS)

Schädel, Matthias

2016-12-01

Multi-nucleon transfer reactions, frequently termed deep-inelastic, between heavy-ion projectiles and actinide targets provide prospects to synthesize unknown isotopes of heavy actinides and superheavy elements with neutron numbers beyond present limits. The 238U on 238U reaction, which revealed essential aspects of those nuclear reactions leading to surviving heavy nuclides, mainly produced in 3n and 4n evaporation channels, is discussed in detail. Positions and widths of isotope distributions are compared. It is shown, as a general rule, that cross sections peak at irradiation energies about 10% above the Coulomb barrier. Heavy target nuclei are essential for maximizing cross sections. Experimental results from the 238U on 248Cm reaction, including empirical extrapolations, are compared with theoretical model calculations predicting relatively high cross sections for neutron-rich nuclei. Experiments to test the validity of such predictions are proposed. Comparisons between rather symmetric heavy-ion reactions like 238U on 248Cm (or heavier targets up to 254Es) with very asymmetric ones like 18O on 254Es reveal that the ones with 238U as a projectile have the highest potential in the superheavy element region while the latter ones can be advantageous for the synthesis of heavy actinide isotopes. Concepts for highly efficient recoil separators designed for transfer products are presented.

Concentrations of Elements in Sediments and Selective Fractions of Sediments, and in Natural Waters in Contact with Sediments from Lake Roosevelt, Washington, September 2004

USGS Publications Warehouse

Paulson, Anthony J.; Wagner, Richard J.; Sanzolone, Richard F.; Cox, Steven E.

2006-01-01

Twenty-eight composite and replicate sediment samples from 8 Lake Roosevelt sites were collected and analyzed for 10 alkali and alkaline earth elements, 2 non-metals, 20 metals, and 4 lanthanide and actinide elements. All elements were detected in all sediment samples except for silver (95 percent of the elements detected for 1,008 analyses), which was detected only in 4 samples. Sequential selective extraction procedures were performed on single composite samples from the eight sites. The percentage of detections for the 31 elements analyzed ranged from 76 percent for the first extraction fraction using a weak extractant to 93 percent for the four-acid dissolution of the sediments remaining after the third sequential selective extraction. Water samples in various degrees of contact with the sediment were analyzed for 10 alkali and alkaline earth elements, 5 non-metals, 25 metals, and 16 lanthanide and actinide elements. The filtered water samples included 10 samples from the reservoir water column at 8 sites, 32 samples of porewater, 55 samples from reservoir water overlying sediments in 8 cores from the site incubated in a field laboratory, and 24 water samples that were filtered after being tumbled with sediments from 8 sites. Overall, the concentrations of only 37 percent of the 6,776 analyses of the 121 water samples were greater than the reporting limit. Selenium, bismuth, chromium, niobium, silver, and zirconium were not detected in any water samples. The percentage of concentrations for the water samples that were above the reporting limit ranged from 14 percent for the lanthanide and actinide elements to 77 percent for the alkali and alkaline earth elements. Concentrations were greater than reporting limits in only 23 percent of the analyses of reservoir water and 29 percent of the analyses of reservoir water overlying incubation cores. In contrast, 47 and 48 percent of the concentrations of porewater and water samples tumbled with sediments, respectively, were greater than the reporting limit.

Neptunium-the neglected actinide: a review of the biological and environmental literature. [Humans, crustaceans, domestic animals, rats

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, R.C.

1982-04-01

Data from 89 references relating to the biological and environmental behavior of neptunium are reviewed with particular attention to the potential risks from possible releases of neptunium isotopes by the nuclear industry. The behavior of neptunium differs in many significant respects from that of other transuranic elements. It is more mobile environmentally and more readily absorbed by man, although some of the higher reported values for gastrointestinal absorption appear to have been influenced by the very high mass levels of /sup 237/Np required for experimental study. In studies with experimental animals its ratio of deposition in bone/liver is greater thanmore » that of other transuranic elements. Its long-term toxicity in experimental animals is similar to that of other transuranics.« less

Uptake and effects of americium-241 on a brackishwater amphipod

NASA Astrophysics Data System (ADS)

Hoppenheit, M.; Murray, C. N.; Woodhead, D. S.

1980-03-01

The present paper reports the results of experimental work undertaken using the brackish-water amphipod Gammarus duebeni duebeni and the transuranium nuclide americium-241. Data on the accumulation of this actinide showed that the larger fraction of the total body burden is associated with the exoskeleton. It was found that the body burden remained constant in the range pH 8.0 6.5 even though the water concentrations changed markedly. It would thus appear that the concept of a concentration factor should be re-examined and it is proposed that a factor should be defined in terms of environmental and chemical parameters which represent the bioavailable fraction of the actinide. The effect of americium on survival and moulting was studied at two activity concentrations; the dose rates and absorbed doses under the experimental conditions employed have been estimated. The differences in survival rates between the control and irradiated groups were statistically analyzed and the significant difference at the higher concentration is believed to be due to a synergism between physiological stress and radiotoxicity of americium rather than the chemical toxicity of the element.

United States Transuranium and Uranium Registries. Annual report February 1, 2000--January 31, 2001

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ehrhart, Susan M.; Filipy, Ronald E.

2001-07-01

The United States Transuranium and Uranium Registries (USTUR) comprise a human tissue research program studying the deposition, biokinetics and dosimetry of the actinide elements in humans with the primary goals of providing data fundamental to the verification, refinement, or future development of radiation protection standards for these and other radionuclides, and of determining possible bioeffects on both a macro and subcellular level attributable to exposure to the actinides. This report covers USTUR activities during the year from February 2000 through January 2001.

United States Transuranium and Uranium Registries. Annual report October 1, 1994 - September 30, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kathren, R.L.; Harwick, L.A.; Markel, M.J.

1996-07-01

The United States Transuranium and Uranium Registries (USTUR) comprise a human tissue research program studying the deposition, biokinetics and dosimetry of the actinide elements in humans with the primary goals of providing data fundamental to the verification, refinement, or future development of radiation protection standards for these and other radionuclides, and of determining possible bioeffects on both a macro and subcellular level attributable to exposure to the actinides. This report covers USTUR activities during the year from October 1994 through September 1995.

Free Energy and Heat Capacity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurata, Masaki; Devanathan, Ramaswami

2015-10-13

Free energy and heat capacity of actinide elements and compounds are important properties for the evaluation of the safety and reliable performance of nuclear fuel. They are essential inputs for models that describe complex phenomena that govern the behaviour of actinide compounds during nuclear fuel fabrication and irradiation. This chapter introduces various experimental methods to measure free energy and heat capacity to serve as inputs for models and to validate computer simulations. This is followed by a discussion of computer simulation of these properties, and recent simulations of thermophysical properties of nuclear fuel are briefly reviewed.

The role of fission in Supernovae r-process nucleosynthesis

NASA Astrophysics Data System (ADS)

Otsuki, Kaori; Kajino, Toshitaka; Sumiyoshi, Kosuke; Ohta, Masahisa; Mathews, J. Grant

2001-10-01

The r-process elements are presumed to be produced in an explosive environment with short timescale at high entropy, like type-II supernova explosion. Intensive flux of free neutrons are absorbed successively by seed elements to form the nuclear reaction flow on extremely unstable nuclei on the neutron rich side. It would probe our knowledge of the properties of nulei far from the beta stability. It is also important in astronomy since this process forms the long-lived nuclear chronometers Thorium and Uranium that are utilised dating the age of the Milky Way. In our previous work, we showed that the succesful r-process nucleosynthesis can occure above young, hot protoneutron star. Although these long-lived heavy elements are produced comparable amounts to observation in several supernova models which we constructed, fission and alpha-decay were not included there. The fission products could play an important role in setting actinide yields which are used as cosmochronometers. In this talk, we report an infulence of fission on actinide yields and on estimate of Galactic age as well. We also discuss fission yields at lighter elements (Z ~ 50).

The Heavy Nuclei eXplorer (HNX) Small Explorer Mission

NASA Astrophysics Data System (ADS)

Mitchell, John; Binns, W. Robert; Hams, Thomas; Israel, Martin; Krizmanic, John; Link, Jason; Rauch, Brian; Sakai, Kenichi; Sasaki, Makoto; Westphal, Andrew; Wiedenbeck, Mark; Heavy Nuclei eXplorer Collaboration

2015-04-01

The Heavy Nuclei eXplorer (HNX) will investigate the nature of the reservoirs of nuclei at the cosmic-ray sources, the mechanisms by which nuclei are removed from the reservoirs and injected into the cosmic accelerators, and the acceleration mechanism. HNX will use two large high-precision instruments, the Extremely-heavy Cosmic-ray Composition Observer (ECCO) and the Cosmic-ray Trans-Iron Galactic Element Recorder (CosmicTIGER), flying in the SpaceX DragonLab, to measure, for the first time, the abundance of every individual element in the periodic table from carbon through the actinides, providing the first measurement of many of these elements. HNX will measure several thousand ultra-heavy galactic cosmic ray (UHGCR) nuclei Z >= 30, including about 50 actinides, and will: determine whether GCRs are accelerated from new or old material, and find their age; measure the mix of nucleosynthesis processes responsible for the UHGCRs; determine how UHGCR elements are selected for acceleration, and measure the mean integrated pathlength traversed by UHGCRs before observation. The scientific motivation and instrument complement of HNX will be discussed.

Dissolution of Used Nuclear Fuel Using a TBP/N-Paraffin Solvent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudisill, T. S.; Shehee, T. C.; Jones, D. H.

2017-10-02

The dissolution of unirradiated used nuclear fuel (UNF) pellets pretreated for tritium removal was demonstrated using a tributly phosphate (TBP) solvent. Dissolution of pretreated fuel in TBP could potentially combine dissolution with two cycle of solvent extraction required for separating the actinides and lanthanides from other fission products. Dissolutions were performed using UNF surrogates prepared from both uranyl nitrate and uranium trioxide produced from the pretreatment process by adding selected actinide and stable fission product elements. In laboratory-scale experiments, the U dissolution efficiency ranged from 80-99+% for both the nitrate and oxide surrogate fuels. On average, 80% of the Pumore » and 50% of the Np and Am in the nitrate surrogate dissolved; however, little of the transuranic elements dissolved in the oxide form. The majority of the 3+ lanthanide elements dissolved. Only small amounts of Sr (0-1.6%) and Mo (0.1-1.7%) and essentially no Cs, Ru, Zr, or Pd dissolved.« less

An optimization methodology for heterogeneous minor actinides transmutation

NASA Astrophysics Data System (ADS)

Kooyman, Timothée; Buiron, Laurent; Rimpault, Gérald

2018-04-01

In the case of a closed fuel cycle, minor actinides transmutation can lead to a strong reduction in spent fuel radiotoxicity and decay heat. In the heterogeneous approach, minor actinides are loaded in dedicated targets located at the core periphery so that long-lived minor actinides undergo fission and are turned in shorter-lived fission products. However, such targets require a specific design process due to high helium production in the fuel, high flux gradient at the core periphery and low power production. Additionally, the targets are generally manufactured with a high content in minor actinides in order to compensate for the low flux level at the core periphery. This leads to negative impacts on the fuel cycle in terms of neutron source and decay heat of the irradiated targets, which penalize their handling and reprocessing. In this paper, a simplified methodology for the design of targets is coupled with a method for the optimization of transmutation which takes into account both transmutation performances and fuel cycle impacts. The uncertainties and performances of this methodology are evaluated and shown to be sufficient to carry out scoping studies. An illustration is then made by considering the use of moderating material in the targets, which has a positive impact on the minor actinides consumption but a negative impact both on fuel cycle constraints (higher decay heat and neutron) and on assembly design (higher helium production and lower fuel volume fraction). It is shown that the use of moderating material is an optimal solution of the transmutation problem with regards to consumption and fuel cycle impacts, even when taking geometrical design considerations into account.

Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

McSkimming, Alex; Su, Jing; Cheisson, Thibault

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO) 4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The saltmore » [U(pyNO) 4] + was isolated by chemical oxidation of [U(pyNO) 4]; spectroscopic and computational data support assignment as a U V cation.« less

Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure

DOE PAGES

McSkimming, Alex; Su, Jing; Cheisson, Thibault; ...

2018-03-23

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO) 4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The saltmore » [U(pyNO) 4] + was isolated by chemical oxidation of [U(pyNO) 4]; spectroscopic and computational data support assignment as a U V cation.« less

Periodic Table of Elements: Los Alamos National Laboratory

Science.gov Websites

Highlighted in Huffington Post 12/6/17 Quantum dots amplify light with electrical pumping 11/20/17 Josh Smith Actinides Transition metals Nonmetals Post-transition metals Halogens Metalloid Noble gases Contact

Method for purifying bidentate organophosphorus compounds

DOEpatents

Schulz, Wallace W.

1977-01-01

Bidentate organophosphorus compounds useful for extracting actinide elements from acidic nuclear waste solutions are purified of undesirable acidic impurities by contacting the compounds with ethylene glycol which preferentially extracts the impurities found in technical grade bidentate compounds.

Evaluation of possible physical-chemical processes that might lead to separations of actinides in ORNL waste tanks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Del Cul, G.D.; Toth, L.M.; Bond, W.D.

The concern that there might be some physical-chemical process which would lead to a separation of the poisoning actinides ({sup 232}Th, {sup 238}U) from the fissionable ones ({sup 239}Pu, {sup 235}U) in waste storage tanks at Oak Ridge National Laboratory has led to a paper study of potential separations processes involving these elements. At the relatively high pH values (>8), the actinides are normally present as precipitated hydroxides. Mechanisms that might then selectively dissolve and reprecipitate the actinides through thermal processes or additions of reagents were addressed. Although redox reactions, pH changes, and complexation reactions were all considered, only themore » last type was regarded as having any significant probability. Furthermore, only carbonate accumulation, through continual unmonitored air sparging of the tank contents, could credibly account for gross transport and separation of the actinide components. From the large amount of equilibrium data in the literature, concentration differences in Th, U, and Pu due to carbonate complexation as a function of pH have been presented to demonstrate this phenomenon. While the carbonate effect does represent a potential separations process, control of long-term air sparging and solution pH, accompanied by routine determinations of soluble carbonate concentration, should ensure that this separations process does not occur.« less

Actinides in metallic waste from electrometallurgical treatment of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Janney, D. E.; Keiser, D. D.

2003-09-01

Argonne National Laboratory has developed a pyroprocessing-based technique for conditioning spent sodium-bonded nuclear-reactor fuel in preparation for long-term disposal. The technique produces a metallic waste form whose nominal composition is stainless steel with 15 wt.% Zr (SS-15Zr), up to ˜ 11 wt.% actinide elements (primarily uranium), and a few percent metallic fission products. Actual and simulated waste forms show similar eutectic microstructures with approximately equal proportions of iron solid solution phases and Fe-Zr intermetallics. This article reports on an analysis of simulated waste forms containing uranium, neptunium, and plutonium.

Development of a standardized sequential extraction protocol for simultaneous extraction of multiple actinide elements

DOE PAGES

Faye, Sherry A.; Richards, Jason M.; Gallardo, Athena M.; ...

2017-02-07

Sequential extraction is a useful technique for assessing the potential to leach actinides from soils; however, current literature lacks uniformity in experimental details, making direct comparison of results impossible. This work continued development toward a standardized five-step sequential extraction protocol by analyzing extraction behaviors of 232Th, 238U, 239,240Pu and 241Am from lake and ocean sediment reference materials. Results produced a standardized procedure after creating more defined reaction conditions to improve method repeatability. A NaOH fusion procedure is recommended following sequential leaching for the complete dissolution of insoluble species.

Implications of human tissue studies for radiation protection.

PubMed

Kathren, R L

1988-08-01

Through radiochemical analysis of voluntary tissue donations, the U.S. Transuranium and Uranium Registries (USTR) are gaining improved understanding of the distribution and biokinetics of actinide elements in occupationally exposed persons. Evaluation of the first two whole-body contributions to the USTR revealed an inverse proportionality between actinide concentration and bone ash. The analysis of a whole body with significant 241Am deposition indicated a significantly shorter half-time in liver and a greater fraction resident in the skeleton than predicted by existing models. Other studies with tissues obtained at autopsy suggest that existing biokinetic models for 238Pu and 241Am and the currently accepted models and limits on intake, which use these models as their basis, may be inaccurately implying that revisions of existing safety standards may be necessary. Other studies of the registries are designed to evaluate in-vivo estimates of actinide deposition with those derived from postmortem tissue analysis, to compare results of animal experiments with human data, and to review histopathologic slides for tissue changes that might be attributable to exposure to transuranic elements. The implications of these recent findings and other work of the registries is discussed from the standpoint of this potential effect on biokinetic modeling, internal dose assessment, and safety standards and operational health physics practices.

Implications of human tissue studies for radiation protection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kathren, R.L.

1988-08-01

Through radiochemical analysis of voluntary tissue donations, the U.S. Transuranium and Uranium Registries (USTR) are gaining improved understanding of the distribution and biokinetics of actinide elements in occupationally exposed persons. Evaluation of the first two whole-body contributions to the USTR revealed an inverse proportionality between actinide concentration and bone ash. The analysis of a whole body with significant /sup 241/Am deposition indicated a significantly shorter half-time in liver and a greater fraction resident in the skeleton than predicted by existing models. Other studies with tissues obtained at autopsy suggest that existing biokinetic models for /sup 238/Pu and /sup 241/Am andmore » the currently accepted models and limits on intake, which use these models as their basis, may be inaccurately implying that revisions of existing safety standards may be necessary. Other studies of the registries are designed to evaluate in-vivo estimates of actinide deposition with those derived from postmortem tissue analysis, to compare results of animal experiments with human data, and to review histopathologic slides for tissue changes that might be attributable to exposure to transuranic elements. The implications of these recent findings and other work of the registries is discussed from the standpoint of this potential effect on biokinetic modeling, internal dose assessment, and safety standards and operational health physics practices.« less

Closed DTU fuel cycle with Np recycle and waste transmutation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beller, D.E.; Sailor, W.C.; Venneri, F.

1999-09-01

A nuclear energy scenario for the 21st century that included a denatured thorium-uranium-oxide (DTU) fuel cycle and new light water reactors (LWRs) supported by accelerator-driven transmutation of waste (ATW) systems was previously described. This coupled system with the closed DTU fuel cycle provides several improvements beyond conventional LWR (CLWR) (once-through, UO{sub 2} fuel) nuclear technology: increased proliferation resistance, reduced waste, and efficient use of natural resources. However, like CLWR fuel cycles, the spent fuel in the first one-third core discharged after startup contains higher-quality Pu than the equilibrium fuel cycle. To eliminate this high-grade Pu, Np is separated and recycledmore » with Th and U--rather than with higher actinides [(HA) including Pu]. The presence of Np in the LWR feed greatly increases the production of {sup 238}Pu so that a few kilograms of Pu generated enough alpha-decay heat that the separated Pu is highly resistant to proliferation. This alternate process also simplifies the pyrochemical separation of fuel elements (Th and U) from HAs. To examine the advantages of this concept, the authors modeled a US deployment scenario for nuclear energy that includes DTU-LWRs plus ATW`s to burn the actinides produced by these LWRs and to close the back-end of the DTU fuel cycle.« less

Fate and transport of plutonium-239 + 240 and Americium-241 in the soil of Rocky Flats, Colorado

DOE Office of Scientific and Technical Information (OSTI.GOV)

Litaor, M.I.; Barth, G.R.; Zika, E.M.

1996-07-01

Actinides contamination of soils around Rocky Flats, CO, resulted from leaking drums of Pu-contaminated oil stored at an outdoor site. The transport of these actinides through the soil to groundwater was studied using an advanced monitoring system (MS). The fully automated, remotely controlled MS gathered real-time data on soil water content, groundwater level, and timing of gravitationally flowing water. Controlled rain simulations coupled with measurements of volume flux and actinide activities provided essential information about the fate and transport of Pu-239 + 240 and Am-241. Volume fluxes at most sampling locations were similar, regardless of the antecedent moisture or themore » duration, frequency, and intensity of the simulated rain. Actinide activities were not correlated with the measured volume flux, or the duration, frequency, and intensity of the simulated rain. Flow was facilitated primarily via macropore channeling. The relatively short residence time precluded a continuous interaction between the soil and the flowing water, which minimized the movement of actinides in the soil. Actinide activities in the interstitial water collected from the upper 20 cm of the soil were significantly higher (P>0.001) than water collected at deeper sampling depths (20-70 cm). Actinide activity in water samples from the deepest sampling depth (40-70 cm) did not exceed 0.4 Bq/L. These results suggest that, under the experimental conditions, the movement of actinides was restricted to the top 20 cm. A transport mechanism involving discrete Pu oxide particles, coupled with macropore channeling is proposed to explain the observed actinide activities in the soil. 31 refs., 6 figs., 7 tabs.« less

Lanthanide/Actinide Opacities

NASA Astrophysics Data System (ADS)

Hungerford, Aimee; Fontes, Christopher J.

2018-06-01

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

The cross sections of fusion-evaporation reactions: the most promising route to superheavy elements beyond Z=118

NASA Astrophysics Data System (ADS)

Jadambaa, Khuyagbaatar

2017-11-01

The synthesis of superheavy elements beyond oganesson (Og), which has atomic number Z = 118, is currently one of the main topics in nuclear physics. An absence of sufficient amounts of target material with atomic numbers heavier than californium (Z = 98) forces the use of projectiles heavier than 48Ca (Z = 20), which has been successfully used for the discoveries of elements with Z = 114 - 118 in complete fusion reactions. Experimental cross sections of 48Ca with actinide targets behave very differently to "cold" and "hot" fusion-evaporation reactions, where doubly-magic lead and deformed actinides are used as targets, respectively. The known cross sections of these reactions have been analysed compared to calculated fission barriers. It has been suggested that observed discrepancies between the cross sections of 48Ca-induced and other fusionevaporation reactions originate from the shell structure of the compound nucleus, which lies in the island of the stability. Besides scarcely known data on other reactions involving heavier projectiles, the most promising projectile for the synthesis of the elements beyond Og seems to be 50Ti. However, detailed studies of 50Ti, 54Cr, 58Fe and 64Ni-induced reactions are necessary to be performed in order to fully understand the complexities of superheavy element formation.

FCRD Advanced Reactor (Transmutation) Fuels Handbook

DOE Office of Scientific and Technical Information (OSTI.GOV)

Janney, Dawn Elizabeth; Papesch, Cynthia Ann

2016-09-01

Transmutation of minor actinides such as Np, Am, and Cm in spent nuclear fuel is of international interest because of its potential for reducing the long-term health and safety hazards caused by the radioactivity of the spent fuel. One important approach to transmutation (currently being pursued by the DOE Fuel Cycle Research & Development Advanced Fuels Campaign) involves incorporating the minor actinides into U-Pu-Zr alloys, which can be used as fuel in fast reactors. U-Pu-Zr alloys are well suited for electrolytic refining, which leads to incorporation rare-earth fission products such as La, Ce, Pr, and Nd. It is, therefore, importantmore » to understand not only the properties of U-Pu-Zr alloys but also those of U-Pu-Zr alloys with concentrations of minor actinides (Np, Am) and rare-earth elements (La, Ce, Pr, and Nd) similar to those in reprocessed fuel. In addition to requiring extensive safety precautions, alloys containing U, Pu, and minor actinides (Np and Am) are difficult to study for numerous reasons, including their complex phase transformations, characteristically sluggish phasetransformation kinetics, tendency to produce experimental results that vary depending on the histories of individual samples, rapid oxidation, and sensitivity to contaminants such as oxygen in concentrations below a hundred parts per million. Although less toxic, rare-earth elements such as La, Ce, Pr, and Nd are also difficult to study for similar reasons. Many of the experimental measurements were made before 1980, and the level of documentation for experimental methods and results varies widely. It is, therefore, not surprising that little is known with certainty about U-Pu-Zr alloys, particularly those that also contain minor actinides and rare-earth elements. General acceptance of results commonly indicates that there is only a single measurement for a particular property. This handbook summarizes currently available information about U, Pu, Zr, Np, Am, La, Ce, Pr, and Nd and alloys of two or three of these elements. It contains information about phase diagrams and related information (including phases and phase transformations); heat capacity, entropy, and enthalpy; thermal expansion; and thermal conductivity and diffusivity. In addition to presenting information about materials properties, the handbook attempts to provide information about how well the property is known and how much variation exists between measurements. Although it includes some results from models, its primary focus is experimental data. The Handbook is organized in two sections: one with information about the U-Pu-Zr ternary and one with information about other elements and binary and vi ternary alloys in the U-Np-Pu-Am-La-Ce-Pr-Nd-Zr system. Within each section, information about elements is presented first, followed by information about binary alloys, then information about ternary alloys. The order in which the elements in each alloy are mentioned follows the order in the first sentence of this paragraph. Much of the information on the U-Pu-Zr system repeats information from the FCRD Transmutation Fuels Handbook 2015. Most of the other data has been published elsewhere (although scattered throughout numerous references, some quite obscure); however, some data from Idaho National Laboratory is presented here for the first time. As the FCRD programmatic mission evolves, future editions of this handbook will begin to include other advanced reactor fuel designs and compositions. Hence, the title of the handbook will transition to the Advanced Reactor Fuels Handbook.« less

Identification of process related trace level impurities in the actinide decorporation agent 3,4,3-LI(1,2-HOPO): Nozzle–skimmer fragmentation via ESI LC–QTOFMS

DOE PAGES

Panyala, Nagender R.; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J.

2014-08-12

We report that 3,4,3-LI(1,2-HOPO) is a chelating ligand and decorporation agent that can remove radioactive lanthanides and actinides from the body. Identification of trace impurities in drug samples is gaining much interest due to their significant influence on drug activity. In this study, trace impurities were detected in manufactured lots of 3,4,3-LI(1,2-HOPO) by a developed method of Liquid Chromatography coupled with photo-diode array UV detection and Electrospray Ionization-Quadrupole Time of Flight Mass spectrometry (LC-QTOFMS), via induced-in-source or collision-induced mass fragmentation (Nozzle-Skimmer Fragmentation). Molecular ions were fragmented within the nozzle-skimmer region of electrospray ionization (ESI) mass spectrometer equipped with a Timemore » of Flight detector. Eight major (detected at levels higher than a 0.1% threshold) and seven minor trace impurities were identified. The respective structures of these impurities were elucidated via analysis of the generated fragment ions using mass fragmentation and elemental composition software. Proposed structures of impurities were further confirmed via isotopic modeling.« less

Potentiometric Sensor for Real-Time Remote Surveillance of Actinides in Molten Salts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Natalie J. Gese; Jan-Fong Jue; Brenda E. Serrano

2012-07-01

A potentiometric sensor is being developed at the Idaho National Laboratory for real-time remote surveillance of actinides during electrorefining of spent nuclear fuel. During electrorefining, fuel in metallic form is oxidized at the anode while refined uranium metal is reduced at the cathode in a high temperature electrochemical cell containing LiCl-KCl-UCl3 electrolyte. Actinides present in the fuel chemically react with UCl3 and form stable metal chlorides that accumulate in the electrolyte. This sensor will be used for process control and safeguarding of activities in the electrorefiner by monitoring the concentrations of actinides in the electrolyte. The work presented focuses onmore » developing a solid-state cation conducting ceramic sensor for detecting varying concentrations of trivalent actinide metal cations in eutectic LiCl-KCl molten salt. To understand the basic mechanisms for actinide sensor applications in molten salts, gadolinium was used as a surrogate for actinides. The ß?-Al2O3 was selected as the solid-state electrolyte for sensor fabrication based on cationic conductivity and other factors. In the present work Gd3+-ß?-Al2O3 was prepared by ion exchange reactions between trivalent Gd3+ from GdCl3 and K+-, Na+-, and Sr2+-ß?-Al2O3 precursors. Scanning electron microscopy (SEM) was used for characterization of Gd3+-ß?-Al2O3 samples. Microfocus X-ray Diffraction (µ-XRD) was used in conjunction with SEM energy dispersive X-ray spectroscopy (EDS) to identify phase content and elemental composition. The Gd3+-ß?-Al2O3 materials were tested for mechanical and chemical stability by exposing them to molten LiCl-KCl based salts. The effect of annealing on the exchanged material was studied to determine improvements in material integrity post ion exchange. The stability of the ß?-Al2O3 phase after annealing was verified by µ-XRD. Preliminary sensor tests with different assembly designs will also be presented.« less

Initial results of metal waste form development activities at ANL-West

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keiser, D.D. Jr.; Westphal, B.R.; Hersbt, R.S.

1997-10-01

Argonne National Laboratory is developing a metal alloy to contain metallic waste constituents from the electrometallurgical treatment of spent nuclear fuel. This alloy will contain stainless steel (from stainless steel-clad fuel elements), {approximately}15 wt.% zirconium (from alloy fuel), fission products noble to the process (e.g., Ru, Pd, Tc, etc.), and minor amounts of actinides. The alloy will serve as a final waste form for these components and will be disposed of in a geologic repository. The alloy ingot is produced in an induction furnace situated in a hot cell using Ar cover gas. This paper discusses results from the meltingmore » campaigns that have been initiated at ANL-West to generate the metal waste form using actual process materials. In addition, metal waste form samples have been doped with Tc and selected actinides and are described in the context of how elements of interest partition between various phases in the alloy and how this distribution of elements in the alloy may affect the leaching behavior of the components in an aqueous environment. 3 refs.« less

Initial results of metal waste-form development activities at ANL-West

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keiser, D.D. Jr.; Westphal, B.R.; Herbst, R.S.

1997-12-01

Argonne National Laboratory (ANL) is developing a metal alloy to contain metallic waste constituent residual from the electrometallurgical treatment of spent nuclear fuel. This alloy will contain stainless steel (from stainless steel-clad fuel elements), {approximately} 15 wt% zirconium (from alloy fuel), fission products noble to the process (e.g., ruthenium, palladium, technetium, etc.), and minor amounts of actinides. The alloy will serve as a final waste form for these components and will be disposed of in a geologic repository. The alloy ingot is produced in an induction furnace situated in a hot cell using argon cover gas. This paper discusses resultsmore » from the melting campaigns that have been initiated at ANL-West to generate the metal waste form using actual process materials. In addition, metal waste form samples have been doped with technetium and selected actinides and are described in the context of how elements of interest partition between various phases in the alloy and how this distribution of elements in the alloy may affect the leaching behavior of the components in an aqueous environment.« less

Standard Materials for Microbeam Analysis of Lanthanides and Actinides

NASA Astrophysics Data System (ADS)

Ellis, I.; Gorton, M.; Rucklidge, J. C.

2010-12-01

Traces of Th and U in naturally-occuring minerals monazite, xenotime and zircon are used for dating host rocks. Natural variations of actinide concentrations in some rock formations are well documented. Microbeam techniques perform dating in-situ where grains of indicator minerals are left intact in thin sections. Separated individual grains of these minerals are also routinely dated by Pb-isotope mass spectrometry. Ideal calibration materials will be compatible with multiple techniques. Quantitative analysis of low levels of lanthanides (REE), U, Th and Pb found in natural minerals requires standards containing similar concentrations of these elements. The ideal low-level standard suite will have materials with each REE cation present below 5%, similar to natural rare-earth phosphate minerals. In contrast, REE orthophosphates LnPO4 have cation concentrations from 59 to 64%, and ultraphosphates LnP5O14 from 27% to 32%. The concentrations of U and Pb must also be in the 1% range in the host REE phosphate. There are two competing limits to the synthesis of crystals with multiple cations in the REE sites. The crystal structure limits potential cation mixtures to selections within groups (La,Ce, Pr, Nd, Sm, Eu), (Gd, Tb, Dy, Ho), and (Er, Tm,Yb, Lu, Y). Complex L X-ray spectra limit the use of contiguous REE in a single material. There are two general synthetic routes for the preparation of lanthanide/actinide standard materials for beam analysis and dating. Lanthanide orthophosphates (LnPO4) are crystallized from lead-free heterogeneous fluxes; oligomers (metaphosphates LnP3O9 and ultraphosphates LnP5O14) are formed by condensation of phosphoric acid in the presence of cations. All of these trivalent lanthanide phosphate crystal structures are hosts for Th+4 and U+4, and in synthetic materals, Ca+2 is used for charge compensation. Our work focuses on the preparation of mixed-cation lanthanide metaphosphates and ultraphosphates. The solvent (essentially P2O5) provides redox conditions that favour Ce+3, Th+4, and U+4 instead of higher oxidation states. The absence of any cations other than those deliberately added permits positive control of cation mixtures in starting materials. The synthetic pathway—condensation of POx units--provides ideal conditions for the homogeneous distribution of cations including those with different charges. We present the results of synthesis, elemental analysis and imaging by XRF and SEM-EDX for mixed lanthanide-actinide phosphate materials.

Statistical analysis of excitation energies in actinide and rare-earth nuclei

NASA Astrophysics Data System (ADS)

Levon, A. I.; Magner, A. G.; Radionov, S. V.

2018-04-01

Statistical analysis of distributions of the collective states in actinide and rare-earth nuclei is performed in terms of the nearest-neighbor spacing distribution (NNSD). Several approximations, such as the linear approach to the level repulsion density and that suggested by Brody to the NNSDs were applied for the analysis. We found an intermediate character of the experimental spectra between the order and the chaos for a number of rare-earth and actinide nuclei. The spectra are closer to the Wigner distribution for energies limited by 3 MeV, and to the Poisson distribution for data including higher excitation energies and higher spins. The latter result is in agreement with the theoretical calculations. These features are confirmed by the cumulative distributions, where the Wigner contribution dominates at smaller spacings while the Poisson one is more important at larger spacings, and our linear approach improves the comparison with experimental data at all desired spacings.

Method for decontamination of nickel-fluoride-coated nickel containing actinide-metal fluorides

DOEpatents

Windt, Norman F.; Williams, Joe L.

1983-01-01

The invention is a process for decontaminating particulate nickel contaminated with actinide-metal fluorides. In one aspect, the invention comprises contacting nickel-fluoride-coated nickel with gaseous ammonia at a temperature effecting nickel-catalyzed dissociation thereof and effecting hydrogen-reduction of the nickel fluoride. The resulting nickel is heated to form a melt and a slag and to effect transfer of actinide metals from the melt into the slag. The melt and slag are then separated. In another aspect, nickel containing nickel oxide and actinide metals is contacted with ammonia at a temperature effecting nickel-catalyzed dissociation to effect conversion of the nickel oxide to the metal. The resulting nickel is then melted and separated as described. In another aspect nickel-fluoride-coated nickel containing actinide-metal fluorides is contacted with both steam and ammonia. The resulting nickel then is melted and separated as described. The invention is characterized by higher nickel recovery, efficient use of ammonia, a substantial decrease in slag formation and fuming, and a valuable increase in the service life of the furnace liners used for melting.

Soft X-ray scanning transmission X-ray microscopy (STXM) of actinide particles.

PubMed

Nilsson, Hans J; Tyliszczak, Tolek; Wilson, Richard E; Werme, Lars; Shuh, David K

2005-09-01

A descriptive account is given of our most recent research on the actinide dioxides with the Advanced Light Source Molecular Environmental Science (ALS-MES) Beamline 11.0.2 soft X-ray scanning transmission X-ray microscope (STXM) at the Lawrence Berkeley National Laboratory (LBNL). The ALS-MES STXM permits near-edge X-ray absorption fine structure (NEXAFS) and imaging with 30-nm spatial resolution. The first STXM spectromicroscopy NEXAFS spectra at the actinide 4d5/2 edges of the imaged transuranic particles, NpO2 and PuO2, have been obtained. Radiation damage induced by the STXM was observed in the investigation of a mixed oxidation state particle (Np(V,VI)) and was minimized during collection of the actual spectra at the 4d5/2 edge of the Np(V,VI) solid. A plutonium elemental map was obtained from an irregular PuO2 particle with the dimensions of 650 x 650 nm. The Pu 4d5/2 NEXAFS spectra were collected at several different locations from the PuO2 particle and were identical. A representative oxygen K-edge spectrum from UO2 was collected and resembles the oxygen K-edge from the bulk material. The unique and current performance of the ALS-MES STXM at extremely low energies (ca. 100 eV) that may permit the successful measurement of the actinide 5d edge is documented. Finally, the potential of STXM as a tool for actinide investigations is briefly discussed.

Magnesium transport extraction of transuranium elements from LWR fuel

DOEpatents

Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Miller, William E.; Pierce, R. Dean

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl.sub.2 and a U-Fe alloy containing not less than about 84% by weight uranium at a temperature in the range of from about 800.degree. C. to about 850.degree. C. to produce additional uranium metal which dissolves in the U-Fe alloy raising the uranium concentration and having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein. The CaCl.sub.2 having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO.sub.2. The Ca metal and CaCl.sub.2 is recycled to reduce additional oxide fuel. The U-Fe alloy having transuranium actinide metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with Mg metal which takes up the actinide and rare earth fission product metals. The U-Fe alloy retains the noble metal fission products and is stored while the Mg is distilled and recycled leaving the transuranium actinide and rare earth fission products isolated.

ORNL actinide materials and a new detection system for superheavy nuclei

NASA Astrophysics Data System (ADS)

Rykaczewski, Krzysztof P.; Roberto, James B.; Brewer, Nathan T.; Utyonkov, Vladimir K.

2016-12-01

The actinide resources and production capabilities at Oak Ridge National Laboratory (ORNL) are reviewed, including potential electromagnetic separation of rare radioactive materials. The first experiments at the Dubna Gas Filled Recoil Separator (DGFRS) with a new digital detection system developed at ORNL and University of Tennessee Knoxville (UTK) are presented. These studies used 240Pu material provided by ORNL and mixed-Cf targets made at ORNL. The proposal to use an enriched 251Cf target and a large dose of 58Fe beam to reach the N = 184 shell closure and to observe new elements with Z = 124, 122 and 120 is discussed.

The New Element Americium (Atomic Number 95)

DOE R&D Accomplishments Database

Seaborg, G.T.; James, R.A.; Morgan, L.O.

1948-01-01

Several isotopes of the new element 95 have been produced and their radiations characterized. The chemical properties of this tripositive element are similar to those of the typical tripositive lanthanide rare-earth elements. Element 95 is different from the latter in the degree and rate of formation of certain compounds of the complex ion type, which makes possible the separation of element 95 from the lanthanide rare-earths. The name americium (after the Americas) and the symbol Am are suggested for the element on the basis of its position as the sixth member of the actinide rare-earth series, analogous to europium, Eu, of the lanthanide series.

Trace Metal-Humic Complexes in Natural Waters: Insights From Speciation Experiments

NASA Astrophysics Data System (ADS)

Stern, J. C.; Salters, V.; Sonke, J.

2006-12-01

The DOM cycle is intimately linked to the cycling and bioavailability of trace metals in aqueous environments. The presence or absence of DOM in the water column can determined whether trace elements will be present in limited quantities as a nutrient, or in surplus quantities as a toxicant. Humic substances (HS), which represent the refractory products of DOM degradation, strongly affect the speciation of trace metals in natural waters. To simulate metal-HS interactions in nature, experiments must be carried out using trace metal concentrations. Sensitive detection systems such as ICP-MS make working with small (nanomolar) concentrations possible. Capillary electrophoresis coupled with ICP-MS (CE-ICP-MS) has recently been identified as a rapid and accurate method to separate metal species and calculate conditional binding constants (log K_c) of metal-humic complexes. CE-ICP-MS was used to measure partitioning of metals between humic substances and a competing ligand (EDTA) and calculate binding constants of rare earth element (REE) and Th, Hf, and Zr-humic complexes at pH 3.5-8 and ionic strength of 0.1. Equilibrium dialysis ligand exchange (EDLE) experiments to validate the CE-ICP-MS method were performed to separate the metal-HS and metal-EDTA species by partitioning due to size exclusion via diffusion through a 1000 Da membrane. CE-ICP-MS experiments were also conducted to compare binding constants of REE with humic substances of various origin, including soil, peat, and aquatic DOM. Results of our experiments show an increase in log K_c with decrease in ionic radius for REE-humic complexes (the lanthanide contraction effect). Conditional binding constants of tetravalent metal-humic complexes were found to be several orders of magnitude higher than REE-humic complexes, indicating that tetravalent metals have a very strong affinity for humic substances. Because thorium is often used as a proxy for the tetravalent actinides, Th-HS binding constants can allow us to assess the importance of tetravalent actinide-humic complexes in groundwater transport from nuclear repositories. Our results suggest that tetravalent actinide-humic complexes couild be more important to account for in predictive speciation models than previously thought.

Chemical properties of the transactinide elements studied inliquid phase with SISAK

DOE Office of Scientific and Technical Information (OSTI.GOV)

Omtvedt, J.P.; Alstad, J.; Bjornstad, T.

2007-05-01

This article starts with a review of the current SISAKliquid-liquid extraction system, as used after the physical preseparatorBGS at LBNL for chemical studies of transactinide elements. Emphasis willbe on new additions and developments. Then the possibilities offered bythe new TASCA separator at GSI and the use of actinide targets at bothGSI and LBNL are discussed with respect to future SISAK transactinideexperiments. Finally, current and future liquid-liquid extraction systemsfor studying elements Rf up to Hs are discussed.

Actinide bioimaging in tissues: Comparison of emulsion and solid track autoradiography techniques with the iQID camera

PubMed Central

Miller, Brian W.; Van der Meeren, Anne; Tazrart, Anissa; Angulo, Jaime F.; Griffiths, Nina M.

2017-01-01

This work presents a comparison of three autoradiography techniques for imaging biological samples contaminated with actinides: emulsion-based, plastic-based autoradiography and a quantitative digital technique, the iQID camera, based on the numerical analysis of light from a scintillator screen. In radiation toxicology it has been important to develop means of imaging actinide distribution in tissues as these radionuclides may be heterogeneously distributed within and between tissues after internal contamination. Actinide distribution determines which cells are exposed to alpha radiation and is thus potentially critical for assessing absorbed dose. The comparison was carried out by generating autoradiographs of the same biological samples contaminated with actinides with the three autoradiography techniques. These samples were cell preparations or tissue sections collected from animals contaminated with different physico-chemical forms of actinides. The autoradiograph characteristics and the performances of the techniques were evaluated and discussed mainly in terms of acquisition process, activity distribution patterns, spatial resolution and feasibility of activity quantification. The obtained autoradiographs presented similar actinide distribution at low magnification. Out of the three techniques, emulsion autoradiography is the only one to provide a highly-resolved image of the actinide distribution inherently superimposed on the biological sample. Emulsion autoradiography is hence best interpreted at higher magnifications. However, this technique is destructive for the biological sample. Both emulsion- and plastic-based autoradiography record alpha tracks and thus enabled the differentiation between ionized forms of actinides and oxide particles. This feature can help in the evaluation of decorporation therapy efficacy. The most recent technique, the iQID camera, presents several additional features: real-time imaging, separate imaging of alpha particles and gamma rays, and alpha activity quantification. The comparison of these three autoradiography techniques showed that they are complementary and the choice of the technique depends on the purpose of the imaging experiment. PMID:29023595

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boggs, S. Jr.; Livermore, D.; Seitz, M.G.

Dissolved humic substances (humic and fulvic acids) occur in surface waters and groundwaters in concentrations ranging from less than 1 mg(C)/L to more than 100 mg(C)/L. Humic substances are strong complexing agents for many trace metals in the environment and are also capable of forming stable soluble complexes or chelates with radionuclides. Concentrations of humic materials as low as 1 mg(C)/L can produce a detectable increase in the mobility of some actinide elements by forming soluble complexes that inhibit sorption of the radionuclides onto rock materials. The stability of trace metal- or radionuclide-organic complexes is commonly measured by an empiricallymore » determined conditional stability constant (K'), which is based on the ratio of complexed metal (radionuclide) in solution to the product concentration of uncomplexed metal and humic complexant. Larger values of stability constants indicate greater complex stability. The stability of radionuclide-organic complexes is affected both by concentration variables and envionmental factors. In general, complexing is favored by increased of radionuclide, increased pH, and decreased ionic strength. Actinide elements are generally most soluble in their higher oxidation states. Radionuclides can also form stable, insoluble complexes with humic materials that tend to reduce radionuclide mobility. These insoluble complexes may be radionuclide-humate colloids that subsequently precipitate from solution, or complexes of radionuclides and humic substances that sorb to clay minerals or other soil particulates strongly enough to immobilize the radionuclides. Colloid formation appears to be favored by increased radionuclide concentration and lowered pH; however, the conditions that favor formation of insoluble complexes that sorb to particulates are still poorly understood. 129 refs., 25 figs., 19 tabs.« less

An Advanced TALSPEAK Concept for Separating Minor Actinides. Part 1. Process Optimization and Flowsheet Development

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lumetta, Gregg J.; Levitskaia, Tatiana G.; Wilden, Andreas

A system is being developed to separate trivalent actinides from lanthanide fission product elements that uses 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester to extract the lanthanide ions into an organic phase, while the actinide ions are held in the citrate-buffered aqueous phase by complexation to N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA). Earlier investigations of this system using a 2-cm centrifugal contactor revealed that the relatively slow extraction of Sm3+, Eu3+, and Gd3+ resulted in low separation factors from Am3+. In the work reported here, adjustments to the aqueous phase chemistry were made to improve the extraction rates. The results suggest that increasing the concentration ofmore » the citric acid buffer from 0.2 to 0.6 mol/L, and lowering the pH from 3.1 to 2.6, significantly improved lanthanide extraction rates resulting in an actinide/lanthanide separation system suitable for deployment in centrifugal contactors. Experiments performed to evaluate whether the lanthanide extraction rates can be improved by replacing aqueous HEDTA with nitrilotriacetic acid (NTA) exhibited promising results. However, NTA exhibited an unsatisfactorily high distribution value for Am3+ under the extraction conditions examined.« less

Kinetics of dissolution of thorium and uranium doped britholite ceramics

NASA Astrophysics Data System (ADS)

Dacheux, N.; Du Fou de Kerdaniel, E.; Clavier, N.; Podor, R.; Aupiais, J.; Szenknect, S.

2010-09-01

In the field of immobilization of actinides in phosphate-based ceramics, several thorium and uranium doped britholite samples were submitted to leaching tests. The normalized dissolution rates determined for several pH values, temperatures and acidic media from the calcium release range from 4.7 × 10 -2 g m -2 d -1 to 21.6 g m -2 d -1. Their comparison with that determined for phosphorus, thorium and uranium revealed that the dissolution is clearly incongruent for all the conditions examined. Whatever the leaching solution considered, calcium and phosphorus elements were always released with higher RL values than the other elements (Nd, Th, U). Simultaneously, thorium was found to quickly precipitate as alteration product, leading to diffusion phenomena for uranium. For all the media considered, the uranium release is higher than that of thorium, probably due to its oxidation from tetravalent oxidation state to uranyl. Moreover, the evaluation of the partial order related to proton concentration and the apparent energy of activation suggest that the reaction of dissolution is probably controlled by surface chemical reactions occurring at the solid/liquid interface. Finally, comparative leaching tests performed in sulphuric acid solutions revealed a significant influence of such media on the chemical durability of the leached pellets, leading to higher normalized dissolution rates for all the elements considered. On the basis of the results of chemical speciation, this difference was mainly explained in the light of higher complexion constants by sulfate ions compared to nitrate, chloride and phosphate.

Discovery of element 117: Super-heavy elements and the “island of stability”

DOE PAGES

Roberto, James B.; Rykaczewski, Krzysztof Piotr

2017-04-12

Element 117 (tennessine) joined the periodic table in November 2016. Two tennessine isotopes were synthesized by bombarding 249Bk from Oak Ridge National Laboratory with 48Ca ions at the Joint Institute of Nuclear Research, Russia, and 11 new heaviest isotopes of odd-Z elements were observed in subsequent decay chains. These isotopes exhibit increasing lifetimes as the closed nuclear shell at neutron number N = 184 is approached, providing evidence for the “island of stability” for super-heavy elements. Here, this article summarizes recent super-heavy element research with a focus on element 117, the role of actinide targets, and opportunities to synthesize elementsmore » 119 and 120.« less

Discovery of element 117: Super-heavy elements and the “island of stability”

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roberto, James B.; Rykaczewski, Krzysztof Piotr

Element 117 (tennessine) joined the periodic table in November 2016. Two tennessine isotopes were synthesized by bombarding 249Bk from Oak Ridge National Laboratory with 48Ca ions at the Joint Institute of Nuclear Research, Russia, and 11 new heaviest isotopes of odd-Z elements were observed in subsequent decay chains. These isotopes exhibit increasing lifetimes as the closed nuclear shell at neutron number N = 184 is approached, providing evidence for the “island of stability” for super-heavy elements. Here, this article summarizes recent super-heavy element research with a focus on element 117, the role of actinide targets, and opportunities to synthesize elementsmore » 119 and 120.« less

Ligand induced shape transformation of thorium dioxide nanocrystals.

PubMed

Wang, Gaoxue; Batista, Enrique R; Yang, Ping

2018-04-27

Nanocrystals (NCs) with size and shape dependent properties are a thriving research field. Remarkable progress has been made in the controlled synthesis of NCs of stable elements in the past two decades; however, the knowledge of the NCs of actinide compounds has been considerably limited due the difficulties in handling them both experimentally and theoretically. Actinide compounds, especially actinide oxides, play a critical role in many stages of the nuclear fuel cycle. Recently, a non-aqueous surfactant assisted approach has been developed for the synthesis of actinide oxide NCs with different morphologies, but an understanding of its control factors is still missing to date. Herein we present a comprehensive study on the low index surfaces of thorium dioxide (ThO2) and their interactions with relevant surfactant ligands using density functional calculations. A systematic picture on the thermodynamic stability of ThO2 NCs of different sizes and shapes is obtained employing empirical models based on the calculated surface energies. It is found that bare ThO2 NCs prefer the octahedral shape terminated by (111) surfaces. Oleic acid displays selective adsorption on the (110) surface, leading to the shape transformation from octahedrons to nanorods. Other ligands such as acetylacetone, oleylamine, and trioctylphosphine oxide do not modify the equilibrium shape of ThO2 NCs. This work provides atomic level insights into the anisotropic growth of ThO2 NCs that was recently observed in experiments, and thus may contribute to the controlled synthesis of actinide oxide NCs with well-defined size and shape for future applications.

The CCONE Code System and its Application to Nuclear Data Evaluation for Fission and Other Reactions

NASA Astrophysics Data System (ADS)

Iwamoto, O.; Iwamoto, N.; Kunieda, S.; Minato, F.; Shibata, K.

2016-01-01

A computer code system, CCONE, was developed for nuclear data evaluation within the JENDL project. The CCONE code system integrates various nuclear reaction models needed to describe nucleon, light charged nuclei up to alpha-particle and photon induced reactions. The code is written in the C++ programming language using an object-oriented technology. At first, it was applied to neutron-induced reaction data on actinides, which were compiled into JENDL Actinide File 2008 and JENDL-4.0. It has been extensively used in various nuclear data evaluations for both actinide and non-actinide nuclei. The CCONE code has been upgraded to nuclear data evaluation at higher incident energies for neutron-, proton-, and photon-induced reactions. It was also used for estimating β-delayed neutron emission. This paper describes the CCONE code system indicating the concept and design of coding and inputs. Details of the formulation for modelings of the direct, pre-equilibrium and compound reactions are presented. Applications to the nuclear data evaluations such as neutron-induced reactions on actinides and medium-heavy nuclei, high-energy nucleon-induced reactions, photonuclear reaction and β-delayed neutron emission are mentioned.

Fuel Sustainability And Actinide Production Of Doping Minor Actinide In Water-Cooled Thorium Reactor

NASA Astrophysics Data System (ADS)

Permana, Sidik

2017-07-01

Fuel sustainability of nuclear energy is coming from an optimum fuel utilization of the reactor and fuel breeding program. Fuel cycle option becomes more important for fuel cycle utilization as well as fuel sustainability capability of the reactor. One of the important issues for recycle fuel option is nuclear proliferation resistance issue due to production plutonium. To reduce the proliferation resistance level, some barriers were used such as matrial barrier of nuclear fuel based on isotopic composition of even mass number of plutonium isotope. Analysis on nuclear fuel sustainability and actinide production composition based on water-cooled thorium reactor system has been done and all actinide composition are recycled into the reactor as a basic fuel cycle scheme. Some important parameters are evaluated such as doping composition of minor actinide (MA) and volume ratio of moderator to fuel (MFR). Some feasible parameters of breeding gains have been obtained by additional MA doping and some less moderation to fuel ratios (MFR). The system shows that plutonium and MA are obtained low compositions and it obtains some higher productions of even mass plutonium, which is mainly Pu-238 composition, as a control material to protect plutonium to be used as explosive devices.

Formation of Neutron-Enriched Heavy and Superheavy Nuclei in Fusion Reactions

NASA Astrophysics Data System (ADS)

Karpov, A. V.; Rachkov, V. A.; Saiko, V. V.

2018-05-01

The formation of new isotopes of heavy and superheavy elements in the fusion of neutron-enriched projectiles with actinide targets is discussed. Cross sections for the formation of evaporation residues in fusion reactions is predicted for several combinations of colliding nuclei.

Enrichment of Thorium (Th) and Lead (Pb) in the early Galaxy

NASA Astrophysics Data System (ADS)

Aoki, Wako; Honda, Satoshi

2010-03-01

We have been determining abundances of Th, Pb and other neutron-capture elements in metal-deficient cool giant stars to constrain the enrichment of heavy elements by the r- and s-processes. Our current sample covers the metallicity range between [Fe/H] = -2.5 and -1.0. (1) The abundance ratios of Pb/Fe and Pb/Eu of most of our stars are approximately constant, and no increase of these ratios with increasing metallicity is found. This result suggests that the Pb abundances of our sample are determined by the r-process with no or little contribution of the s-process. (2) The Th/Eu abundance ratios of our sample show no significant scatter, and the average is lower by 0.2 dex in the logarithmic scale than the solar-system value. This result indicates that the actinides production by the r-process does not show large dispersion, even though r-process models suggest high sensitivity of the actinides production to the nucleosynthesis environment.

The New Element Berkelium (Atomic Number 97)

DOE R&D Accomplishments Database

Seaborg, G. T.; Thompson, S. G.; Ghiorso, A.

1950-04-26

An isotope of the element with atomic number 97 has been discovered as a product of the helium-ion bombardment of americium. The name berkelium, symbol Bk, is proposed for element 97. The chemical separation of element 97 from the target material and other reaction products was made by combinations of precipitation and ion exchange adsorption methods making use of its anticipated (III) and (IV) oxidation states and its position as a member of the actinide transition series. The distinctive chemical properties made use of in its separation and the equally distinctive decay properties of the particular isotope constitute the principal evidence for the new element.

A unified picture of the crystal structures of metals

NASA Astrophysics Data System (ADS)

Söderlind, Per; Eriksson, Olle; Johansson, Börje; Wills, J. M.; Boring, A. M.

1995-04-01

THE crystal structures of the light actinides have intrigued physicists and chemists for several decades1. Simple metals and transition metals have close-packed, high-symmetry structures, such as body-centred cubic, face-centred cubic and hexagonal close packing. In contrast, the structures of the light actinides are very loosely packed and of low symmetry-tetragonal, orthorhombic and monoclinic. To understand these differences, we have performed total-energy calculations, as a function of volume, for both high-and low-symmetry structures of a simple metal (aluminium), a non-magnetic transition metal (niobium), a ferromagnetic transition metal (iron) and a light actinide (uranium). We find that the crystal structure of all of these metals is determined by the balance between electrostatic (Madelung) interactions, which favour high symmetry, and a Peierls distortion of the crystal lattice, which favours low symmetry. We show that simple metals and transition metals can adopt low-symmetry structures on expansion of the lattice; and we predict that, conversely, the light actinides will undergo transitions to structures of higher symmetry on compression.

Method for decontamination of nickel-fluoride-coated nickel containing actinide-metal fluorides

DOEpatents

Windt, N.F.; Williams, J.L.

In one aspect, the invention comprises contacting nickel-fluoride-coated nickel with gaseous ammonia at a temperature effecting nickel-catalyzed dissociation thereof and effecting hydrogen-reduction of the nickel fluoride. The resulting nickel is heated to form a melt and a slag and to effect transfer of actinide metals from the melt into the slag. The melt and slag are then separated. In another aspect, nickel contianing nickel oxide and actinide metals is contacted with ammonia at a temperature effecting nickel-catalyzed dissociation to effect conversion of the nickel oxide to the metal. The resulting nickel is then melted and separated as described. In another aspect nickel-fluoride-coated nickel containing actinide-metal fluorides is contacted with both steam and ammonia. The resulting nickel then is melted and separated as described. The invention is characterized by higher nickel recovery, efficient use of ammonia, a substantial decrease in slag formation and fuming, and a valuable increase in the service life of the furnace liners used for melting.

Prototype Demonstration of Gamma- Blind Tensioned Metastable Fluid Neutron/Multiplicity/Alpha Detector – Real Time Methods for Advanced Fuel Cycle Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

McDeavitt, Sean M.

The content of this report summarizes a multi-year effort to develop prototype detection equipment using the Tensioned Metastable Fluid Detector (TMFD) technology developed by Taleyarkhan [1]. The context of this development effort was to create new methods for evaluating and developing advanced methods for safeguarding nuclear materials along with instrumentation in various stages of the fuel cycle, especially in material balance areas (MBAs) and during reprocessing of used nuclear fuel. One of the challenges related to the implementation of any type of MBA and/or reprocessing technology (e.g., PUREX or UREX) is the real-time quantification and control of the transuranic (TRU)more » isotopes as they move through the process. Monitoring of higher actinides from their neutron emission (including multiplicity) and alpha signatures during transit in MBAs and in aqueous separations is a critical research area. By providing on-line real-time materials accountability, diversion of the materials becomes much more difficult. The Tensioned Metastable Fluid Detector (TMFD) is a transformational technology that is uniquely capable of both alpha and neutron spectroscopy while being “blind” to the intense gamma field that typically accompanies used fuel – simultaneously with the ability to provide multiplicity information as well [1-3]. The TMFD technology was proven (lab-scale) as part of a 2008 NERI-C program [1-7]. The bulk of this report describes the advancements and demonstrations made in TMFD technology. One final point to present before turning to the TMFD demonstrations is the context for discussing real-time monitoring of SNM. It is useful to review the spectrum of isotopes generated within nuclear fuel during reactor operations. Used nuclear fuel (UNF) from a light water reactor (LWR) contains fission products as well as TRU elements formed through neutron absorption/decay chains. The majority of the fission products are gamma and beta emitters and they represent the more significant hazards from a radiation protection standpoint. However, alpha and neutron emitting uranium and TRU elements represent the more significant safeguards and security concerns. Table 1.1 presents a representative PWR inventory of the uranium and actinide isotopes present in a used fuel assembly. The uranium and actinide isotopes (chiefly the Pu, Am and Cm elements) are all emitters of alpha particles and some of them release significant quantities of neutrons through spontaneous fissions« less

Controlling Hexavalent Americium – A Centerpiece to a Compact Nuclear Fuel Cycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shafer /Braley, Jenifer; Nash, Kenneth L; Lumetta, Gregg

2014-10-01

Closing the nuclear fuel cycle could be simplified by recovering the actinides U through Am as a group. This could be achieved by converting U, Np, Pu and Am to the hexavalent state. Uranium, Np and Pu are readily oxidized to the hexavalent state. Generation of hexavalent Am in acidic solutions is more difficult, as the standard reduction potential of the Am(VI) /Am(III) couple (+1.68 V in 1 M HClO4) is well outside of the electrochemical stability window of water. While the oxidation and separation of Am has been demonstrated under laboratory conditions, several issues could plague scale up andmore » implementation of this separation with used fuel. Two primary concerns are considered. The first issue concerns the stability of the oxidized Am. The second involves the undesirable co-extraction of tetravalent f-elements with the hexavalent actinides. To address the first concern regarding Am redox instability, Am reduction will be monitored under a variety of different conditions to establish the means of improving the stability of Am(VI) in the organic phase. Identifying the components contributing most significantly to its reduction will allow thoughtful modification of the process. To address the second concern, we propose to apply branched chain extractants to separate hexavalent actinides from tetravalent f-elements. Both branched monoamide and organophosphorus extractants have demonstrated significant selectivity for UO22+ versus Th4+, with separation factors generally on the order of 100. The efforts of this two-pronged research program should represent a significant step forward in the development of aqueous separations approaches designed to recover the U-Am actinides based on the availability of the hexavalent oxidation state. For the purposes of this proposal, separations based on this approach will be called SAn(VI) separations, indicating the Separation of An(VI).« less

Actinide oxide photodiode and nuclear battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sykora, Milan; Usov, Igor

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

Importance of the (n,gamma) Cm-247 Evaluation on Neutron Emission in Fast Reactor Fuel Cycle Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benoit Forget; Mehdi Asgari; Rodolfo M. Ferrer

2007-11-01

As part of the GNEP program, it is envisioned to build a fast reactor for the transmutation of minor actinides. The spent nuclear fuel from the current fleet of light water reactors would be recycled, the current baseline is the UREX+1a process, and would act as a feed for the fast reactor. As the fuel is irradiated in a fast reactor a certain quantity of minor actinides would thus build up in the fuel stream creating possible concerns with the neutron emission of these minor actinides for fuel transportation, handling and fabrication. Past neutronic analyses had not tracked minor actinidesmore » above Cm-246 in the transmutation chain, because of the small influence on the overall reactor performance and cycle parameters. However, when trying to quantify the neutron emission from the recycled fuel with high minor actinide content, these higher isotopes play an essential role and should be included in the analysis. In this paper, the influence of tracking these minor actinides on the calculated neutron emission is presented. Also presented is the particular influence of choosing a different evaluated cross section data set to represent the minor actinides above Cm-246. The first representation uses the cross-sections provided by MC2-2 for all isotopes, while the second representation uses infinitely diluted ENDF/BVII.0 cross-sections for Cm-247 to Cf-252 and MC2-2 for all other isotopes.« less

Study on separation of minor actinides from HLLW with new extractant of TODGA-DHOA/Kerosene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Guo-an; Zhu, Wen-bin; Li, Feng-feng

2013-07-01

The extraction behavior of U, Np, Pu, Am, rare earth elements and Sr from nitric acid solutions by TODGA/dodecan, DHOA/dodecane and TODGA-DHOA/dodecane were investigated, respectively. Based on experimental results, a separation process was proposed for minor actinide isolation from high level liquid waste (HLLW): the TODGA-DHOA/kerosene system. The multi-stage counter-current cascade experiments were carried out for the purpose by 0.1 mol/l TODGA-1.0 mol/l DHOA/kerosene with miniature mixer- settler contactor rigs (8 stages for extraction, 6 stages for scrubbing, 8 stages for first stripping, 8 stages for second stripping). The results show that the recovery efficiencies of the actinides and lanthanidesmore » are more than 99.9%, whereas less than 1% Sr was extracted by 0.1 mol/l TODGA - 1.0 mol/l DHOA/kerosene. The stripping efficiencies of U, Np and Pu are more than 95% in the first stripping step by 0.5 mol/l HNO{sub 3} + 0.5 mol/l AHA(aceto-hydroxamic acid), all of the remained actinides and lanthanides can be stripped by 0.01 mol/l HNO{sub 3} in the second stripping step. 99% Sr was extracted by 0.1 mol/l TODGA/kerosene, so Sr can be recovered efficiently directly from the raffinate by 0.1 mol/l TODGA/kerosene. (authors)« less

Novel Separation of Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mariella, R

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

Interim waste storage for the Integral Fast Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benedict, R.W.; Phipps, R.D.; Condiff, D.W.

1991-01-01

The Integral Fast Reactor (IFR), which Argonne National Laboratory is developing, is an innovative liquid metal breeder reactor that uses metallic fuel and has a close coupled fuel recovery process. A pyrochemical process is used to separate the fission products from the actinide elements. These actinides are used to make new fuel for the reactor. As part of the overall IFR development program, Argonne has refurbished an existing Fuel Cycle Facility at ANL-West and is installing new equipment to demonstrate the remote reprocessing and fabrication of fuel for the Experimental Breeder Reactor II (EBR-II). During this demonstration the wastes thatmore » are produced will be treated and packaged to produce waste forms that would be typical of future commercial operations. These future waste forms would, assuming Argonne development goals are fulfilled, be essentially free of long half-life transuranic isotopes. Promising early results indicate that actinide extraction processes can be developed to strip these isotopes from waste stream and return them to the IFR type reactors for fissioning. 1 fig.« less

Technical and economic assessment of different options for minor actinide transmutation: the French case

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chabert, C.; Coquelet-Pascal, C.; Saturnin, A.

Studies have been performed to assess the industrial perspectives of partitioning and transmutation of long-lived elements. These studies were carried out in tight connection with GEN-IV systems development. The results include the technical and economic evaluation of fuel cycle scenarios along with different options for optimizing the processes between the minor actinide transmutation in fast neutron reactors, their interim storage and geological disposal of ultimate waste. The results are analysed through several criteria (impacts on waste, on waste repository, on fuel cycle plants, on radiological exposure of workers, on costs and on industrial risks). These scenario evaluations take place inmore » the French context which considers the deployment of the first Sodium-cooled Fast Reactor (SFR) in 2040. 3 management options of minor actinides have been studied: no transmutation, transmutation in SFR and transmutation in an accelerator-driven system (ADS). Concerning economics the study shows that the cost overrun related to the transmutation process could vary between 5 to 9% in SFR and 26 % in the case of ADS.« less

The shortest Th-Th distance from a new type of quadruple bond.

PubMed

Hu, Han-Shi; Kaltsoyannis, Nikolas

2017-02-15

Compounds featuring unsupported metal-metal bonds between actinide elements remain highly sought after yet confined experimentally to inert gas matrix studies. Notwithstanding this paucity, actinide-actinide bonding has been the subject of extensive computational research. In this contribution, high level quantum chemical calculations at both the scalar and spin-orbit levels are used to probe the Th-Th bonding in a range of zero valent systems of general formula LThThL. Several of these compounds have very short Th-Th bonds arising from a new type of Th-Th quadruple bond with a previously unreported electronic configuration featuring two unpaired electrons in 6d-based δ bonding orbitals. H 3 AsThThAsH 3 is found to have the shortest Th-Th bond yet reported (2.590 Å). The Th 2 unit is a highly sensitive probe of ligand electron donor/acceptor ability; we can tune the Th-Th bond from quadruple to triple, double and single by judicious choice of the L group, up to 2.888 Å for singly-bonded ONThThNO.

Actinide targets for fundamental research in nuclear physics

NASA Astrophysics Data System (ADS)

Eberhardt, K.; Düllmann, Ch. E.; Haas, R.; Mokry, Ch.; Runke, J.; Thörle-Pospiech, P.; Trautmann, N.

2018-05-01

Thin actinide layers deposited on various substrates are widely used as calibration sources in nuclear spectroscopy. Other applications include fundamental research in nuclear chemistry and -physics, e.g., the chemical and physical properties of super-heavy elements (SHE, Z > 103) or nuclear reaction studies with heavy ions. For the design of future nuclear reactors like fast-fission reactors and accelerator-driven systems for transmutation of nuclear waste, precise data for neutron absorption as well as neutron-induced fission cross section data for 242Pu with neutrons of different energies are of particular importance, requiring suitable Pu-targets. Another application includes studies of nuclear transitions in 229Th harvested as α-decay recoil product from a thin layer of its 233U precursor. For this, a thin and very smooth layer of 233U is used. We report here on the production of actinide layers mostly obtained by Molecular Plating (MP). MP is currently the only fabrication method in cases where the desired actinide material is available only in very limited amounts or possesses a high specific activity. Here, deposition is performed from organic solution applying a current density of 1-2 mA/cm2. Under these conditions target thicknesses of 500-1000 μg/cm2 are possible applying a single deposition step with deposition yields approaching 100 %. For yield determination α-particle spectroscopy, γ-spectroscopy and Neutron Activation Analysis is routinely used. Layer homogeneity is checked with Radiographic Imaging. As an alternative technique to MP the production of thin lanthanide and actinide layers by the so-called "Drop on Demand"-technique applied e.g., in ink-jet printing is currently under investigation.

Appraisal of available information on uptake by plants of transplutonium elements and neptunium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thomas, R.L.; Healy, J.W.

1976-07-01

A critical review was made of reported information from laboratory studies of plant uptake of transplutonic elements plus neptunium. The available data are meager but indicate that the uptake of Np is the greatest followed by Am and Cm. The data are not sufficient to provide recommended values for use in hazard calculations but they do indicate that the actinides other than plutonium will be accumulated in plants to a greater degree than plutonium.

Assessing theoretical uncertainties in fission barriers of superheavy nuclei

DOE PAGES

Agbemava, S. E.; Afanasjev, A. V.; Ray, D.; ...

2017-05-26

Here, theoretical uncertainties in the predictions of inner fission barrier heights in superheavy elements have been investigated in a systematic way for a set of state-of-the-art covariant energy density functionals which represent major classes of the functionals used in covariant density functional theory. They differ in basic model assumptions and fitting protocols. Both systematic and statistical uncertainties have been quantified where the former turn out to be larger. Systematic uncertainties are substantial in superheavy elements and their behavior as a function of proton and neutron numbers contains a large random component. The benchmarking of the functionals to the experimental datamore » on fission barriers in the actinides allows to reduce the systematic theoretical uncertainties for the inner fission barriers of unknown superheavy elements. However, even then they on average increase on moving away from the region where benchmarking has been performed. In addition, a comparison with the results of non-relativistic approaches is performed in order to define full systematic theoretical uncertainties over the state-of-the-art models. Even for the models benchmarked in the actinides, the difference in the inner fission barrier height of some superheavy elements reaches $5-6$ MeV. This uncertainty in the fission barrier heights will translate into huge (many tens of the orders of magnitude) uncertainties in the spontaneous fission half-lives.« less

Measurement of the first ionization potential of lawrencium, element 103.

PubMed

Sato, T K; Asai, M; Borschevsky, A; Stora, T; Sato, N; Kaneya, Y; Tsukada, K; Düllmann, Ch E; Eberhardt, K; Eliav, E; Ichikawa, S; Kaldor, U; Kratz, J V; Miyashita, S; Nagame, Y; Ooe, K; Osa, A; Renisch, D; Runke, J; Schädel, M; Thörle-Pospiech, P; Toyoshima, A; Trautmann, N

2015-04-09

The chemical properties of an element are primarily governed by the configuration of electrons in the valence shell. Relativistic effects influence the electronic structure of heavy elements in the sixth row of the periodic table, and these effects increase dramatically in the seventh row--including the actinides--even affecting ground-state configurations. Atomic s and p1/2 orbitals are stabilized by relativistic effects, whereas p3/2, d and f orbitals are destabilized, so that ground-state configurations of heavy elements may differ from those of lighter elements in the same group. The first ionization potential (IP1) is a measure of the energy required to remove one valence electron from a neutral atom, and is an atomic property that reflects the outermost electronic configuration. Precise and accurate experimental determination of IP1 gives information on the binding energy of valence electrons, and also, therefore, on the degree of relativistic stabilization. However, such measurements are hampered by the difficulty in obtaining the heaviest elements on scales of more than one atom at a time. Here we report that the experimentally obtained IP1 of the heaviest actinide, lawrencium (Lr, atomic number 103), is 4.96(+0.08)(-0.07) electronvolts. The IP1 of Lr was measured with (256)Lr (half-life 27 seconds) using an efficient surface ion-source and a radioisotope detection system coupled to a mass separator. The measured IP1 is in excellent agreement with the value of 4.963(15) electronvolts predicted here by state-of-the-art relativistic calculations. The present work provides a reliable benchmark for theoretical calculations and also opens the way for IP1 measurements of superheavy elements (that is, transactinides) on an atom-at-a-time scale.

Burning high-level TRU waste in fusion fission reactors

NASA Astrophysics Data System (ADS)

Shen, Yaosong

2016-09-01

Recently, the concept of actinide burning instead of a once-through fuel cycle for disposing spent nuclear fuel seems to get much more attention. A new method of burning high-level transuranic (TRU) waste combined with Thorium-Uranium (Th-U) fuel in the subcritical reactors driven by external fusion neutron sources is proposed in this paper. The thorium-based TRU fuel burns all of the long-lived actinides via a hard neutron spectrum while outputting power. A one-dimensional model of the reactor concept was built by means of the ONESN_BURN code with new data libraries. The numerical results included actinide radioactivity, biological hazard potential, and much higher burnup rate of high-level transuranic waste. The comparison of the fusion-fission reactor with the thermal reactor shows that the harder neutron spectrum is more efficient than the soft. The Th-U cycle produces less TRU, less radiotoxicity and fewer long-lived actinides. The Th-U cycle provides breeding of 233U with a long operation time (>20 years), hence significantly reducing the reactivity swing while improving safety and burnup.

Benchmark Evaluation of Dounreay Prototype Fast Reactor Minor Actinide Depletion Measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hess, J. D.; Gauld, I. C.; Gulliford, J.

2017-01-01

Historic measurements of actinide samples in the Dounreay Prototype Fast Reactor (PFR) are of interest for modern nuclear data and simulation validation. Samples of various higher-actinide isotopes were irradiated for 492 effective full-power days and radiochemically assayed at Oak Ridge National Laboratory (ORNL) and Japan Atomic Energy Research Institute (JAERI). Limited data were available regarding the PFR irradiation; a six-group neutron spectra was available with some power history data to support a burnup depletion analysis validation study. Under the guidance of the Organisation for Economic Co-Operation and Development Nuclear Energy Agency (OECD NEA), the International Reactor Physics Experiment Evaluation Projectmore » (IRPhEP) and Spent Fuel Isotopic Composition (SFCOMPO) Project are collaborating to recover all measurement data pertaining to these measurements, including collaboration with the United Kingdom to obtain pertinent reactor physics design and operational history data. These activities will produce internationally peer-reviewed benchmark data to support validation of minor actinide cross section data and modern neutronic simulation of fast reactors with accompanying fuel cycle activities such as transportation, recycling, storage, and criticality safety.« less

Electrochemical reduction of (U-40Pu-5Np)O 2 in molten LiCl electrolyte

NASA Astrophysics Data System (ADS)

Iizuka, Masatoshi; Sakamura, Yoshiharu; Inoue, Tadashi

2006-12-01

The electrochemical reduction of neptunium-containing MOX ((U-40Pu-5Np)O 2) was performed in molten lithium chloride melt at 923 K to investigate fundamental behavior of the transuranium elements and applicability of the method to reduction process for these materials. The Np-MOX was electrochemically reduced at the potential lower than -0.6 V vs. Bi-35 mol% Li reference electrode. The reduced metal grains in the surface region of the sample cohered with each other and made the layer of relatively high density, although it did not prevent the reduction of the sample toward the center. Complete reduction of the Np-MOX was shown by the weight change measurement through the electrochemical reduction and also by SEM-EDX observation. The chemical composition of the reduction products was homogeneous and agreed to that of the initial Np-MOX, which indicates that the reduction was completed and not selective among the actinides. The concentrations of the actinide elements, especially plutonium and americium in the electrolyte, increased with the progress of the tests, although their absolute values were very small. It is quite likely that plutonium and americium dissolve into the melt in the same manner as the lanthanide elements in the lithium reduction process.

Utilization of Methacrylates and Polymer Matrices for the Synthesis of Ion Specific Resins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Czerwinski, Kenneth

2013-10-29

Disposal, storage, and/or transmutation of actinides such as americium (Am) will require the development of specific separation schemes. Existing efforts focus on solvent extraction systems for achieving suitable separation of actinide from lanthanides. However, previous work has shown the feasibility of ion-imprinting polymer-based resins for use in ion-exchange-type separations with metal ion recognition. Phenolic-based resins have been shown to function well for Am-Eu separations, but these resins exhibited slow kinetics and difficulties in the imprinting process. This project addresses the need for new and innovative methods for the selective separation of actinides through novel ion-imprinted resins. The project team willmore » explore incorporation of metals into extended frameworks, including the possibility of 3D polymerized matrices that can serve as a solid-state template for specific resin preparation. For example, an anhydrous trivalent f-element chain can be formed directly from a metal carbonate, and methacrylic acid from water. From these simple coordination complexes, molecules of discrete size or shape can be formed via the utilization of coordinating ligands or by use of an anionic multi-ligand system incorporating methacrylate. Additionally, alkyl methyl methacrylates have been used successfully to create template nanospaces, which underscores their potential utility as 3D polymerized matrices. This evidence provides a unique route for the preparation of a specific metal ion template for the basis of ion-exchange separations. Such separations may prove to be excellent discriminators of metal ions, even between f-elements. Resins were prepared and evaluated for sorption behavior, column properties, and proton exchange capacity.« less

ECCO: Th/U/Pu/Cm Dating of Galactic Cosmic Ray Nuclei

NASA Technical Reports Server (NTRS)

Westphal, A. J.; Weaver, B. A.; Solarz, M.; Dominquez, G.; Craig, N.; Adams, J. H.; Barbier, L. M.; Christian, E. R.; Mitchell, J. W.; Binns, W. R.;

Decay heat power of spent nuclear fuel of power reactors with high burnup at long-term storage

NASA Astrophysics Data System (ADS)

Ternovykh, Mikhail; Tikhomirov, Georgy; Saldikov, Ivan; Gerasimov, Alexander

2017-09-01

Decay heat power of actinides and fission products from spent nuclear fuel of power VVER-1000 type reactors at long-term storage is calculated. Two modes of storage are considered: mode in which single portion of actinides or fission products is loaded in storage facility, and mode in which actinides or fission products from spent fuel of one VVER reactor are added every year in storage facility during 30 years and then accumulated nuclides are stored without addition new nuclides. Two values of fuel burnup 40 and 70 MW·d/kg are considered for the mode of storage of single fuel unloading. For the mode of accumulation of spent fuel with subsequent storage, one value of burnup of 70 MW·d/kg is considered. Very long time of storage 105 years accepted in calculations allows to simulate final geological disposal of radioactive wastes. Heat power of fission products decreases quickly after 50-100 years of storage. The power of actinides decreases very slow. In passing from 40 to 70 MW·d/kg, power of actinides increases due to accumulation of higher fraction of 244Cm. These data are important in the back end of fuel cycle when improved cooling system of the storage facility will be required along with stronger radiation protection during storage, transportation and processing.

Study of extraterrestrial disposal of radioactive wastes. Part 3: Preliminary feasibility screening study of space disposal of the actinide radioactive wastes with 1 percent and 0.1 percent fission product contamination

NASA Technical Reports Server (NTRS)

Hyland, R. E.; Wohl, M. L.; Finnegan, P. M.

1973-01-01

A preliminary study was conducted of the feasibility of space disposal of the actinide class of radioactive waste material. This waste was assumed to contain 1 and 0.1 percent residual fission products, since it may not be feasible to completely separate the actinides. The actinides are a small fraction of the total waste but they remain radioactive much longer than the other wastes and must be isolated from human encounter for tens of thousands of years. Results indicate that space disposal is promising but more study is required, particularly in the area of safety. The minimum cost of space transportation would increase the consumer electric utility bill by the order of 1 percent for earth escape and 3 percent for solar escape. The waste package in this phase of the study was designed for normal operating conditions only; the design of next phase of the study will include provisions for accident safety. The number of shuttle launches per year required to dispose of all U.S. generated actinide waste with 0.1 percent residual fission products varies between 3 and 15 in 1985 and between 25 and 110 by 2000. The lower values assume earth escape (solar orbit) and the higher values are for escape from the solar system.

Fission and quasifission of composite systems with Z =108 -120 : Transition from heavy-ion reactions involving S and Ca to Ti and Ni ions

NASA Astrophysics Data System (ADS)

Kozulin, E. M.; Knyazheva, G. N.; Novikov, K. V.; Itkis, I. M.; Itkis, M. G.; Dmitriev, S. N.; Oganessian, Yu. Ts.; Bogachev, A. A.; Kozulina, N. I.; Harca, I.; Trzaska, W. H.; Ghosh, T. K.

2016-11-01

Background: Suppression of compound nucleus formation in the reactions with heavy ions by a quasifission process in dependence on the reaction entrance channel. Purpose: Investigation of fission and quasifission processes in the reactions 36S,48Ca,48Ti , and 64Ni+238U at energies around the Coulomb barrier. Methods: Mass-energy distributions of fissionlike fragments formed in the reaction 48Ti+238U at energies of 247, 258, and 271 MeV have been measured using the double-arm time-of-flight spectrometer CORSET at the U400 cyclotron of the Flerov Laboratory of Nuclear Reactions and compared with mass-energy distributions for the reactions 36S,48Ca,64Ni+238U . Results: The most probable fragment masses as well as total kinetic energies and their dispersions in dependence on the interaction energies have been investigated for asymmetric and symmetric fragments for the studied reactions. The fusion probabilities have been deduced from the analysis of mass-energy distributions. Conclusion: The estimated fusion probability for the reactions S, Ca, Ti, and Ni ions with actinide nuclei shows that it depends exponentially on the mean fissility parameter of the system. For the reactions with actinide nuclei leading to the formation of superheavy elements the fusion probabilities are of several orders of magnitude higher than in the case of cold fusion reactions.

Speciation of the trivalent f-elements Eu(III) and Cm(III) in digestive media.

PubMed

Wilke, Claudia; Barkleit, Astrid; Stumpf, Thorsten; Ikeda-Ohno, Atsushi

2017-10-01

In case radioactive materials are released into the environment, their incorporation into our digestive system would be a significant concern. Trivalent f-elements, i.e., trivalent actinides and lanthanides, could potentially represent a serious health risk due to their chemo- and radiotoxicity, nevertheless the biochemical behavior of these elements are mostly unknown even to date. This study, therefore, focuses on the chemical speciation of trivalent f-elements in the human gastrointestinal tract. To simulate the digestive system artificial digestive juices (saliva, gastric juice, pancreatic juice and bile fluid) were prepared. The chemical speciation of lanthanides (as Eu(III)) and actinides (as Cm(III)) was determined experimentally by time-resolved laser-induced fluorescence spectroscopy (TRLFS) and the results were compared with thermodynamic modeling. The results indicate a dominant inorganic species with phosphate/carbonate in the mouth, while the aquo ion is predominantly formed with a minor contribution of the enzyme pepsin in the stomach. In the intestinal tract the most significant species are with the protein mucin. We demonstrated the first experimental results on the chemical speciation of trivalent f-elements in the digestive media by TRLFS. The results highlight a significant gap in chemical speciation between experiments and thermodynamic modeling due to the limited availability of thermodynamic stability constants particularly for organic species. Chemical speciation strongly influences the in vivo behavior of metal ions. Therefore, the results of this speciation study will help to enhance the assessment of health risks and to improve decorporation strategies after ingestion of these (radio-)toxic heavy metal ions. Copyright © 2017 Elsevier Inc. All rights reserved.

The chemistry of TALSPEAK: A review of the science

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash, Kenneth L.

Here, the TALSPEAK Process (Trivalent Actinide Lanthanide Separation with Phosphorus-reagent Extraction from Aqueous Komplexes) was originally developed at Oak Ridge National Laboratory by B. Weaver and F.A. Kappelmann in the 1960s. It was envisioned initially as an alternative to the TRAMEX process (selective extraction of trivalent actinides by tertiary or quaternary amines over fission product lanthanides from concentrated LiCl solutions). TALSPEAK proposed the selective extraction of trivalent lanthanides away from the actinides, which are retained in the aqueous phase as aminopolycarboxylate complexes. After several decades of research and development, the conventional TALSPEAK process (based on di-(2-ethylhexyl) phosphoric acid (extractant) inmore » 1,4-di-isopropylbenzene (diluent) and a concentrated lactate buffer containing diethylenetriamine-N,N,N',N",N"-pentaacetic acid (actinide-selective holdback reagent)) has become a widely recognized benchmark for advanced aqueous partitioning of the trivalent 4f/5f elements. TALSPEAK chemistry has also been utilized as an actinide-selective stripping agent (Reverse TALSPEAK) with some notable success. Under ideal conditions, conventional TALSPEAK separates Am 3+ from Nd 3+ (the usual limiting pair) with a single-stage separation factor of about 100; both lighter and heavier lanthanides are more completely separated from Am 3+. Despite this apparent efficiency, TALSPEAK has not seen enthusiastic adoption for advanced partitioning of nuclear fuels at process scale for two principle reasons: 1) all adaptations of TALSPEAK chemistry to process scale applications require rigid pH control within a narrow range of pH, and 2) phase transfer kinetics are often slower than ideal. To compensate for these effects, high concentrations of the buffer (0.5-2 M H/Na lactate) are required. Acknowledgement of these complications in TALSPEAK process development has inspired significant research activities dedicated to improving understanding of the basic chemistry that controls TALSPEAK (and related processes based on the application of actinide-selective holdback reagents). In the following report, advances in understanding of the fundamental chemistry of TALSPEAK that have occurred during the past decade will be reviewed and discussed.« less

The chemistry of TALSPEAK: A review of the science

DOE PAGES

Nash, Kenneth L.

2014-11-13

Here, the TALSPEAK Process (Trivalent Actinide Lanthanide Separation with Phosphorus-reagent Extraction from Aqueous Komplexes) was originally developed at Oak Ridge National Laboratory by B. Weaver and F.A. Kappelmann in the 1960s. It was envisioned initially as an alternative to the TRAMEX process (selective extraction of trivalent actinides by tertiary or quaternary amines over fission product lanthanides from concentrated LiCl solutions). TALSPEAK proposed the selective extraction of trivalent lanthanides away from the actinides, which are retained in the aqueous phase as aminopolycarboxylate complexes. After several decades of research and development, the conventional TALSPEAK process (based on di-(2-ethylhexyl) phosphoric acid (extractant) inmore » 1,4-di-isopropylbenzene (diluent) and a concentrated lactate buffer containing diethylenetriamine-N,N,N',N",N"-pentaacetic acid (actinide-selective holdback reagent)) has become a widely recognized benchmark for advanced aqueous partitioning of the trivalent 4f/5f elements. TALSPEAK chemistry has also been utilized as an actinide-selective stripping agent (Reverse TALSPEAK) with some notable success. Under ideal conditions, conventional TALSPEAK separates Am 3+ from Nd 3+ (the usual limiting pair) with a single-stage separation factor of about 100; both lighter and heavier lanthanides are more completely separated from Am 3+. Despite this apparent efficiency, TALSPEAK has not seen enthusiastic adoption for advanced partitioning of nuclear fuels at process scale for two principle reasons: 1) all adaptations of TALSPEAK chemistry to process scale applications require rigid pH control within a narrow range of pH, and 2) phase transfer kinetics are often slower than ideal. To compensate for these effects, high concentrations of the buffer (0.5-2 M H/Na lactate) are required. Acknowledgement of these complications in TALSPEAK process development has inspired significant research activities dedicated to improving understanding of the basic chemistry that controls TALSPEAK (and related processes based on the application of actinide-selective holdback reagents). In the following report, advances in understanding of the fundamental chemistry of TALSPEAK that have occurred during the past decade will be reviewed and discussed.« less

Californium

NASA Astrophysics Data System (ADS)

Haire, Richard G.

The discovery of californium came in the era of the syntheses and identifications of other transplutonium elements, following the end of World War II. The discovery of the element californium, like many of the other actinide elements, hinged on the development of new experimental techniques in conjunction with predictions based on nuclear systematics. Californium was named after the University and State of California where many of the transuranium elements were first identified. This element was discovered by Thompson, Street, Ghiorso, and Seaborg (Hyde et al., 1971; Seaborg and Loveland, 1990) in February, 1950. The discovery of californium came only 2 months after the preparation and identification of the first isotope of berkelium, element 97 (see Chapter 10). An account of the discovery and reminiscences about the early work on californium has been given by Ghiorso (1983).

Detection of actinides and rare earths in natural matrices with the AGLAE new, high sensitivity detection set-up

NASA Astrophysics Data System (ADS)

Zucchiatti, Alessandro; Alonso, Ursula; Lemasson, Quentin; Missana, Tiziana; Moignard, Brice; Pacheco, Claire; Pichon, Laurent; Camarena de la Mora, Sandra

2014-08-01

A series of granite samples (Grimsel and Äspö) enriched by sorption with natU (10-3 M, 10-4 M, 10-5 M in solution) and La (10-3 M, 10-4 M in solution) has been scanned by PIXE over a surface of 1920 × 1920 mm2 together with non-enriched Grimsel and Äspö granites and a glass standard. An assessment of minimum detection limits, MDL's, for several elements has been performed with the use of standard materials. Due to mapping and the high sensitivity of the new AGLAE detection system, U levels around 30 ppm can be detected from the whole PIXE spectrum (one low energy detector and four summed filtered detectors) while U reach grains, inhomogeneously distributed over the surface can be clearly identified through the multi elemental maps and analyzed separately. Even the nominally enriched samples have La levels below the MDL, probably because precipitation of the element (and not adsorption) mostly took place, and precipitates were eliminated after surface cleaning carried out before PIXE analyses. A multi detector system that implies a PIXE detection solid angle much wider than in any other similar set-up (a factor of 2-5); a higher events selectivity, given by the possibility of filtering individually up to 4 PIXE detectors; a double RBS detector, the new Ion Beam Induced Luminescence (IBIL) spectrometry and gamma spectrometry. Full mapping capability in air, assisted by a powerful event by event reconstruction software. These features allow lower Minimum Detection Limits (MDL) which are highly beneficial to the analysis of cultural heritage objects, meaning generally a reduction of irradiation time. Paintings will then be studied without any damage to the pigments that have color change tendencies which is a major drawback of the previous system. Alternatively they could allow an increase in information collected at equal time, particularly considering the detector's fast response and therefore the potential for high beam currents when sample damage can be tolerated.This kind of set-up should be advantageous for the detection of elements that are present in a geological, archaeological or artistic samples to the level of a few tens ppm. This is true in particular for the rare earths which are relevant to the provenance attribution of various classes of cultural heritage objects (clays, glasses, …) and the actinides which are relevant in very specific and highly impacting dating problems and, more generally, critical environmental elements with special reference to the radionuclide mobility in deep geological formations hosting radioactive waste [2]. Geological materials are highly heterogeneous and consequently their retention of contaminants is heterogeneous as well. In this frame, the capabilities of the AGLAE set-up would allow an improved characterization of natural heterogeneous rock, detecting the presence of the elements of interest (actinides and rare earth) at concentration levels of tens of ppm. This provides a better definition of the initial system, avoiding biased interpretation of the retention properties of the material for the analysis of possible contamination. Additionally, if lower detection limits were achieved, new perspectives to evaluate retention of low solubility contaminants in a wider range of geochemical conditions would be opened.A glass standard and a series of reference granite samples (Grimsel and Äspö), either enriched by sorption with natU and La or kept natural, have been scanned by PIXE at the New-AGLAE detection system, to test measurement protocols and assess the MDL's allowed by the five detectors system.

Calcium titanium silicate based glass-ceramic for nuclear waste immobilisation

NASA Astrophysics Data System (ADS)

Sharma, K.; Srivastav, A. P.; Goswami, M.; Krishnan, Madangopal

2018-04-01

Titanate based ceramics (synroc) have been studied for immobilisation of nuclear wastes due to their high radiation and thermal stability. The aim of this study is to synthesis glass-ceramic with stable phases from alumino silicate glass composition and study the loading behavior of actinides in glass-ceramics. The effects of CaO and TiO2 addition on phase evolution and structural properties of alumino silicate based glasses with nominal composition x(10CaO-9TiO2)-y(10Na2O-5 Al2O3-56SiO2-10B2O3); where z = x/y = 1.4-1.8 are reported. The glasses are prepared by melt-quench technique and characterized for thermal and structural properties using DTA and Raman Spectroscopy. Glass transition and peak crystallization temperatures decrease with increase of CaO and TiO2 content, which implies the weakening of glass network and increased tendency of glasses towards crystallization. Sphene (CaTiSiO5) and perovskite (CaTiO3) crystalline phases are confirmed from XRD which are well known stable phase for conditioning of actinides. The microsturcture and elemental analysis indicate the presence of actinide in stable crystalline phases.

Progress toward accurate high spatial resolution actinide analysis by EPMA

NASA Astrophysics Data System (ADS)

Jercinovic, M. J.; Allaz, J. M.; Williams, M. L.

2010-12-01

High precision, high spatial resolution EPMA of actinides is a significant issue for geochronology, resource geochemistry, and studies involving the nuclear fuel cycle. Particular interest focuses on understanding of the behavior of Th and U in the growth and breakdown reactions relevant to actinide-bearing phases (monazite, zircon, thorite, allanite, etc.), and geochemical fractionation processes involving Th and U in fluid interactions. Unfortunately, the measurement of minor and trace concentrations of U in the presence of major concentrations of Th and/or REEs is particularly problematic, especially in complexly zoned phases with large compositional variation on the micro or nanoscale - spatial resolutions now accessible with modern instruments. Sub-micron, high precision compositional analysis of minor components is feasible in very high Z phases where scattering is limited at lower kV (15kV or less) and where the beam diameter can be kept below 400nm at high current (e.g. 200-500nA). High collection efficiency spectrometers and high performance electron optics in EPMA now allow the use of lower overvoltage through an exceptional range in beam current, facilitating higher spatial resolution quantitative analysis. The U LIII edge at 17.2 kV precludes L-series analysis at low kV (high spatial resolution), requiring careful measurements of the actinide M series. Also, U-La detection (wavelength = 0.9A) requires the use of LiF (220) or (420), not generally available on most instruments. Strong peak overlaps of Th on U make highly accurate interference correction mandatory, with problems compounded by the ThMIV and ThMV absorption edges affecting peak, background, and interference calibration measurements (especially the interference of the Th M line family on UMb). Complex REE bearing phases such as monazite, zircon, and allanite have particularly complex interference issues due to multiple peak and background overlaps from elements present in the activation volume, as well as interferences from fluorescence at a distance from adjacent phases or distinct compositional domains in the same phase. Interference corrections for elements detected during boundary fluorescence are further complicated by X-ray focusing geometry considerations. Additional complications arise from the high current densities required for high spatial resolution and high count precision, such as fluctuations in internal charge distribution and peak shape changes as satellite production efficiency varies from calibration to analysis. No flawless method has yet emerged. Extreme care in interference corrections, especially where multiple and sometime mutual overlaps are present, and maximum care (and precision) in background characterization to account for interferences and curvature (e.g., WDS scan or multipoint regression), are crucial developments. Calibration curves from multiple peak and interference calibration measurements at different concentrations, and iterative software methodologies for incorporating absorption edge effects, and non-linearities in interference corrections due to peak shape changes and off-axis X-ray defocussing during boundary fluorescence at a distance, are directions with significant potential.

Experimental geochemistry of Pu and Sm and the thermodynamics of trace element partitioning

NASA Technical Reports Server (NTRS)

Jones, John H.; Burnett, Donald S.

1987-01-01

An experimental study of the partitioning of Pu and Sm between diopside/liquid and whitlockite/liquid supports the hypothesis that Pu behaves as a light rare earth element during igneous processes in reducing environments. D-Pu/D-Sm is found to be about 2 for both diopsidic pyroxene and whitlockite, and the amount of fractionation would be decreased further if Pu were compared to Ce or Nd. Data indicate that temperature, rather than melt composition, is the most important control on elemental partitioning, and that P2O5 in aluminosilicate melts serves as a complexing agent for the actinides and lanthanides.

Trends in the short-term release of fission products and actinides to aqueous solution from used CANDU fuels at elevated temperature

NASA Astrophysics Data System (ADS)

Stroes-Gascoyne, S.

1992-08-01

A large number of short-term leaching experiments has been performed to determine fission product and actinide release from used CANDU (CANada Deuterium Uranium) fuels and to establish which factors affect release. Results are reported after30 ± 10 d leaching at 100-150°C under oxidizing (air) or reducing (Ar-3% H 2 or Ar) conditions, in various synthetic groundwaters. Cesium-137 release (0.007-6%) was positively correlated with increases in fuel power, leachant temperature and ionic strength. Strontium-90 release (0.0003-0.3%) generally increased with ionic strength, higher temperature and redox conditions. Actinide and Tc concentrations were compared to ranges calculated with a thermodynamic equilibrium model, that accounts for the uncertain geochemical parameters of a nuclear waste vault by calculating concentration ranges based on 40000 hypothetical cases. Experimental U concentrations (10 -8.5 to 10 -3 mol/kg) were higher than the model range, probably because of higher redox potentials in the experiments. Measured Pu concentrations (10 -12.5 to 10 -7 mol/kg) were at the low end of the calculated range. Americium and Cm concentrations (10 -12.5 to 10 -7 and 10 -15 to 10 -9 mol/kg, respectively) were highest under oxidizing conditions and higher temperatures. Technetium-99 concentrations (10 -5.5 to 10 -10.5 mol/kg) covered a much narrower range than calculated by the model.

Extractant composition

DOEpatents

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

1990-01-01

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

Chemistry of transuranium elements in salt-base repository

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borkowski, Marian; Reed, Donald T; Lucchini, Jean - Francois

2010-12-02

The mobility and potential release of actinides into the accessible environment continues to be the key performance assessment concern of nuclear repositories. Actinide, in particular plutonium speciation under the wide range of conditions that can exist in the subsurface is complex and depends strongly on the coupled effects of redox conditions, inorganic/organic complexation, and the extent/nature of aggregation. Understanding the key factors that define the potential for actinide migration is, in this context, an essential and critical part of making and sustaining a licensing case for a nuclear repository. Herein we report on recent progress in a concurrent modeling andmore » experimental study to determine the speciation of plutonium, uranium and americium in high ionic strength Na-CI-Mg brines. This is being done as part of the ongomg recertification effort m the Waste Isolation Pilot Plant (WIPP). The oxidation-state specific solubility of actinides were established in brine as function of pC{sub H+}, brine composition and the presence and absence of organic chelating agents and carbonate. An oxidation-state invariant analog approach using Nd{sup 3+} and Th{sup 4+} was used for An{sup 3+} and An{sup 4+} respectively. These results show that organic ligands and hydrolysis are key factors for An(III) solubility, hydrolysis at pC{sub H+} above 8 is predominate for An(IV) and carbonates are the key factor for U(VI) solubility. The effect of high ionic strength and brine components measured in absence of carbonates leads to measurable increased in overall solubility over analogous low ionic strength groundwater. Less is known about the bioreduction of actinides by halo-tolerant microorganisms, but there is now evidence that bioreduction does occur and is analogous, in many ways, to what occurs with soil bacteria. Results of solubility studies that focus on Pitzer parameter corrections, new species (e.g. borate complexation), and the thermodynamic parameters for modeling are discussed.« less

Removal of actinide elements from liquid scintillation cocktail wastes using liquid-liquid extraction and demulsification techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foltz, K.; Landsberger, S.; Srinivasan, B.

1994-12-31

For many years liquid scintillation cocktail (LSC) wastes have been generated and stored at Argonne National Laboratory (ANL). These wastes are stored in thousands of 10--20 m scintillation vials, many of which contain elements with Z > 88. Because storage space is limited, disposal of this waste is pressing. These wastes could be commercially incinerated if the radionuclides with Z>88 are reduced to sufficiently low levels. However, there is currently no deminimus level for these radionuclides, and separation techniques are still being tested. The University of Illinois is conducting experiments to separate radionuclides with Z > 88 from simulated LSCmore » wastes by using liquid-liquid extraction (LLX) and demulsification techniques. The actinide elements are removed from the LSC by extraction into an aqueous phase after the cocktail has been demulsified. The aqueous and organic phases are separated and the organic phase, now free from radionuclides with Z > 88, can be sent to a commercial incineration facility. The aqueous phase may be treated and disposed of using existing techniques. The LLX separation techniques used solutions of sodium oxalate, aluminum nitrate, and tetrasodium EDTA at varying concentrations. These extractants were mixed with the simulated waste in a 1:1 volume ratio. Using 1.0M Na{sub 4} EDTA salt solutions, decontamination ratios as high as 230 were achieved.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pacold, J. I.; Altman, A. B.; Donald, S B

Materials of interest for nuclear forensic science are often highly heterogeneous, containing complex mixtures of actinide compounds in a wide variety of matrices. Scanning transmission X-ray microscopy (STXM) is ideally suited to study such materials, as it can be used to chemically image specimens by acquiring X-ray absorption near-edge spectroscopy (XANES) data with 25 nm spatial resolution. In particular, STXM in the soft X-ray synchrotron radiation regime (approximately 120 – 2000 eV) can collect spectroscopic information from the actinides and light elements in a single experiment. Thus, STXM combines the chemical sensitivity of X-ray absorption spectroscopy with high spatial resolutionmore » in a single non-destructive characterization method. This report describes the application of STXM to a broad range of nuclear materials. Where possible, the spectroscopic images obtained by STXM are compared with information derived from other analytical methods, and used to make inferences about the process history of each material. STXM measurements can yield information including the morphology of a sample, “elemental maps” showing the spatial distribution of major chemical constituents, and XANES spectra from localized regions of a sample, which may show spatial variations in chemical composition.« less

Analysis of Advanced Fuel Assemblies and Core Designs for the Current and Next Generations of LWRs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ragusa, Jean; Vierow, Karen

2011-09-01

The objective of the project is to design and analyze advanced fuel assemblies for use in current and future light water reactors and to assess their ability to reduce the inventory of transuranic elements, while preserving operational safety. The reprocessing of spent nuclear fuel can delay or avoid the need for a second geological repository in the US. Current light water reactor fuel assembly designs under investigation could reduce the plutonium inventory of reprocessed fuel. Nevertheless, these designs are not effective in stabilizing or reducing the inventory of minor actinides. In the course of this project, we developed and analyzedmore » advanced fuel assembly designs with improved thermal transmutation capability regarding transuranic elements and especially minor actinides. These designs will be intended for use in thermal spectrum (e.g., current and future fleet of light water reactors in the US). We investigated various fuel types, namely high burn-up advanced mixed oxides and inert matrix fuels, in various geometrical designs that are compliant with the core internals of current and future light water reactors. Neutronic/thermal hydraulic effects were included. Transmutation efficiency and safety parameters were used to rank and down-select the various designs.« less

Morphological and compositional study of 238U thin film targets for nuclear experiments

NASA Astrophysics Data System (ADS)

Sibbens, Goedele; Ernstberger, Markus; Gouder, Thomas; Marouli, Maria; Moens, André; Seibert, Alice; Vanleeuw, David; Zúñiga, Martin Vargas; Wiss, Thierry; Zampella, Mariavittoria; Zuleger, Evelyn

2018-05-01

The uncertainty in neutron cross section values strongly depends on the quality and characteristics of the deposited actinide films which are used as "targets" in the nuclear experiments. Until recently, at the Joint Research Centre in Geel (JRC-Geel), mass and areal densities of actinide layers were determined by measuring activity (using alpha-particle counting), isotopic composition (using thermal ionisation mass spectrometry) and diameter. In this study a series of 238U deposits, prepared by molecular plating and vacuum deposition on different substrates, were characterized with additional non-destructive and destructive analysis techniques. The quality of the deposits was investigated by autoradiography, high-resolution alpha-particle spectrometry, and scanning electron microscopy. The elemental composition was determined by x-ray photoelectron spectroscopy and inductively coupled plasma mass spectrometry. The latter technique was also applied on the U3O8 starting material and the converted UF4 powder. This paper compares the quality and morphology of deposited 238U films prepared by molecular plating and vacuum deposition on various backings, including their elemental composition determined by different characterization techniques. Also discussed are problems in target preparation and characterization.

Heavy Nucleus Collector (HNC) project for the NASA Long Duration Exposure Facility (LDEF)

NASA Technical Reports Server (NTRS)

Tarle, Gregory

1990-01-01

The primary goal of the heavy nucleus collector (HNC) experiment was to obtain high resolution composition measurements for cosmic ray nuclei in the platinum-lead and actinide region of the periodic table. Secondary objectives include studies of selected groups of elements of lower charge. These goals were to be realized by orbiting a large area array of dielectric nuclear track detectors in space for several years. In this time sufficient actinide nuclei would be collected to determine the nucleosynthetic age of the cosmic radiation and the relative mix of r- and s-process elements in the cosmic ray source. The detector consists of approximately 50 trays assembled in pressurized canisters. Each tray would contain 8 half-stacks (4 stacks total) and an event thermometer which would record the temperature of each event at the time of exposure. Each stack would contain 7 layers of Rodyne-P, CR-39 and Cronar plastic track detectors interleaved with copper stripping foils. Upon return to Earth, detectors would be removed for analysis. Ultraheavy nuclei would have left tracks through the detector sheets that would be made visible after etching in a hot sodium hydroxide solution.

Actinide metal processing

DOEpatents

Sauer, Nancy N.; Watkin, John G.

1992-01-01

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

Actinide metal processing

DOEpatents

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

1992-03-24

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

Method for preparing actinide nitrides

DOEpatents

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

1975-12-01

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

Actinide-ion sensor

DOEpatents

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

2015-01-13

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

Ionic Interactions in Actinide Tetrahalides

NASA Astrophysics Data System (ADS)

Akdeniz, Z.; Karaman, A.; Tosi, M. P.

2001-05-01

We determine a model of the ionic interactions in AX 4 compounds (where A is an atom in the actinide series from Th to Am and X = F, Cl, Br or I) by an analysis of data on the static and dynamic structure of their molecular monomers. The potential energy function that we adopt is taken from earlier work on rare-earth trihalides [Z. Akdeniz, Z. Q q e k and M. P. Tosi, Z. Naturforsch. 55a, 861 (2000)] and in particular allows for the electronic polarizability of the actinide ion. This polarizability quantitatively determines the antisymmetric-bending vibrational mode, but its magnitude remains compatible with a symmetric tetrahedral shape of the molecule at equilibrium. The fluorides have an especially high degree of ionic character, and the interionic-force parameters for each halide of the U, Np, Pu and Am series show regular trends, suggesting that extrapolations to the other transuranic-element halides may usefully be made. The Th compounds show some deviations from these trends, and the interionic-force model that we determine for ThCl4 differs somewhat from that obtained in a previous study. We therefore return on the evaluation of the relative stability of charged oligomers of ThCl4 and ZrCl4 and find confirmation of our earlier results on this problem.

Method for the recovery of actinide elements from nuclear reactor waste

DOEpatents

Horwitz, E. Philip; Delphin, Walter H.; Mason, George W.

1979-01-01

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

Frontiers of Chemistry for Americium and Curium

DOE R&D Accomplishments Database

Keller, O. L. Jr.

1984-01-01

The discoveries of americium and curium were made only after Seaborg had formulated his actinide concept in order to design the chemistry needed to separate them from irradiated /sup 239/Pu targets. Their discoveries thus furnished the first clear-cut evidence that the series exists and justified Seaborg`s bold assumption that even though Th and Pa appeared to presage a following 6d series, the pattern established by the periodic table after Cs and Ba would be repeated exactly after Fr and Ra. That is to say, a new 5f element rare earth series (the actinides) would follow Ac in the same way the 4f rare earth series (the lanthanides) follows La. The consequences of the resulting half-filled 5f/sup 7/ shell at Cm were originally presented by Seaborg as a test of his hypothesis. Recent research is outlined that substantiates Seaborg`s predictions in new and definitive ways.

A Heterobimetallic Complex With an Unsupported Uranium(III)-Aluminum(I) Bond: (CpSiMe3)3U-AlCp* (Cp* = C5Me5)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minasian, Stefan; Krinsky Ph.D., Jamin; Williams, Valerie

2008-07-23

The discovery of molecular metal-metal bonds has been of fundamental importance to the understanding of chemical bonding. For the actinides, examples of unsupported metal-metal bonds are relatively uncommon, consisting of Cp{sub 3}U-SnPh{sub 3}, and several actinide-transition metal complexes. Traditionally, bonding in the f-elements has been described as electrostatic; however, elucidating the degree of covalency is a subject of recent research. In carbon monoxide complexes of the trivalent uranium metallocenes, decreased {nu}{sub CO} values relative to free CO suggest that the U(III) atom acts as a {pi}-donor. Ephritikhine and coworkers have demonstrated that {pi}-accepting ligands can differentiate trivalent lanthanide and actinidemore » ions, an effect that renders this chemistry of interest in the context of nuclear waste separation technology.« less

Development of spent fuel reprocessing process based on selective sulfurization: Study on the Pu, Np and Am sulfurization

NASA Astrophysics Data System (ADS)

Kirishima, Akira; Amano, Yuuki; Nihei, Toshifumi; Mitsugashira, Toshiaki; Sato, Nobuaki

2010-03-01

For the recovery of fissile materials from spent nuclear fuel, we have proposed a novel reprocessing process based on selective sulfurization of fission products (FPs). The key concept of this process is utilization of unique chemical property of carbon disulfide (CS2), i.e., it works as a reductant for U3O8 but works as a sulfurizing agent for minor actinides and lanthanides. Sulfurized FPs and minor actinides (MA) are highly soluble to dilute nitric acid while UO2 and PuO2 are hardly soluble, therefore, FPs and MA can be removed from Uranium and Plutonium matrix by selective dissolution. As a feasibility study of this new concept, the sulfurization behaviours of U, Pu, Np, Am and Eu are investigated in this paper by the thermodynamical calculation, phase analysis of chemical analogue elements and tracer experiments.

Electron binding energy of uranium-ligand and uranyl-ligand anions

NASA Astrophysics Data System (ADS)

Wang, Lei; Horowitz, Steven; Marston, Brad

2012-02-01

Electron binding energies of the early actinide element uranium in gas-phase anion complexes are calculated by relativistic density functional theory (DFT) with two different exchange-correlation functions (RPBE and B3LYP) and also in the Hartree-Fock (HF) approximationootnotetextADF2010.02, SCM.com. Scalar and spin-orbit calculations are performed, and the calculated energies are compared to available experimental measurements and shown to disagree by energies of order 1 eV. Strong correlations that are poorly treated in DFT and HF can be included by a hybrid approach in which a generalized Anderson impurity model is numerically diagonalized. Reduction-oxidation (redox) potentials of aqueous actinide ions show improved agreement with measured values in the hybrid approachootnotetextS. E. Horowitz and J. B. Marston, J. Chem. Phys 134 064510 (2011).. We test whether or not similar improvements are found in the gas-phase.

Flammability Analysis For Actinide Oxides Packaged In 9975 Shipping Containers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laurinat, James E.; Askew, Neal M.; Hensel, Steve J.

2013-03-21

Packaging options are evaluated for compliance with safety requirements for shipment of mixed actinide oxides packaged in a 9975 Primary Containment Vessel (PCV). Radiolytic gas generation rates, PCV internal gas pressures, and shipping windows (times to reach unacceptable gas compositions or pressures after closure of the PCV) are calculated for shipment of a 9975 PCV containing a plastic bottle filled with plutonium and uranium oxides with a selected isotopic composition. G-values for radiolytic hydrogen generation from adsorbed moisture are estimated from the results of gas generation tests for plutonium oxide and uranium oxide doped with curium-244. The radiolytic generation ofmore » hydrogen from the plastic bottle is calculated using a geometric model for alpha particle deposition in the bottle wall. The temperature of the PCV during shipment is estimated from the results of finite element heat transfer analyses.« less

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

DOEpatents

Crisler, L.R.

1975-11-11

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

SOLVENT EXTRACTION PROCESS FOR SEPARATING URANIUM AND PLUTONIUM FROM AQUEOUS ACIDIC SOLUTIONS OF NEUTRON IRRADIATED URANIUM

DOEpatents

Bruce, F.R.

1962-07-24

A solvent extraction process was developed for separating actinide elements including plutonium and uranium from fission products. By this method the ion content of the acidic aqueous solution is adjusted so that it contains more equivalents of total metal ions than equivalents of nitrate ions. Under these conditions the extractability of fission products is greatly decreased. (AEC)

DOE Office of Scientific and Technical Information (OSTI.GOV)

P.E.D. Morgan; R.M. Housley; J.B. Davis

A very import, extremely-long-term, use for monazite as a radwaste encapsulant has been proposed. THe use of ceramic La-monazite for sequestering actinides (isolating them from the environment), especially plutonium and some other radioactive elements )e.g., fission-product rare earths), had been especially championed by Lynn Boatner of ORNL. Monazite may be used alone or, copying its compatibility with many other minerals in nature, may be used in diverse composite combinations.

The interaction of human serum albumin with selected lanthanide and actinide ions: Binding affinities, protein unfolding and conformational changes.

PubMed

Ali, Manjoor; Kumar, Amit; Kumar, Mukesh; Pandey, Badri N

2016-04-01

Human serum albumin (HSA), the most abundant soluble protein in blood plays critical roles in transportation of biomolecules and maintenance of osmotic pressure. In view of increasing applications of lanthanides- and actinides-based materials in nuclear energy, space, industries and medical applications, the risk of exposure with these metal ions is a growing concern for human health. In present study, binding interaction of actinides/lanthanides [thorium: Th(IV), uranium: U(VI), lanthanum: La(III), cerium: Ce(III) and (IV)] with HSA and its structural consequences have been investigated. Ultraviolet-visible, Fourier transform-infrared, Raman, Fluorescence and Circular dichroism spectroscopic techniques were applied to study the site of metal ions interaction, binding affinity determination and the effect of metal ions on protein unfolding and HSA conformation. Results showed that these metal ions interacted with carbonyl (CO..:)/amide(N..-H) groups and induced exposure of aromatic residues of HSA. The fluorescence analysis indicated that the actinide binding altered the microenvironment around Trp214 in the subdomain IIA. Binding affinity of U(VI) to HSA was slightly higher than that of Th(IV). Actinides and Ce(IV) altered the secondary conformation of HSA with a significant decrease of α-helix and an increase of β-sheet, turn and random coil structures, indicating a partial unfolding of HSA. A correlation was observed between metal ion's ability to alter HSA conformation and protein unfolding. Both cationic effects and coordination ability of metal ions seemed to determine the consequences of their interaction with HSA. Present study improves our understanding about the protein interaction of these heavy ions and their impact on its secondary structure. In addition, binding characteristics may have important implications for the development of rational antidote for the medical management of health effects of actinides and lanthanides. Copyright © 2016 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

Dehydration of plutonium or neptunium trichloride hydrate

DOEpatents

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

1992-01-01

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

Dehydration of plutonium or neptunium trichloride hydrate

DOEpatents

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

1992-03-24

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

Salt transport extraction of transuranium elements from LWR fuel

DOEpatents

Pierce, R.D.; Ackerman, J.P.; Battles, J.E.; Johnson, T.R.; Miller, W.E.

1992-11-03

A process is described for separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl[sub 2] and a Cu--Mg alloy containing not less than about 25% by weight Mg at a temperature in the range of from about 750 C to about 850 C to precipitate uranium metal and some of the noble metal fission products leaving the Cu--Mg alloy having transuranium actinide metals and rare earth fission product metals and some of the noble metal fission products dissolved therein. The CaCl[sub 2] having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO[sub 2]. The Ca metal and CaCl[sub 2] is recycled to reduce additional oxide fuel. The Cu--Mg alloy having transuranium metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with a transport salt including MgCl[sub 2] to transfer Mg values from the transport salt to the Cu--Mg alloy while transuranium actinide and rare earth fission product metals transfer from the Cu--Mg alloy to the transport salt. Then the transport salt is mixed with a Mg--Zn alloy to transfer Mg values from the alloy to the transport salt while the transuranium actinide and rare earth fission product values dissolved in the salt are reduced and transferred to the Mg--Zn alloy. 2 figs.

Salt transport extraction of transuranium elements from lwr fuel

DOEpatents

Pierce, R. Dean; Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Miller, William E.

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels which contain rare earth and noble metal fission products. The oxide fuel is reduced with Ca metal in the presence of CaCl.sub.2 and a Cu--Mg alloy containing not less than about 25% by weight Mg at a temperature in the range of from about 750.degree. C. to about 850.degree. C. to precipitate uranium metal and some of the noble metal fission products leaving the Cu--Mg alloy having transuranium actinide metals and rare earth fission product metals and some of the noble metal fission products dissolved therein. The CaCl.sub.2 having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein is separated and electrolytically treated with a carbon electrode to reduce the CaO to Ca metal while converting the carbon electrode to CO and CO.sub.2. The Ca metal and CaCl.sub.2 is recycled to reduce additional oxide fuel. The Cu--Mg alloy having transuranium metals and rare earth fission product metals and the noble metal fission products dissolved therein is contacted with a transport salt including Mg Cl.sub.2 to transfer Mg values from the transport salt to the Cu--Mg alloy while transuranium actinide and rare earth fission product metals transfer from the Cu--Mg alloy to the transport salt. Then the transport salt is mixed with a Mg--Zn alloy to transfer Mg values from the alloy to the transport salt while the transuranium actinide and rare earth fission product values dissolved in the salt are reduced and transferred to the Mg--Zn alloy.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

This report contains viewgraphs on the following topics. The advanced light source U8 undulator beamline, 20--300 eV; gas-phase actinide studies with synchrotron radiation; atomic structure calculations for heavy atoms; flux growth of single crystal uranium intermetallics: Extension to transuranics; x-ray absorption near-edge structure studies of actinide compounds; surface as a new stage for studying actinides: Theoretical study of the surface electronic structure of uranium; magnetic x-ray scattering experiments at resonant energies; beamline instruments for radioactive materials; the search for x-ray absorption magnetic circular dichroism in actinide materials: preliminary experiments using UFe[sub 2] and U-S; the laser plasma laboratory light source:more » a source of preliminary transuranic data; electron spectroscopy of heavy fermion actinide materials; study of thin layers of actinides. Present status and future use of synchrotron radiation; electronic structure and correlated-electron theory for actinide materials; and heavy fermion and kondo phenomena in actinide materials.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

This report contains viewgraphs on the following topics. The advanced light source U8 undulator beamline, 20--300 eV; gas-phase actinide studies with synchrotron radiation; atomic structure calculations for heavy atoms; flux growth of single crystal uranium intermetallics: Extension to transuranics; x-ray absorption near-edge structure studies of actinide compounds; surface as a new stage for studying actinides: Theoretical study of the surface electronic structure of uranium; magnetic x-ray scattering experiments at resonant energies; beamline instruments for radioactive materials; the search for x-ray absorption magnetic circular dichroism in actinide materials: preliminary experiments using UFe{sub 2} and U-S; the laser plasma laboratory light source:more » a source of preliminary transuranic data; electron spectroscopy of heavy fermion actinide materials; study of thin layers of actinides. Present status and future use of synchrotron radiation; electronic structure and correlated-electron theory for actinide materials; and heavy fermion and kondo phenomena in actinide materials.« less

Actinide migration in Johnston Atoll soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolf, S. F.; Bates, J. K.; Buck, E. C.

1997-02-01

Characterization of the actinide content of a sample of contaminated coral soil from Johnston Atoll, the site of three non-nuclear destructs of nuclear warhead-carrying THOR missiles in 1962, revealed that >99% of the total actinide content is associated with discrete bomb fragments. After removal of these fragments, there was an inverse correlation between actinide content and soil particle size in particles from 43 to 0.4 {micro}m diameter. Detailed analyses of this remaining soil revealed no discrete actinide phase in these soil particles, despite measurable actinide content. Observations indicate that exposure to the environment has caused the conversion of relatively insolublemore » actinide oxides to the more soluble actinyl oxides and actinyl carbonate coordinated complexes. This process has led to dissolution of actinides from discrete particles and migration to the surrounding soil surfaces, resulting in a dispersion greater than would be expected by physical transport of discrete particles alone.« less

From Actinides to Zinc: Using the Full Abundance Pattern of the Brightest Star in Reticulum II to Distinguish between Different r-process Sites

NASA Astrophysics Data System (ADS)

Ji, Alexander P.; Frebel, Anna

2018-04-01

The ultra-faint dwarf galaxy Reticulum II was enriched by a rare and prolific r-process event, such as a neutron star merger (NSM). To investigate the nature of this event, we present high-resolution Magellan/MIKE spectroscopy of the brightest star in this galaxy. The high signal-to-noise allows us to determine the abundances of 41 elements, including the radioactive actinide element Th and first ever detections of third r-process peak elements (Os and Ir) in a star outside the Milky Way. The observed neutron-capture element abundances closely match the solar r-process component, except for the first r-process peak, which is significantly lower than solar but matches other r-process enhanced stars. The ratio of the first peak to heavier r-process elements implies that the r-process site produces roughly equal masses of high and low electron fraction ejecta, within a factor of 2. We compare the detailed abundance pattern to predictions from nucleosynthesis calculations of NSMs and magnetorotationally driven jet supernovae, finding that nuclear physics uncertainties dominate over astrophysical uncertainties. We measure {log}{{Th/Eu}}=-0.84+/- 0.06 ({stat})+/- 0.22 ({sys}), somewhat lower than all previous Th/Eu observations. The youngest age we derive from this ratio is 21.7 ± 2.8 (stat) ± 10.3 (sys) Gyr, indicating that current initial production ratios do not describe the r-process event in Reticulum II. The abundances of light elements up to Zn are consistent with extremely metal-poor Milky Way halo stars. They may eventually provide a way to distinguish between NSMs and magnetorotationally driven jet supernovae, but this would require more detailed knowledge of the chemical evolution of Reticulum II. This paper includes data gathered with the 6.5 m Magellan Telescopes located at Las Campanas Observatory, Chile.

Synthesis and Characterization of Templated Ion Exchange Resins for the Selective Complexion of Actinide Ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murrray, George M.; Uy, O. Manuel

The purpose of this research is to develop polymeric extractants for the selective complexation of uranyl ions (and subsequently other actinyl and actinide ions) from aqueous solutions. Selectivity for a specific actinide ion is obtained by providing the polymers with cavities lined with complexing ligands so arranged as to match the charge, coordination number, coordination geometry, and size of the actinide ion. These cavity-containing polymers are produced by using a specific actinide ion (or surrogate) as a template around which monomeric complexing ligands are polymerized. The polymers provide useful sequestering agents for removing actinide ions from wastes and will formmore » the basis for a variety of analytical techniques for actinide determination.« less

Positron Spectroscopy of Hydrothermally Grown Actinide Oxides

DTIC Science & Technology

2014-03-27

POSITRON SPECTROSCOPY OF HYDROTHERMALLY GROWN ACTINIDE OXIDES THESIS Edward C. Schneider...United States Government. AFIT-ENP-14-M-33 POSITRON SPECTROSCOPY OF HYDROTHERMALLY GROWN ACTINIDE OXIDES THESIS...33 POSITRON SPECTROSCOPY OF HYDROTHERMALLY GROWN ACTINIDE OXIDES Edward C. Schneider, BS Captain, USAF Approved

Actinide Waste Forms and Radiation Effects

NASA Astrophysics Data System (ADS)

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

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

EPR and ENDOR Studies of Point Defects in Lithium Tetraborate Crystals

DTIC Science & Technology

2012-12-14

the US and its allies. Terrorist groups have shown interest in seeking and deploying weapons of mass destruction and mass disruption--weapons that...5]. Lithium tetraborate, has been grown pure and doped with many different elements including transition metals, actinides , and rare earth...microwave cavity is said to be “ critically coupled” when there is no reflected microwave power. Absorption of microwaves, which occurs when the magnetic

THE EFFECT OF IONIZING RADIATION ON U6+ -PHASES

DOE Office of Scientific and Technical Information (OSTI.GOV)

S. Utsunomiya; R.C. Ewing

2005-07-07

U{sup 6+}-minerals commonly form during the alteration of uraninite and spent nuclear fuel under oxidizing conditions. By the incorporation of actinides and fissiogenic elements into their structures, U{sup 6+}-minerals may be important in retarding the migration of radionuclides released during corrosion of spent nuclear fuel. Thus, the stability and the structural transformation of the U{sup 6+}-minerals in radiation fields are of great interest.

Ultratrace analysis of transuranic actinides by laser-induced fluorescence

DOEpatents

Miller, S.M.

1983-10-31

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

Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)

DOE PAGES

Dau, Phuong D.; Shuh, David K.; Sturzbecher-Hoehne, Manuel; ...

2016-07-07

The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf II is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf II(CH 3SO 2) 3-, prepared in the gas phase by reductive elimination of CH 3SO 2 from Cf III(CH 3SO 2) 4-. Comparison with synthesis of the corresponding Sm and Cm complexes revealsmore » reduction of CfIII and SmIII, and no evidence for reduction of Cm III. This reflects the comparative 3+/2+ reduction potentials: Cf 3+ (-1.60 V) ≈ Sm 3+ (-1.55 V) >> Cm 3+ (-3.7 V). Association of O 2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. Lastly, the new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf II coordination complexes and similar chemistry of Cf and Sm.« less

Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dau, Phuong D.; Shuh, David K.; Sturzbecher-Hoehne, Manuel

The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf II is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf II(CH 3SO 2) 3-, prepared in the gas phase by reductive elimination of CH 3SO 2 from Cf III(CH 3SO 2) 4-. Comparison with synthesis of the corresponding Sm and Cm complexes revealsmore » reduction of CfIII and SmIII, and no evidence for reduction of Cm III. This reflects the comparative 3+/2+ reduction potentials: Cf 3+ (-1.60 V) ≈ Sm 3+ (-1.55 V) >> Cm 3+ (-3.7 V). Association of O 2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. Lastly, the new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf II coordination complexes and similar chemistry of Cf and Sm.« less

Biogeochemical Investigations to Evaluate the Performance of the Waste Isolation Pilot Plant (WIPP) (Invited)

NASA Astrophysics Data System (ADS)

Gillow, J. B.

2009-12-01

The Waste Isolation Pilot Plant (WIPP) is a U.S. Department of Energy facility located in southeastern New Mexico, approximately 655 m (2150 ft.) below ground surface in a bedded salt, Permian evaporite formation. This mined geologic repository has been receiving transuranic (TRU) waste from defense-related and environmental-management activities since March 1999. TRU waste contains alpha-emitting transuranic nuclides with half-lives greater than twenty years at concentrations greater than 100 nCi/gram. These actinide-contaminated wastes were generated from nuclear-weapons production and related processing activities. They include various organics, adsorbed liquids, sludges, cellulosics, plastics, rubber, and a variety of metals and cemented materials. An extensive set of investigations were performed to establish the basis for TRU waste disposal at WIPP and to support initial certification from the U.S. Environmental Protection Agency. A significant element of the conceptual geochemical model for WIPP is the microbiologically-driven reactions leading to biodegradation of organic constituents in TRU wastes, as well as interactions with actinides present in the waste. This presentation will discuss the biogeochemical investigations that were performed to evaluate microbiological activity at WIPP, including studies of gas generation due to biodegradation of cellulose, plastic, and rubber materials and actinide-microbe interactions leading to changes in actinide chemical speciation. Highlights of this work are discussed here. Cellulose biodegradation in salt-brine systems results in the generation of carbon dioxide and hydrogen, and aqueous fermentation products (low molecular weight organic acids). Hypersaline brine can limit the range of microbial metabolic pathways, due to the energetic stresses of maintaining osmotic balance compatible with metabolic processes. Methanogenesis yields the lowest free energy per mole of carbon and as such is often not detected in microorganisms that thrive in salt-brine environments (halophilic bacteria). However, laboratory tests performed over a period of 10 years demonstrated the production of methane gas from cellulose metabolism. Studies of actinide-microbe interactions revealed the bioaccumulation of uranium in phosphate-rich intracellular granules. These studies advanced the understanding of the metabolism of bacteria in salt-brine systems and the influence of halophilic microbiological activity on WIPP geochemistry.

Physical and chemical characterization of actinides in soil from Johnston Atoll

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolf, S.F.; Bates, J.K.; Buck, E.C.

1997-02-01

Characterization of the actinide content of a sample of contaminated coral soil from Johnston Atoll, the site of three non-nuclear destructs of nuclear warhead-carrying THOR missiles in 1962, revealed that >99% of the total actinide content is associated with discrete bomb fragments. After removal of these fragments, there was an inverse correlation between actinide content and soil particle size in particles from 43 to 0.4 {mu}m diameter. Detailed analyses of this remaining soil revealed no discrete actinide phase in these soil particles, despite measurable actinide content. Observations indicate that exposure to the environment has caused the conversion of relatively insolublemore » actinide oxides to the more soluble actinyl oxides and actinyl carbonate coordinated complexes. This process has led to dissolution of actinides from discrete particles and migration to the surrounding soil surfaces, resulting in a dispersion greater than would be expected by physical transport of discrete particles alone. 26 refs., 4 figs., 1 tab.« less

Synthesis and characterization of a novel aminopolycarboxylate complexant for efficient trivalent f-element differentiation: N-butyl-2-acetamide-diethylenetriamine- N, N', N", N"-tetraacetic acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heathman, Colt R.; Grimes, Travis S.; Jansone-Popova, Santa

The novel metal ion complexant N-butyl-2-acetamide-diethylenetriamine-N,N',N",N"-tetraacetic acid (DTTA-BuA) uses an amide functionalization to increase the total ligand acidity and attain efficient 4f/5f differentiation in low pH conditions. The amide, when located on the diethylenetriamine platform containing four acetate pendant arms maintains the octadentate coordination sphere for all investigated trivalent f-elements. This compact coordination environment inhibits the protonation of LnL- complexes, as indicated by lower K 111 constants relative to the corresponding protonation site of the free ligand. For actinide ions, the enhanced stability of AnL- lowers the K 111 for americium and curium beyond the aptitude of potentiometric detection. Densitymore » functional theory computations indicate the difference in the back-donation ability of Am 3+ and Eu 3+ f-orbitals is mainly responsible for stronger proton affinity of EuL- compared to AmL-. The measured stability constants for the formation of AmL- and CmL- complexes are consistently higher, relative to ML- complexes with lanthanides of similar charge density. When compared with the conventional aminopolycarboxylate diethylenetriamine pentaacetic acid (DTPA), the modified DTTA-BuA complexant features higher ligand acidity and the important An 3+/Ln 3+ differentiation when deployed on a liquid–liquid distribution platform.« less

Phytosiderophore effects on subsurface actinide contaminants: potential for phytostabilization and phytoextraction.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruggiero, C. E.; Twary, S. N.; Deladurantaye, E.

2003-01-01

In recognition of the need for a safe, effective technology for long term Pu/Th/Actinide stabilization or removal from soils, we have begun an investigation of the potential for phytoremediation (phytostabilization and/or phytoextraction) of Pu and other actinide soil contaminants at DOE sites using phytosiderophore producing plants, and are investigating the contribution of phytosiderophores to actinide mobility in the subsurface environment. Phytoremediation and Phytostabilization have been proven to be a cost-effective, safe, efficient, and publicly acceptable technology for clean up and/or stabilization of contaminant metals . However, no phyto-based technologies have been developed for stabilization or removal of plutonium from soilsmore » and groundwater, and very few have been investigated for other actinides . Current metal-phytostabilization and phytoremediation techniques, predominately based around lead, nickel, and other soft-metal phytoextraction, will almost certainly be inadequate for plutonium due its distinct chemical properties . Phytosiderophore-based phytoremediation may provide technically and financially practical methods for remediation and long-term stewardship of soils that have low to moderate, near surface actinide contamination . We plan to demonstrate potential benefits of phytosiderophore-producing plants for long-term actinide contaminant stabilization by the plant's prevention of soil erosion and actinide migration through hydraulic control and/or through actinide removal through phytoextraction . We may also show possible harm caused by these plants through increased presence of actinide chelators that could increase actinide mobilization and migration in the subsurface environment. This information can then be directly applied by either removal of harmful plants, or be used to develop plant-based soil stabilization/remediation technologies .« less

Multi-podant diglycolamides and room temperature ionic liquid impregnated resins: An excellent combination for extraction chromatography of actinides.

PubMed

Gujar, R B; Ansari, S A; Verboom, W; Mohapatra, P K

2016-05-27

Extraction chromatography resins, prepared by impregnating two multi-podant diglycolamide ligands, viz. diglycolamide-functionalized calix[4]arene (C4DGA) and tripodal diglycolamide (T-DGA) dissolved in the room temperature ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (RTIL: C4mimTf2N) on Chromosorb-W (an inert solid support), gave excellent results for the removal of trivalent actinides from acidic waste solutions. Distribution coefficient measurements on several metal ions showed selective sorption of Am(III) over hexavalent uranyl ions and other fission product elements such as strontium and cesium. The sorbed metal ions could be efficiently desorbed with a complexing solution containing guanidine carbonate and EDTA buffer. The sorption of Am(III) on both resins followed pseudo-second order rate kinetics with rate constants of 1.37×10(-6) and 6.88×10(-7)g/cpmmin for T-DGA and C4DGA resins, respectively. The metal sorption on both resins indicated the Langmuir monolayer chemisorption phenomenon with Eu(III) sorption capacities of 4.83±0.21 and 0.52±0.05mg per g of T-DGA and C4DGA resins, respectively. The results of column studies show that these resins are of interest for a possible application for the recovery of hazardous trivalent actinides from dilute aqueous solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

Uranium chloride extraction of transuranium elements from LWR fuel

DOEpatents

Miller, W.E.; Ackerman, J.P.; Battles, J.E.; Johnson, T.R.; Pierce, R.D.

1992-08-25

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels containing rare earth and noble metal fission products as well as other fission products is disclosed. The oxide fuel is reduced with Ca metal in the presence of Ca chloride and a U-Fe alloy which is liquid at about 800 C to dissolve uranium metal and the noble metal fission product metals and transuranium actinide metals and rare earth fission product metals leaving Ca chloride having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein. The Ca chloride and CaO and the fission products contained therein are separated from the U-Fe alloy and the metal values dissolved therein. The U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel is contacted with a mixture of one or more alkali metal or alkaline earth metal halides selected from the class consisting of alkali metal or alkaline earth metal and Fe or U halide or a combination thereof to transfer transuranium actinide metals and rare earth metals to the halide salt leaving the uranium and some noble metal fission products in the U-Fe alloy and thereafter separating the halide salt and the transuranium metals dissolved therein from the U-Fe alloy and the metals dissolved therein. 1 figure.

Uranium chloride extraction of transuranium elements from LWR fuel

DOEpatents

Miller, William E.; Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Pierce, R. Dean

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels containing rare earth and noble metal fission products as well as other fission products is disclosed. The oxide fuel is reduced with Ca metal in the presence of Ca chloride and a U-Fe alloy which is liquid at about 800.degree. C. to dissolve uranium metal and the noble metal fission product metals and transuranium actinide metals and rare earth fission product metals leaving Ca chloride having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein. The Ca chloride and CaO and the fission products contained therein are separated from the U-Fe alloy and the metal values dissolved therein. The U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel is contacted with a mixture of one or more alkali metal or alkaline earth metal halides selected from the class consisting of alkali metal or alkaline earth metal and Fe or U halide or a combination thereof to transfer transuranium actinide metals and rare earth metals to the halide salt leaving the uranium and some noble metal fission products in the U-Fe alloy and thereafter separating the halide salt and the transuranium metals dissolved therein from the U-Fe alloy and the metals dissolved therein.

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

DOEpatents

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

1984-09-12

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

Actinide extraction methods

DOEpatents

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

2010-09-21

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

Gas core reactors for actinide transmutation. [uranium hexafluoride

NASA Technical Reports Server (NTRS)

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

1979-01-01

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

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin, Southwestern India.

PubMed

Gurumurthy, G P; Balakrishna, K; Tripti, M; Audry, Stéphane; Riotte, Jean; Braun, J J; Udaya Shankar, H N

2014-04-01

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary-Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.

Monte Carlo calculations of the incineration of plutonium and minor actinides of laser fusion inertial confinement fusion fission energy (LIFE) engine

NASA Astrophysics Data System (ADS)

Adem, ACIR; Eşref, BAYSAL

2018-07-01

In this paper, neutronic analysis in a laser fusion inertial confinement fusion fission energy (LIFE) engine fuelled plutonium and minor actinides using a MCNP codes was investigated. LIFE engine fuel zone contained 10 vol% TRISO particles and 90 vol% natural lithium coolant mixture. TRISO fuel compositions have Mod①: reactor grade plutonium (RG-Pu), Mod②: weapon grade plutonium (WG-Pu) and Mod③: minor actinides (MAs). Tritium breeding ratios (TBR) were computed as 1.52, 1.62 and 1.46 for Mod①, Mod② and Mod③, respectively. The operation period was computed as ∼21 years when the reference TBR > 1.05 for a self-sustained reactor for all investigated cases. Blanket energy multiplication values (M) were calculated as 4.18, 4.95 and 3.75 for Mod①, Mod② and Mod③, respectively. The burnup (BU) values were obtained as ∼1230, ∼1550 and ∼1060 GWd tM–1, respectively. As a result, the higher BU were provided with using TRISO particles for all cases in LIFE engine.

Potential benefits of waste transmutation to the U.S. high-level waste respository

DOE Office of Scientific and Technical Information (OSTI.GOV)

Michaels, G.E.

1995-10-01

This paper reexamines the potential benefits of waste transmutation to the proposed U.S. geologic repository at the Yucca Mountain site based on recent progress in the performance assessment for the Yucca Mountain base case of spent fuel emplacement. It is observed that actinides are assumed to have higher solubility than in previous studies and that Np and other actinides now dominate the projected aqueous releases from a Yucca Mountain repository. Actinides are also indentified as the dominant source of decay heat in the repository, and the effect of decay heat in perturbing the hydrology, geochemistry, and thermal characteristics of Yuccamore » Mountain are reviewed. It is concluded that the potential for thermally-driven, buoyant, gas-phase flow at Yucca Mountain introduces data and modeling requirements that will increase the costs of licensing the site and may cause the site to be unattractive for geologic disposal of wastes. A transmutation-enabled cold repository is proposed that might allow licensing of a repository to be based upon currently observable characteristics of the Yucca Mountain site.« less

Evaluation of Mass Filtered, Time Dilated, Time-of-Flight Mass Spectrometry

DTIC Science & Technology

2010-01-01

Figure 4.4: Mass resolution dependence on field for selected actinides and surrogates...45 Figure 4.7: Mass resolution dependence on field for selected actinides and actinide surrogates, modeled with no initial...system. A somewhat better mass resolution would need to be achieved in order to separate hydride molecules in the actinide region. However, the

Exploring actinide materials through synchrotron radiation techniques.

PubMed

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

2014-12-10

Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of actinide-based materials. This trend is partially driven by the basic needs for multi-scale actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X-ray absorption spectroscopy, X-ray diffraction and scattering spectroscopy, which are powerful tools to characterize actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with actinides are illustrated as well. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separation of actinides from lanthanides utilizing molten salt electrorefining

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grimmett, D.L.; Fusselman, S.P.; Roy, J.J.

1996-10-01

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

Understanding Release from Actinide Targets -- Recent Results from RIB Development

NASA Astrophysics Data System (ADS)

Kronenberg, Andreas; Carter, H. K.; Spejewski, E. H.; Stracener, D. W.

2006-10-01

Development of ion beams of short-lived isotopes is crucial for modern nuclear structure and nuclear astrophysics. The Holifield Radioactive Ion Beam Facility at Oak Ridge National Laboratory uses the ISOL (Isotope Separation Online) technique to provide radioactive ion beams. So far, uranium carbide has been used as a target to produce neutron-rich fission fragments. Thermodynamic calculations indicate the possibility of in-situ chemical side band formations of volatile species of refractory metals, such as V and Re. These elements release out of oxide targets after production in a nuclear reaction, and can occur only through in-situ formation of their volatile oxide. These have been confirmed experimentally. The results from recent, more detailed investigations of ThO2, UB4 and other actinide targets as well as conclusions from systematic studies will be presented. This research was sponsored by the NNSA under Stewardship Science Academic Alliance program through DOE Cooperative Agreement # DE-FC03-3NA00143.

The Heavy Nuclei eXplorer (HNX) Mission

NASA Technical Reports Server (NTRS)

Binns, W. R.; Adams, J. H.; Barbier, L. M.; Craig, N.; Cummings, A. C.; Cummings, J. R.; Doke, T.; Hasebe, N.; Hayashi, T.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

The primary scientific objectives of HNX, which was recently selected by NASA for a Small Explorer (SMEX) Mission Concept Study, are to measure the age of the galactic cosmic rays (GCR) since nucleosynthesis, determine the injection mechanism for the GCR accelerator (Volatility or FIP), and study the mix of nucleosynthetic processes that contribute to the source of GCRs. The experimental goal of HNX is to measure the elemental abundances of all individual stable nuclei from neon through the actinides and possibly beyond. HNX is composed of two instruments: ECCO, which measures elemental abundances of nuclei with Z greater than or equal to 72, and ENTICE. which measures elemental abundances of nuclei with Z between 10 and 82. We describe the mission and the science that can be addressed by HNX.

Challenges in the quality assurance of elemental and isotopic analyses in the nuclear domain benefitting from high resolution ICP-OES and sector field ICP-MS.

PubMed

Krachler, Michael; Alvarez-Sarandes, Rafael; Van Winckel, Stefaan

Accurate analytical data reinforces fundamentally the meaningfulness of nuclear fuel performance assessments and nuclear waste characterization. Regularly lacking matrix-matched certified reference materials, quality assurance of elemental and isotopic analysis of nuclear materials remains a challenging endeavour. In this context, this review highlights various dedicated experimental approaches envisaged at the European Commission-Joint Research Centre-Institute for Transuranium Elements to overcome this limitation, mainly focussing on the use of high resolution-inductively coupled plasma-optical emission spectrometry (HR-ICP-OES) and sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS). However, also α- and γ-spectrometry are included here to help characterise extensively the investigated actinide solutions for their actual concentration, potential impurities and isotopic purity.

RECOVERY OF ACTINIDES FROM AQUEOUS NITRIC ACID SOLUTIONS

DOEpatents

Ader, M.

1963-11-19

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

Actinide abundances in ordinary chondrites

USGS Publications Warehouse

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

1990-01-01

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

Bidentate organophosphorus solvent extraction process for actinide recovery and partition

DOEpatents

Schulz, Wallace W.

1976-01-01

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

Impact of minor actinide recycling on sustainable fuel cycle options

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heidet, F.; Kim, T. K.; Taiwo, T. A.

The recent Evaluation and Screening study chartered by the U.S. Department of Energy, Office of Nuclear Energy, has identified four fuel cycle options as being the most promising. Among these four options, the two single-stage fuel cycles rely on a fast reactor and are differing in the fact that in one case only uranium and plutonium are recycled while in the other case minor actinides are also recycled. The two other fuel cycles are two-stage and rely on both fast and thermal reactors. They also differ in the fact that in one case only uranium and plutonium are recycled whilemore » in the other case minor actinides are also recycled. The current study assesses the impact of recycling minor actinides on the reactor core design, its performance characteristics, and the characteristics of the recycled material and waste material. The recycling of minor actinides is found not to affect the reactor core performance, as long as the same cycle length, core layout and specific power are being used. One notable difference is that the required transuranics (TRU) content is slightly increased when minor actinides are recycled. The mass flows are mostly unchanged given a same specific power and cycle length. Although the material mass flows and reactor performance characteristics are hardly affected by recycling minor actinides, some differences are observed in the waste characteristics between the two fuel cycles considered. The absence of minor actinides in the waste results in a different buildup of decay products, and in somewhat different behaviors depending on the characteristic and time frame considered. Recycling of minor actinides is found to result in a reduction of the waste characteristics ranging from 10% to 90%. These results are consistent with previous studies in this domain and depending on the time frame considered, packaging conditions, repository site, repository strategy, the differences observed in the waste characteristics could be beneficial and help improve the repository performance. On the other hand, recycling minor actinides also results in an increase of the recycled fuel characteristics and therefore of the charged fuel. The radioactivity is slightly increased while the decay heat and radiotoxicities are very significantly increased. Despite these differences, the characteristics of the fuel at time of discharge remain similar whether minor actinides are recycled or not, with the exception of the inhalation radiotoxicity which is significantly larger with minor actinide recycling. After some cooling the characteristics of the discharged fuel become larger when minor actinides are recycled, potentially affecting the reprocessing plant requirements. Recycling minor actinides has a negative impact on the characteristics of the fresh fuel and will make it more challenging to fabricate fuel containing minor actinides.« less

DISTRIBUTION OF ACTINIDES BETWEEN THE AQUEOUS AND ORGANIC PHASES IN THE TALSPEAK PROCESS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudisill, T.; Kyser, E.

2010-09-02

One objective of the US Department of Energy's Office of Nuclear Energy (DOE-NE) is the development of sustainable nuclear fuel cycles which improve uranium resource utilization, maximize energy generation, minimize waste generation, improve safety, and complement institutional measures limiting proliferation risks. Activities in progress which support this objective include the development of advanced separation technologies to recover the actinides from used nuclear fuels. With the increased interest in the development of technology to allow closure of the nuclear fuel cycle, the TALSPEAK process is being considered for the separation of Am and Cm from the lanthanide fission products in amore » next generation reprocessing plant. However, at this time, the level of understanding associated with the chemistry and the control of the process variables is not acceptable for deployment of the process on an industrial scale. To address this issue, DOE-NE is supporting basic scientific studies focused on the TALSPEAK process through its Fuel Cycle Research and Development (R&D) program. One aspect of these studies is an experimental program at the Savannah River National Laboratory (SRNL) in which temperature-dependent distribution coefficients for the extraction of actinide elements in the TALSPEAK process were measured. The data were subsequently used to calculate conditional enthalpies and entropies of extraction by van't Hoff analysis to better understand the thermodynamic driving forces for the TALSPEAK process. In the SRNL studies, the distribution of Pu(III) in the TALSPEAK process was of particular interest. A small amount of Pu(III) would be present in the feed due to process losses and valence adjustment in prior recovery operations. Actinide elements such as Np and Pu have multiple stable oxidation states in aqueous solutions; therefore the oxidation state for these elements must be controlled in the TALSPEAK process, as the extraction chemistry is dependent upon the actinide's valence. Since our plans included the measurement of Pu(III) distribution coefficients using a Np(V) solution containing small amounts of {sup 238}Pu, it was necessary to demonstrate that the desired oxidation states of Np and Pu are produced and could be stabilized in a buffered lactate solution containing diethylenetriaminepentaacetic (DTPA). The stability of Np(V) and Pu(III) in lactic acid/DTPA solutions was evaluated by ultraviolet-visible (UV-vis) spectroscopy. To perform the evaluation, Np and Pu were added to solutions containing either hydroxylamine nitrate (HAN) or ferrous sulfamate (FS) as the reductant and nominally 1.5 M lactic acid/0.05 M DTPA. The pH of the solution was subsequently adjusted to nominally 2.8 as would be performed in the TALSPEAK process. In the valence adjustment study, we found that it was necessary to reduce Pu to Pu(III) prior to combining with the lactic acid and DTPA. The Pu reduction was performed using either HAN or FS. When FS was used, Np was reduced to Np(IV). The spectroscopic studies showed that Np(V) and Pu(III) are not stable in lactic acid/DTPA solutions. The stability of Np(IV)- and Pu(IV)-DTPA complexes are much greater than the stability of the Np(V)- and Pu(III)-DTPA complexes, and as a result, Np is slowly reduced to Np(IV) and Pu is slowly oxidized to Pu(IV) due to the reduced activity of the more stable complexes. When Np(V) was added to a solution containing a 1.5 M lactic acid/ammonium lactate buffer and 0.05 M DTPA, approximately 50% of the Np was reduced to Np(IV) in the first day. The fraction of Np(V) in the solution continued to diminish with time and was essentially reduced to Np(IV) after one week. When Pu(III) was added to a lactic acid/DTPA solution of the same composition, the spectrum recorded following at least two days after preparation of the solution continued to show some sign of Pu(III). The Pu(III) was completely oxidized to Pu(IV) after 3-4 days. The UV-vis spectroscopy demonstrated that Np(V) and Pu(III) were the predominate valences in the lactic acid/DTPA solution for the better part of a day following solution preparation. Based on these results, we chose to initially add HAN to the actinide tracer solution prepared for the distribution coefficient measurements (to produce Pu(III)) prior to combining with lactic acid and DTPA. The distribution coefficient measurements were expected to be complete in 2-3 h; therefore, Np(V) and Pu(III) valences would predominate in the solution during this time. Prior to adding the HAN to the actinide tracers, we added sufficient Am(III) activity to allow the measurement of distribution coefficients during the extraction experiments. Protactinium (V) distribution coefficients were also measured using the activity which was in secular equilibrium with the {sup 237}Np. The actinide distribution coefficients were measured at pH 2.8 and 3.5 and covered a range of temperatures from nominally 20 to 60 C.« less

Differential lead retention in zircons: implications for nuclear waste containment.

PubMed

Gentry, R V; Sworski, T J; McKown, H S; Smith, D H; Eby, R E; Christie, W H

1982-04-16

An innovative ultrasensitive technique was used for lead isotopic analysis of individual zircons extracted from granite core samples at depths of 960, 2170, 2900, 3930, and 4310 meters. The results show that lead, a relatively mobile element compared to the nuclear waste-related actinides uranium and thorium, has been highly retained at elevated temperatures (105 degrees to 313 degrees C) under conditions relevant to the burial of synthetic rock waste containers in deep granite holes.

Capabilities of the LDEF-2 heavy nuclei collection

NASA Technical Reports Server (NTRS)

Drach, J.; Price, P. B.; Salamon, M. H.; Tarle, G.; Ahlen, S. P.

1985-01-01

To take the next big step beyond High Energy Astronomy Observatory (HEAO-3) the Heavy Nuclei Collector (HNC), to be carried on an LDEF reflight, has the goals of greatly increased collecting power ( 30 actinides) and charge resolution sigma sub Z or = 0.25 E for Z up to approximately 100, which will provide abundances of all the charges 40 or Z or = 96 and permit sensitive searches for hypothetical particles such as monopoles, superheavy elements, and quark nuggets.

Functionalization of mesoporous materials for lanthanide and actinide extraction.

PubMed

Florek, Justyna; Giret, Simon; Juère, Estelle; Larivière, Dominic; Kleitz, Freddy

2016-10-14

Among the energy sources currently available that could address our insatiable appetite for energy and minimize our CO2 emission, solar, wind, and nuclear energy currently occupy an increasing portion of our energy portfolio. The energy associated with these sources can however only be harnessed after mineral resources containing valuable constituents such as actinides (Ac) and rare earth elements (REEs) are extracted, purified and transformed into components necessary for the conversion of energy into electricity. Unfortunately, the environmental impacts resulting from their manufacture including the generation of undesirable and, sometimes, radioactive wastes and the non-renewable nature of the mineral resources, to name a few, have emerged as challenges that should be addressed by the scientific community. In this perspective, the recent development of functionalized solid materials dedicated to selective elemental separation/pre-concentration could provide answers to several of the above-mentioned challenges. This review focuses on recent advances in the field of mesoporous solid-phase (SP) sorbents designed for REEs and Ac liquid-solid extraction. Particular attention will be devoted to silica and carbon sorbents functionalized with commonly known ligands, such as phosphorus or amide-containing functionalities. The extraction performances of these new systems are discussed in terms of sorption capacity and selectivity. In order to support potential industrial applications of the silica and carbon-based sorbents, their main drawbacks and advantages are highlighted and discussed.

Actinide ion sensor for pyroprocess monitoring

DOEpatents

Jue, Jan-fong; Li, Shelly X.

2014-06-03

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

Two new rodent models for actinide toxicity studies. [/sup 237/Pu, /sup 241/Am

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, G.N.; Jones, C.W.; Gardner, P.A.

1981-04-01

Two small rodent species, the grasshopper mouse (Onychomys leucogaster) and the deer mouse (Peromyscus maniculatus), have tenacious and high retention in the liver and skeleton of plutonium and americium following intraperitoneal injection of Pu and Am in citrate solution. Liver retention of Pu and Am in the grasshopper mouse is higher than liver retention in the deer mouse. Both of these rodents are relatively long-lived, breed well in captivity, and adapt suitably to laboratory conditions. It is suggested that these two species of mice, in which plutonium retention is high and prolonged in both the skeleton and liver, as itmore » is in man, may be useful animal models for actinide toxicity studies.« less

Method for fluorination of actinide fluorides and oxyfluorides using O/sub 2/F/sub 2/

DOEpatents

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

1984-08-01

The present invention relates generally to methods of fluorination and more particularly to the use of O/sub 2/F/sub 2/ for the preparation of actinide hexafluorides, and for the extraction of deposited actinides and fluorides and oxyfluorides thereof from reaction vessels. The experiments set forth hereinabove demonstrate that the room temperature or below use of O/sub 2/F/sub 2/ will be highly beneficial for the preparation of pure actinide hexafluorides from their respective tetrafluorides without traces of HF being present as occurs using other fluorinating agents: and decontamination of equipment previously exposed to actinides: e.g., walls, feed lines, etc.

Actinides-1981

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

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.

Transuranic Computational Chemistry.

PubMed

Kaltsoyannis, Nikolas

2018-02-26

Recent developments in the chemistry of the transuranic elements are surveyed, with particular emphasis on computational contributions. Examples are drawn from molecular coordination and organometallic chemistry, and from the study of extended solid systems. The role of the metal valence orbitals in covalent bonding is a particular focus, especially the consequences of the stabilization of the 5f orbitals as the actinide series is traversed. The fledgling chemistry of transuranic elements in the +II oxidation state is highlighted. Throughout, the symbiotic interplay of experimental and computational studies is emphasized; the extraordinary challenges of experimental transuranic chemistry afford computational chemistry a particularly valuable role at the frontier of the periodic table. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study on the leaching behavior of actinides from nuclear fuel debris

NASA Astrophysics Data System (ADS)

Kirishima, Akira; Hirano, Masahiko; Akiyama, Daisuke; Sasaki, Takayuki; Sato, Nobuaki

2018-04-01

For the prediction of the leaching behavior of actinides contained in the nuclear fuel debris generated by the Fukushima Daiichi nuclear power plant accident in Japan, simulated fuel debris consisting of a UO2-ZrO2 solid solution doped with 137Cs, 237Np, 236Pu, and 241Am tracers was synthesized and investigated. The synthesis of the debris was carried out by heat treatment at 1200 °C at different oxygen partial pressures, and the samples were subsequently used for leaching tests with Milli-Q water and seawater. The results of the leaching tests indicate that the leaching of actinides depends on the redox conditions under which the debris was generated; for example, debris generated under oxidative conditions releases more actinide nuclides to water than that generated under reductive conditions. Furthermore, we found that, as Zr(IV) increasingly substituted U(IV) in the fluorite crystal structure of the debris, the actinide leaching from the debris decreased. In addition, we found that seawater leached more actinides from the debris than pure water, which seems to be caused by the complexation of actinides by carbonate ions in seawater.

Implications of Fast Reactor Transuranic Conversion Ratio

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steven J. Piet; Edward A. Hoffman; Samuel E. Bays

2010-11-01

Theoretically, the transuranic conversion ratio (CR), i.e. the transuranic production divided by transuranic destruction, in a fast reactor can range from near zero to about 1.9, which is the average neutron yield from Pu239 minus 1. In practice, the possible range will be somewhat less. We have studied the implications of transuranic conversion ratio of 0.0 to 1.7 using the fresh and discharge fuel compositions calculated elsewhere. The corresponding fissile breeding ratio ranges from 0.2 to 1.6. The cases below CR=1 (“burners”) do not have blankets; the cases above CR=1 (“breeders”) have breeding blankets. The burnup was allowed to floatmore » while holding the maximum fluence to the cladding constant. We graph the fuel burnup and composition change. As a function of transuranic conversion ratio, we calculate and graph the heat, gamma, and neutron emission of fresh fuel; whether the material is “attractive” for direct weapon use using published criteria; the uranium utilization and rate of consumption of natural uranium; and the long-term radiotoxicity after fuel discharge. For context, other cases and analyses are included, primarily once-through light water reactor (LWR) uranium oxide fuel at 51 MWth-day/kg-iHM burnup (UOX-51). For CR<1, the heat, gamma, and neutron emission increase as material is recycled. The uranium utilization is at or below 1%, just as it is in thermal reactors as both types of reactors require continuing fissile support. For CR>1, heat, gamma, and neutron emission decrease with recycling. The uranium utilization exceeds 1%, especially as all the transuranic elements are recycled. exceeds 1%, especially as all the transuranic elements are recycled. At the system equilibrium, heat and gamma vary by somewhat over an order of magnitude as a function of CR. Isotopes that dominate heat and gamma emission are scattered throughout the actinide chain, so the modest impact of CR is unsurprising. Neutron emitters are preferentially found among the higher actinides, so the neutron emission varies much stronger with CR, about three orders of magnitude.« less

Effect of Temperature on the Protonation of the TALSPEAK Ligands: Lactic and Diethylenetrinitropentaacetic Acids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Guoxin; Rao, Linfeng

2009-10-20

The protonation reactions of two ligands that play important roles in the TALSPEAK process for the separation of trivalent actinides from lanthanides, lactic acid and diethylenetrinitropentaacetic acid (DTPA), have been studied at variable temperatures. The protonation constants at 10-70 C were determined by titration potentiometry and the protonation enthalpies were determined at 25 C by titration microcalorimetry. The protonation constants remain essentially unchanged (25-70 C) within the experimental uncertainties, indicating that the effect of temperature on the protonation of lactate is insignificant. In contrast, the protonation constants of DTPA (log {beta}H's) generally decrease as the temperature is increased. Results frommore » this study indicate that the effect of temperature on the protonation of DTPA could alter the speciation of metal ions (actinides and lanthanides) in the TALSPEAK system, since lower values of log{beta}H at higher temperatures suggest that the hydrogen ions would compete less strongly with the metal ions for the complexation of DTPA at higher temperatures.« less

Method for producing nuclear fuel

DOEpatents

Haas, Paul A.

1983-01-01

Nuclear fuel is made by contacting an aqueous solution containing an actinide salt with an aqueous solution containing ammonium hydroxide, ammonium oxalate, or oxalic acid in an amount that will react with a fraction of the actinide salt to form a precipitate consisting of the hydroxide or oxalate of the actinide. A slurry consisting of the precipitate and solution containing the unreacted actinide salt is formed into drops which are gelled, calcined, and pressed to form pellets.

Zirconium behaviour during electrorefining of actinide-zirconium alloy in molten LiCl-KCl on aluminium cathodes

NASA Astrophysics Data System (ADS)

Meier, R.; Souček, P.; Malmbeck, R.; Krachler, M.; Rodrigues, A.; Claux, B.; Glatz, J.-P.; Fanghänel, Th.

2016-04-01

A pyrochemical electrorefining process for the recovery of actinides from metallic nuclear fuel based on actinide-zirconium alloys (An-Zr) in a molten salt is being investigated. In this process actinides are group-selectively recovered on solid aluminium cathodes as An-Al alloys using a LiCl-KCl eutectic melt at a temperature of 450 °C. In the present study the electrochemical behaviour of zirconium during electrorefining was investigated. The maximum amount of actinides that can be oxidised without anodic co-dissolution of zirconium was determined at a selected constant cathodic current density. The experiment consisted of three steps to assess the different stages of the electrorefining process, each of which employing a fresh aluminium cathode. The results indicate that almost a complete dissolution of the actinides without co-dissolution of zirconium is possible under the applied experimental conditions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paton, Ian

The Rocky Flats Environmental Technology Site (RFETS) is a Department of Energy facility located approximately 16 miles northwest of Denver, Colorado. Processing and fabrication of nuclear weapons components occurred at Rocky Flats from 1952 through 1989. Operations at the Site included the use of several radionuclides, including plutonium-239/240 (Pu), americium-241 (Am), and various uranium (U) isotopes, as well as several types of chlorinated solvents. The historic operations resulted in legacy contamination, including contaminated facilities, process waste lines, buried wastes and surface soil contamination. Decontamination and removal of buildings at the site was completed in late 2005, culminating more than tenmore » years of active environmental remediation work. The Corrective Action Decision/Record of Decision was subsequently approved in 2006, signifying regulatory approval and closure of the site. The use of RFETS as a National Wildlife Refuge is scheduled to be in full operation by 2012. To develop a plan for remediating different types of radionuclide contaminants present in the RFETS environment required understanding the different environmental transport pathways for the various actinides. Developing this understanding was the primary objective of the Actinide Migration Evaluation (AME) project. Findings from the AME studies were used in the development of RFETS remediation strategies. The AME project focused on issues of actinide behavior and mobility in surface water, groundwater, air, soil and biota at RFETS. For the purposes of the AME studies, actinide elements addressed included Pu, Am, and U. The AME program, funded by DOE, brought together personnel with a broad range of relevant expertise in technical investigations. The AME advisory panel identified research investigations and approaches that could be used to solve issues related to actinide migration at the Site. An initial step of the AME was to develop a conceptual model to provide a qualitative description of the relationships among potential actinide sources and transport pathways at RFETS. One conceptual model was developed specifically for plutonium and americium, because of their similar geochemical and transport properties. A separate model was developed for uranium because of its different properties and mobility in the environment. These conceptual models were guidelines for quantitative analyses described in the RFETS Pathway Analysis Report, which used existing data from the literature as well as site-specific analyses, including field, laboratory and modeling studies to provide quantitative estimates of actinide migration in the RFETS environment. For pathways where more than one method was used to estimate offsite loads for a specific pathway, the method yielding the highest estimated off-site was used for comparison purposes. For all actinides studied, for pre-remediation conditions, air and surface water were identified to be the dominant transport mechanisms. The estimated annual airborne plutonium-239/240 load transported off site exceeded the surface water load by roughly a factor of 40. However, despite being the largest transport pathway, airborne radionuclide concentrations at the monitoring location with the highest measurements during the period studied were less than two percent of the allowable 10 milli-rem standard governing DOE facilities. Estimated actinide loads for other pathways were much less. Shallow groundwater was approximately two orders of magnitude lower, or 1/100 of the load conveyed in surface water. The estimated biological pathway load for plutonium was approximately five orders of magnitude less, or 1/100,000, of the load estimated for surface-water. The pathway analysis results were taken into consideration during subsequent remediation activities that occurred at the site. For example, when the 903 Pad area was remediated to address elevated concentrations of Pu and Am in the surface soil, portable tent structures were constructed to prevent wind and water erosion from occurring while remediation activities took place. Following remediation of the 903 Pad and surrounding area, coconut erosion blankets were installed to mitigate erosion effects while vegetation was reestablished [2]. These measures were effective tools to address the primary transport mechanisms identified, coupling the scientific understanding of the site with the remediation strategy.« less

Anomalous elastic properties across the γ to α volume collapse in cerium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lipp, Magnus J.; Jenei, Zs.; Cynn, H.

2017-10-31

The behavior of the f-electrons in the lanthanides and actinides governs important macroscopic properties but their pressure and temperature dependence is not fully explored. Cerium with nominally just one 4f electron offers a case study with its iso-structural volume collapse from the γ-phase to the α-phase ending in a critical point (pC, VC, TC), unique among the elements, whose mechanism remains controversial. Here, we present longitudinal (cL) and transverse sound speeds (cT) versus pressure from higher than room temperature to TC for the first time. While cL experiences a non-linear dip at the volume collapse, cT shows a step-like change.more » This produces very peculiar macroscopic properties: the minimum in the bulk modulus becomes more pronounced, the step-like increase of the shear modulus diminishes and the Poisson’s ratio becomes negative—meaning that cerium becomes auxetic. At the critical point itself cerium lacks any compressive strength but offers resistance to shear.« less

Hyperfine interactions of trans-lead elements studied by nuclear radiations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ansaldo, E.J.

1973-09-16

The applications of nuclear radiation methods to the study of hyperfine interactions (hfi) for elements beyond Pb in the periodic table are reviewed. A general discussion of hfi is presented along with a review of specific methods. The techniques are illustrated whenever possible by their application to the actinides, with emphasis on the unsolved aspects of the results. A special method of sample preparation is ion implantation, in which stable or radioactive ions of practically any element are shot into the host, either by means of isotope separators or the recoil energy of nuclear reactions or radioactive decays. The locationmore » of the implanted (recoiled) atom in the lattice has to be assessed for a reliable determination of the hfi. Therefore, a chapter on the channeling technique is also included. (JRD)« less

Method for fluorination of actinide fluorides and oxyfluorides thereof using O.sub.2 F.sub.2

DOEpatents

Eller, Phillip G.; Malm, John G.; Penneman, Robert A.

1988-01-01

Method for fluorination of actinides and fluorides and oxyfluorides thereof using O.sub.2 F.sub.2 which generates actinide hexafluorides, and for removal of actinides and compounds thereof from surfaces upon which they appear as unwanted deposits. The fluorinating agent, O.sub.2 F.sub.2, has been observed to readily perform the above-described tasks at sufficiently low temperatures that there is virtually no damage to the containment vessels. Moreover, the resulting actinide hexafluorides are thereby not destroyed by high temperature reactions with the walls of the reaction vessel. Dioxygen difluoride is easily prepared, stored and transferred to the desired place of reaction.

Method for fluorination of actinide fluorides and oxyfluorides thereof using O[sub 2]F[sub 2

DOEpatents

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

1988-11-08

Method is described for fluorination of actinides and fluorides and oxyfluorides thereof using O[sub 2]F[sub 2] which generates actinide hexafluorides, and for removal of actinides and compounds thereof from surfaces upon which they appear as unwanted deposits. The fluorinating agent, O[sub 2]F[sub 2], has been observed to readily perform the above-described tasks at sufficiently low temperatures that there is virtually no damage to the containment vessels. Moreover, the resulting actinide hexafluorides are thereby not destroyed by high temperature reactions with the walls of the reaction vessel. Dioxygen difluoride is easily prepared, stored and transferred to the desired place of reaction.

Separation of actinides using capillary extraction chromatography-inductively coupled plasma mass spectrometry.

PubMed

Peterson, Dominic S; Montoya, Velma M

2009-08-01

Trace levels of actinides have been separated on capillary extraction chromatography columns. Detection of the actinides was achieved using an inductively coupled plasma mass spectrometer, which was coupled with the extraction chromatography system. In this study, we compare 30-cm long, 4.6 mm i.d. columns to capillary columns (750 microm i.d.) with lengths from 30 cm up to 150 cm. The columns that were tested were packed with TRU resin. We were able to separate a mixture of five actinides ((232)Th, (238)U, (237)Np, (239)Pu, and (241)Am). This work has application to rapid bioassay as well as automated separations of actinide materials.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Bo-Young; Choi, Daewoong; Park, Se Hwan

Korea Atomic Energy Research Institute (KAERI) have been developing the design and deployment methodology of Laser- Induced Breakdown Spectroscopy (LIBS) instrument for safeguards application within the argon hot cell environment at Advanced spent fuel Conditioning Process Facility (ACPF), where ACPF is a facility being refurbished for the laboratory-scaled demonstration of advanced spent fuel conditioning process. LIBS is an analysis technology used to measure the emission spectra of excited elements in the local plasma of a target material induced by a laser. The spectra measured by LIBS are analyzed to verify the quality and quantity of the specific element in themore » target matrix. Recently LIBS has been recognized as a promising technology for safeguards purposes in terms of several advantages including a simple sample preparation and in-situ analysis capability. In particular, a feasibility study of LIBS to remotely monitor the nuclear material in a high radiation environment has been carried out for supporting the IAEA safeguards implementation. Fiber-Optic LIBS (FO-LIBS) deployment was proposed by Applied Photonics Ltd because the use of fiber optics had benefited applications of LIBS by delivering the laser energy to the target and by collecting the plasma light. The design of FO-LIBS instrument for the measurement of actinides in the spent fuel and high temperature molten salt at ACPF had been developed in cooperation with Applied Photonics Ltd. FO-LIBS has some advantages as followings: the detectable plasma light wavelength range is not limited by the optical properties of the thick lead-glass shield window and the potential risk of laser damage to the lead-glass shield window is not considered. The remote LIBS instrument had been installed at ACPF and then the feasibility study for monitoring actinide elements such as uranium, plutonium, and curium in process materials has been carried out. (authors)« less

REGENERATION OF REACTOR FUEL ELEMENTS

DOEpatents

Lyon, W.L.

1960-04-01

A process is described for concentrating uranium and/or plutonium metal in aluminum alloys in which the actinide content was partially consumed by neutron bombardinent. Two embodiments are claimed: Either the alloy is heated, together with zinc chloride to at least 1000 deg C whereby some aluminum, in the form of aluminum chloride, and any zinc formed volatilize; or else aluminum fluoride is added and reacted at 800 to 1000 deg O and substmospheric pressure whereby pant of the aluminum volatilizes and aluminum subfluoride.

Assessment of Metaborate Fusion for the Rapid Dissolution of Solid Samples: Suitability with the Northstar ARSIIe

DTIC Science & Technology

2016-07-01

goal of this project was to develop a rapid dissolution methodology for solid environmental samples and a crude pre- concentration of actinides ...environmental solid samples needed to be removed from the samples prior to actinide separation on the ARSIIe system. As a result of this project, two...procedures were developed, one applicable to the pre-concentration of the actinides only and a second for the pre-concentration of both actinides and

Method for the concentration and separation of actinides from biological and environmental samples

DOEpatents

Horwitz, E. Philip; Dietz, Mark L.

1989-01-01

A method and apparatus for the quantitative recover of actinide values from biological and environmental sample by passing appropriately prepared samples in a mineral acid solution through a separation column of a dialkyl(phenyl)-N,N-dialylcarbamoylmethylphosphine oxide dissolved in tri-n-butyl phosphate on an inert substrate which selectively extracts the actinide values. The actinide values can be eluted either as a group or individually and their presence quantitatively detected by alpha counting.

The efficacy of denaturing actinide elements as a means of decreasing materials attractiveness

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hase, K.R.; Bathke, C.G.; Ebbinghaus, B.B.

2013-07-01

This study considers the concept of denaturing as applied to the actinide elements present in spent fuel as a means to reduce materials attractiveness. Highly attractive materials generally have low values of bare critical mass, heat content, and dose. To denature an attractive element, its spent-fuel isotopic composition (isotopic vector) is intentionally modified by introducing sufficient quantities of a significantly less attractive isotope to dilute the concentration of a highly attractive isotope so that the overall attractiveness of the element is reduced. The authors used FOM (Figure of Merit) formula as the material attractiveness metric for their parametric determination ofmore » the attractiveness of the Pu and U. Materials attractiveness needs to be considered in three distinct phases in the process to construct a nuclear explosive device (NED): the acquisition phase, processing phase, and utilization phase. The results show that denaturing uranium with {sup 238}U is actually an effective means of reducing the attractiveness. For uranium with a large minority of {sup 235}U, a mixture of 80% {sup 238}U to 20% {sup 235}U is required to reduce the attractiveness to low. For uranium with a large concentration of {sup 233}U, a mixture of 88% {sup 238}U to 12% {sup 233}U is required to reduce the attractiveness to low. The results also show that denaturing plutonium with {sup 238}Pu is less effective than denaturing uranium with {sup 238}U. Using {sup 238}Pu as the denaturing agent would require 80% or more by mass in order to reduce the attractiveness to low. No amount of {sup 240}Pu is enough to reduce the plutonium attractiveness below medium. The combination of {sup 238}Pu and {sup 240}Pu would require approximately 70% {sup 238}Pu and 25% {sup 240}Pu by mass to reduce the plutonium attractiveness to low.« less

Actinide Sorption in Rainier Mesa Tunnel Waters from the Nevada Test Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, P; Zavarin, M; Leif, R

2007-12-17

The sorption behavior of americium (Am), plutonium (Pu), neptunium (Np), and uranium (U) in perched Rainier Mesa tunnel water was investigated. Both volcanic zeolitized tuff samples and groundwater samples were collected from Rainier Mesa, Nevada Test Site, NV for a series of batch sorption experiments. Sorption in groundwater with and without the presence of dissolved organic matter (DOM) was investigated. Am(III) and Pu(IV) are more soluble in groundwater that has high concentrations of DOM. The sorption K{sub d} for Am(III) and Pu(IV) on volcanic zeolitized tuff was up to two orders of magnitude lower in samples with high DOM (15more » to 19 mg C/L) compared to samples with DOM removed (< 0.4 mg C/L) or samples with naturally low DOM (0.2 mg C/L). In contrast, Np(V) and U(VI) sorption to zeolitized tuff was much less affected by the presence of DOM. The Np(V) and U(VI) sorption Kds were low under all conditions. Importantly, the DOM was not found to significantly sorb to the zeolitized tuff during these experiment. The concentration of DOM in groundwater affects the transport behavior of actinides in the subsurface. The mobility of Am(III) and Pu(IV) is significantly higher in groundwater with elevated levels of DOM resulting in potentially enhanced transport. To accurately model the transport behavior of actinides in groundwater at Rainier Mesa, the low actinide Kd values measured in groundwater with high DOM concentrations must be incorporated in predictive transport models.« less

Analysis of large soil samples for actinides

DOEpatents

Maxwell, III; Sherrod, L [Aiken, SC

2009-03-24

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

On-line Monitoring of Actinide Concentrations in Molten Salt Electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Curtis W. Johnson; Mary Lou Dunzik-Gougar; Shelly X. Li

2006-11-01

Pyroprocessing, a treatment method for spent nuclear fuel (SNF), is currently being studied at the Idaho National Laboratory. The key operation of pyroprocessing which takes place in an electrorefiner is the electrochemical separation of actinides from other constituents in spent fuel. Efficient operation of the electrorefiner requires online monitoring of actinide concentrations in the molten salt electrolyte. Square-wave voltammetry (SWV) and normal pulse voltammetry (NPV) are being investigated to assess their applicability to the measurement of actinide concentrations in the electrorefiner.

Method for the concentration and separation of actinides from biological and environmental samples

DOEpatents

Horwitz, E.P.; Dietz, M.L.

1989-05-30

A method and apparatus for the quantitative recover of actinide values from biological and environmental sample by passing appropriately prepared samples in a mineral acid solution through a separation column of a dialkyl(phenyl)-N,N-dialylcarbamoylmethylphosphine oxide dissolved in tri-n-butyl phosphate on an inert substrate which selectively extracts the actinide values. The actinide values can be eluted either as a group or individually and their presence quantitatively detected by alpha counting. 3 figs.

How elements up to 118 were reached and how to go beyond

NASA Astrophysics Data System (ADS)

Düllmann, Christoph E.

2017-11-01

The new superheavy elements with Z=113, 115, 117, and 118 were recently accepted into the periodic table and have been named. Elements with Z≥112 are predominantly produced in 48Ca-induced fusion reactions on actinide targets. This pathway is exhausted at Z=118 due to the lack of target materials with sufficiently high proton number to reach elements with Z≥119. Search experiments for yet heavier elements were performed at GSI Darmstadt and FLNR Dubna. The reactions 50Ti + 249Bk, which leads to Z=119, as well as 64Ni + 238U, 58Fe + 244Pu, 54Cr + 248Cm, and 50Ti + 249Cf, leading to Z=120, have been studied. Despite a total duration of these experiments of more than one year, neither succeeded in the identification of a new element. To obtain improved guidance for better-informed search experiments, nuclear reaction studies appear necessary and have recently started. Also technical advances will be an important pillar to this end. At GSI, work towards a new continuous-wave linear accelerator is ongoing and is briefly described.

Rapid determination of alpha emitters using Actinide resin.

PubMed

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

2004-01-01

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

THERMODYNAMICS OF THE ACTINIDES

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 frommore » 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)« less

Uranium (VI) solubility in carbonate-free ERDA-6 brine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lucchini, Jean-francois; Khaing, Hnin; Reed, Donald T

2010-01-01

When present, uranium is usually an element of importance in a nuclear waste repository. In the Waste Isolation Pilot Plant (WIPP), uranium is the most prevalent actinide component by mass, with about 647 metric tons to be placed in the repository. Therefore, the chemistry of uranium, and especially its solubility in the WIPP conditions, needs to be well determined. Long-term experiments were performed to measure the solubility of uranium (VI) in carbonate-free ERDA-6 brine, a simulated WIPP brine, at pC{sub H+} values between 8 and 12.5. These data, obtained from the over-saturation approach, were the first repository-relevant data for themore » VI actinide oxidation state. The solubility trends observed pointed towards low uranium solubility in WIPP brines and a lack of amphotericity. At the expected pC{sub H+} in the WIPP ({approx} 9.5), measured uranium solubility approached 10{sup -7} M. The objective of these experiments was to establish a baseline solubility to further investigate the effects of carbonate complexation on uranium solubility in WIPP brines.« less

The OASIS Mission

NASA Technical Reports Server (NTRS)

Adams, James H., Jr.; Barghouty, Abdulnasser F.; Binns, W. robert; Christl, Mark; Cosse, Charles B.; Guzik, T. Gregory; deNolfo, Georgia A.; Hams,Thomas; Isbert, Joachim; Israel, Martin H.;

A comparison of two micro-beam X-ray emission techniques for actinide elemental distribution in microscopic particles originating from the hydrogen bombs involved in the Palomares (Spain) and Thule (Greenland) accidents

NASA Astrophysics Data System (ADS)

Jimenez-Ramos, M. C.; Eriksson, M.; García-López, J.; Ranebo, Y.; García-Tenorio, R.; Betti, M.; Holm, E.

2010-09-01

In order to validate and to gain confidence in two micro-beam techniques: particle induced X-ray emission with nuclear microprobe technique (μ-PIXE) and synchrotron radiation induced X-ray fluorescence in a confocal alignment (confocal SR μ-XRF) for characterization of microscopic particles containing actinide elements (mixed plutonium and uranium) a comparative study has been performed. Inter-comparison of the two techniques is essential as the X-ray production cross-sections for U and Pu are different for protons and photons and not well defined in the open literature, especially for Pu. The particles studied consisted of nuclear weapons material, and originate either in the so called Palomares accident in Spain, 1966 or in the Thule accident in Greenland, 1968. In the determination of the average Pu/U mass ratios (not corrected by self-absorption) in the analysed microscopic particles the results from both techniques show a very good agreement. In addition, the suitability of both techniques for the analysis with good resolution (down to a few μm) of the Pu/U distribution within the particles has been proved. The set of results obtained through both techniques has allowed gaining important information concerning the characterization of the remaining fissile material in the areas affected by the aircraft accidents. This type of information is essential for long-term impact assessments of contaminated sites.

PROCESS OF PRODUCING ACTINIDE METALS

DOEpatents

Magel, T.T.

1959-07-14

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

Process to remove actinides from soil using magnetic separation

DOEpatents

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

1996-01-01

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

Preparation of actinide boride materials via solid-state metathesis reactions and actinide dicarbollide precursors

NASA Astrophysics Data System (ADS)

Lupinetti, Anthony J.; Fife, Julie; Garcia, Eduardo; Abney, Kent D.

2000-07-01

Information gaps exist in the knowledge base needed for choosing among the alternate processes to be used in the safe conversion of fissile materials to optimal forms for safe interim storage, long-term storage, and ultimate disposition. The current baseline storage technology for various wastes uses borosilicate glasses.1 The focus of this paper is the synthesis of actinide-containing ceramic materials at low and moderate temperatures (200 °C-1000 °C) using molecular and polymeric actinide borane and carborane complexes.

Actinides in the Geosphere

NASA Astrophysics Data System (ADS)

Runde, Wolfgang; Neu, Mary P.

Since the 1950s actinides have been used to benefit industry, science, health, and national security. The largest industrial application, electricity generation from uranium and thorium fuels, is growing worldwide. Thus, more actinides are being mined, produced, used and processed than ever before. The future of nuclear energy hinges on how these increasing amounts of actinides are contained in each stage of the fuel cycle, including disposition. In addition, uranium and plutonium were built up during the Cold War between the United States and the Former Soviet Union for defense purposes and nuclear energy.

Characterization of extreme ultraviolet laser ablation mass spectrometry for actinide trace analysis and nanoscale isotopic imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Green, Tyler; Kuznetsov, Ilya; Willingham, David

The purpose of this research was to characterize Extreme Ultraviolet Time-of-Flight (EUV TOF) Laser Ablation Mass Spectrometry for high spatial resolution elemental and isotopic analysis. We compare EUV TOF results with Secondary Ionization Mass Spectrometry (SIMS) to orient the EUV TOF method within the overall field of analytical mass spectrometry. Using the well-characterized NIST 61x glasses, we show that the EUV ionization approach produces relatively few molecular ion interferences in comparison to TOF SIMS. We demonstrate that the ratio of element ion to element oxide ion is adjustable with EUV laser pulse energy and that the EUV TOF instrument hasmore » a sample utilization efficiency of 0.014%. The EUV TOF system also achieves a lateral resolution of 80 nm and we demonstrate this lateral resolution with isotopic imaging of closely spaced particles or uranium isotopic standard materials.« less

Mendelevium: The Way It Was

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

A reel of black & white film shot nearly 60 years ago has surfaced at Berkeley Lab, depicting the discovery of Mendelevium - or Element 101 - as reenacted by some of the legendary scientists who did the actual work at that time. Since the 1940s, Berkeley Lab scientists were locked in a race to synthesize new elements, and more often than not, they came out winners. Sixteen elements, most of them in the actinide series at the bottom of the periodic table, were discovered and synthesized by its researchers. Retired Berkeley Lab physicist Claude Lyneis found the reel inmore » a box of dusty and deteriorating films slated for disposal. Using digital editing skills he acquired to make videos of his son's lacrosse team, Lyneis has produced and narrated an excerpt of this nearly-lost footage. It is an entertaining and informative look at the pioneering physics performed at UC Berkeley and Lawrence Berkeley National Laboratory's hillside campus.« less

Mendelevium: The Way It Was

ScienceCinema

None

2018-05-30

A reel of black & white film shot nearly 60 years ago has surfaced at Berkeley Lab, depicting the discovery of Mendelevium - or Element 101 - as reenacted by some of the legendary scientists who did the actual work at that time. Since the 1940s, Berkeley Lab scientists were locked in a race to synthesize new elements, and more often than not, they came out winners. Sixteen elements, most of them in the actinide series at the bottom of the periodic table, were discovered and synthesized by its researchers. Retired Berkeley Lab physicist Claude Lyneis found the reel in a box of dusty and deteriorating films slated for disposal. Using digital editing skills he acquired to make videos of his son's lacrosse team, Lyneis has produced and narrated an excerpt of this nearly-lost footage. It is an entertaining and informative look at the pioneering physics performed at UC Berkeley and Lawrence Berkeley National Laboratory's hillside campus.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hobart, David E.

In celebrating the centennial anniversary of the birth of Glenn T. Seaborg it is fitting that we recount and pay tribute to his legacy. Many know of the scientific accomplishments of this man who became a legend and anyone who has attended his lectures can attest to how informative, educational, and entertaining he was. He had a beguiling and whimsical sense of humor and used this to drive home his points and share his passion and quest for discovery. The periodic table is a fundamental cornerstone of science and remains a central unifying principal. Seaborg was the architect of themore » actinide series of elements and their proper placement in the periodic table and co-discoverer of ten transuranium elements - one of which bears his name, element 106, seaborgium. The work and achievements of this Nobel laureate have touched the lives of many and his legacy will continue for generations to come.« less

Solid-phase extraction microfluidic devices for matrix removal in trace element assay of actinide materials

DOE PAGES

Gao, Jun; Manard, Benjamin Thomas; Castro, Alonso; ...

2017-02-02

Advances in sample nebulization and injection technology have significantly reduced the volume of solution required for trace impurity analysis in plutonium and uranium materials. Correspondingly, we have designed and tested a novel chip-based microfluidic platform, containing a 100-µL or 20-µL solid-phase microextraction column, packed by centrifugation, which supports nuclear material mass and solution volume reductions of 90% or more compared to standard methods. Quantitative recovery of 28 trace elements in uranium was demonstrated using a UTEVA chromatographic resin column, and trace element recovery from thorium (a surrogate for plutonium) was similarly demonstrated using anion exchange resin AG MP-1. Of ninemore » materials tested, compatibility of polyvinyl chloride (PVC), polypropylene (PP), and polytetrafluoroethylene (PTFE) chips with the strong nitric acid media was highest. Finally, the microcolumns can be incorporated into a variety of devices and systems, and can be loaded with other solid-phase resins for trace element assay in high-purity metals.« less

Solid-phase extraction microfluidic devices for matrix removal in trace element assay of actinide materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Jun; Manard, Benjamin Thomas; Castro, Alonso

Advances in sample nebulization and injection technology have significantly reduced the volume of solution required for trace impurity analysis in plutonium and uranium materials. Correspondingly, we have designed and tested a novel chip-based microfluidic platform, containing a 100-µL or 20-µL solid-phase microextraction column, packed by centrifugation, which supports nuclear material mass and solution volume reductions of 90% or more compared to standard methods. Quantitative recovery of 28 trace elements in uranium was demonstrated using a UTEVA chromatographic resin column, and trace element recovery from thorium (a surrogate for plutonium) was similarly demonstrated using anion exchange resin AG MP-1. Of ninemore » materials tested, compatibility of polyvinyl chloride (PVC), polypropylene (PP), and polytetrafluoroethylene (PTFE) chips with the strong nitric acid media was highest. Finally, the microcolumns can be incorporated into a variety of devices and systems, and can be loaded with other solid-phase resins for trace element assay in high-purity metals.« less

Defense Technical Information Center Thesaurus

DTIC Science & Technology

2000-10-01

acquisition radar 4 + Indicates existence of further generic levels of the term DTIC Thesaurus Actuators Acridines Actinide series (cont.) Activated sintering...BT Heterocyclic compounds+ Uranium+ BT Sintering Acrilan Actinide series compounds Activated sludge process use Acrylonitrile polymers RT Actinide...Waste treatment+ Protactinium compounds Acronyms Thorium compounds+ Activation use Abbreviations Transuranium compounds+ UF Energizing Uranium compounds

Utilization of Minor Actinides as a Fuel Component for Ultra-Long Life Bhr Configurations: Designs, Advantages and Limitations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dr. Pavel V. Tsvetkov

2009-05-20

This project assessed the advantages and limitations of using minor actinides as a fuel component to achieve ultra-long life Very High Temperature Reactor (VHTR) configurations. Researchers considered and compared the capabilities of pebble-bed and prismatic core designs with advanced actinide fuels to achieve ultra-long operation without refueling. Since both core designs permit flexibility in component configuration, fuel utilization, and fuel management, it is possible to improve fissile properties of minor actinides by neutron spectrum shifting through configuration adjustments. The project studied advanced actinide fuels, which could reduce the long-term radio-toxicity and heat load of high-level waste sent to a geologicmore » repository and enable recovery of the energy contained in spent fuel. The ultra-long core life autonomous approach may reduce the technical need for additional repositories and is capable to improve marketability of the Generation IV VHTR by allowing worldwide deployment, including remote regions and regions with limited industrial resources. Utilization of minor actinides in nuclear reactors facilitates developments of new fuel cycles towards sustainable nuclear energy scenarios.« less

A Summary of Actinide Enrichment Technologies and Capability Gaps

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patton, Bradley D.; Robinson, Sharon M.

2017-01-01

The evaluation performed in this study indicates that a new program is needed to efficiently provide a national actinide radioisotope enrichment capability to produce milligram-to-gram quantities of unique materials for user communities. This program should leverage past actinide enrichment, the recent advances in stable isotope enrichment, and assessments of the future requirements to cost effectively develop this capability while establishing an experience base for a new generation of researchers in this vital area. Preliminary evaluations indicate that an electromagnetic isotope separation (EMIS) device would have the capability to meet the future needs of the user community for enriched actinides. Themore » EMIS technology could be potentially coupled with other enrichment technologies, such as irradiation, as pre-enrichment and/or post-enrichment systems to increase the throughput, reduce losses of material, and/or reduce operational costs of the base EMIS system. Past actinide enrichment experience and advances in the EMIS technology applied in stable isotope separations should be leveraged with this new evaluation information to assist in the establishment of a domestic actinide radioisotope enrichment capability.« less

Actinide Sorption in a Brine/Dolomite Rock System: Evaluating the Degree of Conservatism in Kd Ranges used in Performance Assessment Modeling for the WIPP Nuclear Waste Repository

NASA Astrophysics Data System (ADS)

Dittrich, T. M.; Reed, D. T.

2015-12-01

The Waste Isolation Pilot Plant (WIPP) near Carlsbad, NM is the only operating nuclear waste repository in the US and has been accepting transuranic (TRU) waste since 1999. The WIPP is located in a salt deposit approximately 650 m below the surface and performance assessment (PA) modeling for a 10,000 year period is required to recertify the operating license with the US EPA every five years. The main pathway of concern for environmental release of radioactivity is a human intrusion caused by drilling into a pressurized brine reservoir below the repository. This could result in the flooding of the repository and subsequent transport in the high transmissivity layer (dolomite-rich Culebra formation) above the waste disposal rooms. We evaluate the degree of conservatism in the estimated sorption partition coefficients (Kds) ranges used in the PA based on an approach developed with granite rock and actinides (Dittrich and Reimus, 2015; Dittrich et al., 2015). Sorption onto the waste storage material (Fe drums) may also play a role in mobile actinide concentrations. We will present (1) a conceptual overview of how Kds are used in the PA model, (2) technical background of the evolution of the ranges and (3) results from batch and column experiments and model predictions for Kds with WIPP dolomite and clays, brine with various actinides, and ligands (e.g., acetate, citrate, EDTA) that could promote transport. The current Kd ranges used in performance models are based on oxidation state and are 5-400, 0.5-10,000, 0.03-200, and 0.03-20 mL g-1 for elements with oxidation states of III, IV, V, and VI, respectively. Based on redox conditions predicted in the brines, possible actinide species include Pu(III), Pu(IV), U(IV), U(VI), Np(IV), Np(V), Am(III), and Th(IV). We will also discuss the challenges of upscaling from lab experiments to field scale predictions, the role of colloids, and the effect of engineered barrier materials (e.g., MgO) on transport conditions. Dittrich, T.M., Reimus, P.W. 2015. Uranium transport in a crushed granodiorite: experiments and reactive transport modeling. J Contam Hydrol 175-176: 44-59. Dittrich, T.M., Boukhalfa, H., Ware, S.D., Reimus, P.W. 2015. Laboratory investigation of the role of desorption kinetics on americium transport associated with bentonite colloids. J Environ Radioactiv 148: 170-182.

Method for recovery of actinides from refractory oxides thereof using O.sub. F.sub.2

DOEpatents

Asprey, Larned B.; Eller, Phillip G.

1988-01-01

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayes, S. L.; Harp, J. M.; Chichester, H. J. M.

Research and development activities on metallic fuels in the US are focused on their potential use for actinide transmutation in future sodium fast reactors. As part of this application, there is a desire to demonstrate a multifold increase in burnup potential. A number of metallic fuel design innovations are under investigation with a view toward significantly increasing the burnup potential of metallic fuels, since higher discharge burnups equate to lower potential actinide losses during recycle. Promising innovations under investigation include: 1) lowering the fuel smeared density in order to accommodate the additional swelling expected as burnups increase, 2) utilizing anmore » annular fuel geometry for better geometrical stability at low smeared densities, as well as the potential to eliminate the need for a sodium bond, and 3) minor alloy additions to immobilize lanthanide fission products inside the metallic fuel matrix and prevent their transport to the cladding resulting in fuel-cladding chemical interaction. This paper presents results from these efforts to advance metallic fuel technology in support of high burnup and actinide transmutation objectives. Highlights include examples of fabrication of low smeared density annular metallic fuels, experiments to identify alloy additions effective in immobilizing lanthanide fission products, and early postirradiation examinations of annular metallic fuels having low smeared densities and palladium additions for fission product immobilization.« less

Rapid determination of actinides in seawater samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2014-03-09

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

Actinide recovery process

DOEpatents

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

1987-07-28

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

Improved method for extracting lanthanides and actinides from acid solutions

DOEpatents

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

1983-07-26

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

Prompt fission neutron spectra of actinides

DOE PAGES

Capote, R.; Chen, Y. -J.; Hambsch, F. -J.; ...

2016-01-06

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

Actinide recovery process

DOEpatents

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

1985-06-13

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

Process for making a ceramic composition for immobilization of actinides

DOEpatents

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

2001-01-01

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

Quantum Chemical Studies of Actinides and Lanthanides: From Small Molecules to Nanoclusters

NASA Astrophysics Data System (ADS)

Vlaisavljevich, Bess

Research into actinides is of high interest because of their potential applications as an energy source and for the environmental implications therein. Global concern has arisen since the development of the actinide concept in the 1940s led to the industrial scale use of the commercial nuclear energy cycle and nuclear weapons production. Large quantities of waste have been generated from these processes inspiring efforts to address fundamental questions in actinide science. In this regard, the objective of this work is to use theory to provide insight and predictions into actinide chemistry, where experimental work is extremely challenging because of the intrinsic difficulties of the experiments themselves and the safety issues associated with this type of chemistry. This thesis is a collection of theoretical studies of actinide chemistry falling into three categories: quantum chemical and matrix isolation studies of small molecules, the electronic structure of organoactinide systems, and uranyl peroxide nanoclusters and other solid state actinide compounds. The work herein not only spans a wide range of systems size but also investigates a range of chemical problems. Various quantum chemical approaches have been employed. Wave function-based methods have been used to study the electronic structure of actinide containing molecules of small to middle-size. Among these methods, the complete active space self consistent field (CASSCF) approach with corrections from second-order perturbation theory (CASPT2), the generalized active space SCF (GASSCF) approach, and Moller-Plesset second-order perturbation theory (MP2) have been employed. Likewise, density functional theory (DFT) has been used along with analysis tools like bond energy decomposition, bond orders, and Bader's Atoms in Molecules. From these quantum chemical results, comparison with experimentally obtained structures and spectra are made.

The separation of lanthanides and actinides in supercritical fluid carbon dioxide

DOE PAGES

Mincher, Bruce J.; Wai, Chien M.; Fox, Robert V.; ...

2015-10-28

Supercritical fluid carbon dioxide presents an attractive alternative to conventional solvents for recovery of the actinides and lanthanides. Carbon dioxide is a good solvent for fluorine and phosphate-containing ligands, including the traditional tributylphosphate ligand used in process-scale uranium separations. Actinide and lanthanide oxides may even be directly dissolved in carbon dioxide containing the complexes formed between these ligands and mineral acids, obviating the need for large volumes of acids for leaching and dissolution, and the corresponding organic liquid–liquid solvent extraction solutions. As a result, examples of the application of this novel technology for actinide and lanthanide separations are presented.

Hydrothermal Synthesis and Crystal Structures of Actinide Compounds

NASA Astrophysics Data System (ADS)

Runde, Wolfgang; Neu, Mary P.

Since the 1950s actinides have been used to benefit industry, science, health, and national security. The largest industrial application, electricity generation from uranium and thorium fuels, is growing worldwide. Thus, more actinides are being mined, produced, used and processed than ever before. The future of nuclear energy hinges on how these increasing amounts of actinides are contained in each stage of the fuel cycle, including disposition. In addition, uranium and plutonium were built up during the Cold War between the United States and the Former Soviet Union for defense purposes and nuclear energy. These stockpiles have been significantly reduced in the last decade.

Nuclear waste forms for actinides

PubMed Central

Ewing, Rodney C.

1999-01-01

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

Gas core reactors for actinide transmutation and breeder applications

NASA Technical Reports Server (NTRS)

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

1978-01-01

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

The R-Process Alliance: 2MASS J09544277+5246414, the Most Actinide-enhanced R-II Star Known

NASA Astrophysics Data System (ADS)

Holmbeck, Erika M.; Beers, Timothy C.; Roederer, Ian U.; Placco, Vinicius M.; Hansen, Terese T.; Sakari, Charli M.; Sneden, Christopher; Liu, Chao; Lee, Young Sun; Cowan, John J.; Frebel, Anna

2018-06-01

We report the discovery of a new actinide-boost star, 2MASS J09544277+5246414, originally identified as a very bright (V = 10.1), extremely metal-poor ([Fe/H] = ‑2.99) K giant in the LAMOST survey, and found to be highly r-process-enhanced (r-II; [Eu/Fe] = +1.28]), during the snapshot phase of the R-Process Alliance (RPA). Based on a high signal-to-noise ratio (S/N), high-resolution spectrum obtained with the Harlan J. Smith 2.7 m telescope, this star is the first confirmed actinide-boost star found by RPA efforts. With an enhancement of [Th/Eu] = +0.37, 2MASS J09544277+5246414 is also the most actinide-enhanced r-II star yet discovered, and only the sixth metal-poor star with a measured uranium abundance ([U/Fe] = +1.40). Using the Th/U chronometer, we estimate an age of 13.0 ± 4.7 Gyr for this star. The unambiguous actinide-boost signature of this extremely metal-poor star, combined with additional r-process-enhanced and actinide-boost stars identified by the RPA, will provide strong constraints on the nature and origin of the r-process at early times.

Quantification of Cation Sorption to Engineered Barrier Materials Under Extreme Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Powell, Brian; Schlautman, Mark; Rao, Linfeng

The objective of this research is to examine mechanisms and thermodynamics of actinide sorption to engineered barrier materials (iron (oxyhydr)oxides and bentonite clay) for nuclear waste repositories under high temperature and high ionic strength conditions using a suite of macroscopic and microscopic techniques which will be coupled with interfacial reaction models. Gaining a mechanistic understanding of interfacial processes governing the sorption/sequestration of actinides at mineral-water interfaces is fundamental for the accurate prediction of actinide behavior in waste repositories. Although macroscale sorption data and various spectroscopic techniques have provided valuable information regarding speciation of actinides at solid-water interfaces, significant knowledge gapsmore » still exist with respect to sorption mechanisms and the ability to quantify sorption, particularly at high temperatures and ionic strengths. This objective is addressed through three major tasks: (1) influence of oxidation state on actinide sorption to iron oxides and clay minerals at elevated temperatures and ionic strengths; (2) calorimetric titrations of actinide-mineral suspensions; (3) evaluation of bentonite performance under repository conditions. The results of the work will include a qualitative conceptual model and a quantitative thermodynamic speciation model describing actinide partitioning to minerals and sediments, which is based upon a mechanistic understanding of specific sorption processes as determined from both micro-scale and macroscale experimental techniques. The speciation model will be a thermodynamic aqueous and surface complexation model of actinide interactions with mineral surfaces that is self-consistent with macroscopic batch sorption data, calorimetric and potentiometric titrations, X-ray absorption Spectroscopy (XAS, mainly Extended X-ray Absorption Fine Structure (EXAFS)), and electron microscopy analyses. The novelty of the proposed work lies largely in the unique system conditions which will be examined (i.e. elevated temperature and ionic strength) and the manner in which the surface complexation model will be developed in terms of specific surface species identified using XAS. These experiments will thus provide a fundamental understanding of the chemical and physical processes occurring at the solid-solution interface under expected repository conditions. Additionally, the focus on thermodynamic treatment of actinide ion interactions with minerals as proposed will provide information on the driving forces involved and contribute to the overall understanding of the high affinity many actinide ions have for oxide surfaces. The utility of this model will be demonstrated in this work through a series of advective and diffusive flow experiments.« less

Synthesis of Actinide Materials for the Study of Basic Actinide Science and Rapid Separation of Fission Products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dorhout, Jacquelyn Marie

This dissertation covers several distinct projects relating to the fields of nuclear forensics and basic actinide science. Post-detonation nuclear forensics, in particular, the study of fission products resulting from a nuclear device to determine device attributes and information, often depends on the comparison of fission products to a library of known ratios. The expansion of this library is imperative as technology advances. Rapid separation of fission products from a target material, without the need to dissolve the target, is an important technique to develop to improve the library and provide a means to develop samples and standards for testing separations.more » Several materials were studied as a proof-of-concept that fission products can be extracted from a solid target, including microparticulate (< 10 μm diameter) dUO 2, porous metal organic frameworks (MOFs) synthesized from depleted uranium (dU), and other organicbased frameworks containing dU. The targets were irradiated with fast neutrons from one of two different neutron sources, contacted with dilute acids to facilitate the separation of fission products, and analyzed via gamma spectroscopy for separation yields. The results indicate that smaller particle sizes of dUO 2 in contact with the secondary matrix KBr yield higher separation yields than particles without a secondary matrix. It was also discovered that using 0.1 M HNO 3 as a contact acid leads to the dissolution of the target material. Lower concentrations of acid were used for future experiments. In the case of the MOFs, a larger pore size in the framework leads to higher separation yields when contacted with 0.01 M HNO 3. Different types of frameworks also yield different results.« less

LLNL SFA OBER SBR FY17 Program Management and Performance Report: Subsurface Biogeochemistry of Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kersting, Annie B.

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 anthropogenic plutonium (Pu) has accumulated 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 inmore » 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.« less

Enhancing the actinide sciences in Europe through hot laboratories networking and pooling: from ACTINET to TALISMAN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bourg, S.; Poinssot, C.

2013-07-01

Since 2004, Europe supports the strengthening of the European actinides sciences scientific community through the funding of dedicated networks: (i) from 2004 to 2008, the ACTINET6 network of excellence (6. Framework Programme) gathered major laboratories involved in nuclear research and a wide range of academic research organisations and universities with the specific aims of funding and implementing joint research projects to be performed within the network of pooled facilities; (ii) from 2009 to 2013, the ACTINET-I3 integrated infrastructure initiative (I3) supports the cost of access of any academics in the pooled EU hot laboratories. In this continuation, TALISMAN (Trans-national Accessmore » to Large Infrastructures for a Safe Management of Actinides) gathers now the main European hot laboratories in actinides sciences in order to promote their opening to academics and universities and strengthen the EU-skills in actinides sciences. Furthermore, a specific focus is set on the development of advanced cutting-edge experimental and spectroscopic capabilities, the combination of state-of-the art experimental with theoretical first-principle methods on a quantum mechanical level and to benefit from the synergy between the different scientific and technical communities. ACTINET-I3 and TALISMAN attach a great importance and promote the Education and Training of the young generation of actinides scientists in the Trans-national access but also by organizing Schools (general Summer Schools or Theoretical User Lab Schools) or by granting students to attend International Conference on actinide sciences. (authors)« less

Solar r-process-constrained actinide production in neutrino-driven winds of supernovae

NASA Astrophysics Data System (ADS)

Goriely, S.; Janka, H.-Th.

2016-07-01

Long-lived radioactive nuclei play an important role as nucleo-cosmochronometers and as cosmic tracers of nucleosynthetic source activity. In particular, nuclei in the actinide region like thorium, uranium, and plutonium can testify to the enrichment of an environment by the still enigmatic astrophysical sources that are responsible for the production of neutron-rich nuclei by the rapid neutron-capture process (r-process). Supernovae and merging neutron-star (NS) or NS-black hole binaries are considered as most likely sources of the r-nuclei. But arguments in favour of one or the other or both are indirect and make use of assumptions; they are based on theoretical models with remaining simplifications and shortcomings. An unambiguous observational determination of a production event is still missing. In order to facilitate searches in this direction, e.g. by looking for radioactive tracers in stellar envelopes, the interstellar medium or terrestrial reservoirs, we provide improved theoretical estimates and corresponding uncertainty ranges for the actinide production (232Th, 235, 236, 238U, 237Np, 244Pu, and 247Cm) in neutrino-driven winds of core-collapse supernovae. Since state-of-the-art supernova models do not yield r-process viable conditions - but still lack, for example, the effects of strong magnetic fields - we base our investigation on a simple analytical, Newtonian, adiabatic and steady-state wind model and consider the superposition of a large number of contributing components, whose nucleosynthesis-relevant parameters (mass weight, entropy, expansion time-scale, and neutron excess) are constrained by the assumption that the integrated wind nucleosynthesis closely reproduces the Solar system distribution of r-process elements. We also test the influence of uncertain nuclear physics.

Organic and Aqueous Redox Speciation of Cu(III) Periodate Oxidized Transuranium Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCann, Kevin; Sinkov, Sergey I.; Lumetta, Gregg J.

A hexavalent group actinide separation process could streamline used nuclear fuel recycle and waste management. The limiting factor to such a process compatible with current fuel dissolution practices is obtaining and maintaining hexavalent Am, in molar nitric acid due to the high reduction potential of the Am(VI)/Am(III) couple (1.68 V vs SCE). Two strong oxidants, sodium bismuthate and Cu(III) periodate, have demonstrated quantitative oxidation of Am under molar acid conditions and better than 50% recovery by diamyl amylphosphonate (DAAP) is possible under these same conditions. This work considers the use of Cu(III) periodate to oxidize Np(V) to Np(VI) and Pu(IV)more » to Pu(VI) and recover these elements by extraction with DAAP. A metal:oxidant ratio of 1:1.2 and 1:3 was necessary to quantitatively oxidize Np(V) and Pu(IV), respectively, to the hexavalent state. Extraction of hexavalent Np, Pu, and Am by 1 M DAAP in n-dodecane was measured using UV-Vis [Pu(VI), Am (VI)] and NIR [Np(VI)]. Distribution values of Am(VI) were found to match previous tracer level studies. The organic phase spectra of Np, Pu, and Am are presented and molar absorptivities are calculated for characteristic peaks. Hexavalent Pu was found to be stable in the organic phase while Np(VI) showed some reduction to Np(V) and Am was present as Am(III), Am(V), and Am(VI) species in aqueous and organic phases during the extraction experiments. These results demonstrate, for the first time, the ability to recover macroscopic amounts of americium that would be present during fuel reprocessing and are the first characterization of Am organic phase oxidation state speciation relevant to a hexavalent group actinide separation process under acidic conditions.« less

Dissolution behavior of MgO based inert matrix fuel for the transmutation of minor actinides

NASA Astrophysics Data System (ADS)

Mühr-Ebert, E. L.; Lichte, E.; Bukaemskiy, A.; Finkeldei, S.; Klinkenberg, M.; Brandt, F.; Bosbach, D.; Modolo, G.

2018-07-01

This study explores the dissolution properties of magnesia-based inert matrix nuclear fuel (IMF) containing transuranium elements (TRU). Pure MgO pellets as well as MgO pellets containing CeO2, as surrogate for TRU oxides, and are considered as model systems for genuine magnesia based inert matrix fuel were fabricated. The aim of this study is to identify conditions at which the matrix material can be selectively dissolved during the head-end reprocessing step, allowing a separation of MgO from the actinides, whereas the actinides remain undissolved. The dissolution behavior was studied in macroscopic batch experiments as a function of nitric acid concentration, dissolution medium volume, temperature, stirring velocity, and pellet density (85, 90, 96, and 99%TD). To mimic pellets with various burn-ups the density of the here fabricated pellets was varied. MgO is soluble even under mild conditions (RT, 2.5 mol/L HNO3). The dissolution rates of MgO at different acid concentrations are rather similar, whereas the dissolution rate is strongly dependent on the temperature. Via a microscopic approach, a model was developed to describe the evolution of the pellet surface area during dissolution and determine a surface normalized dissolution rate. Moreover, dissolution rates of the inert matrix fuel containing CeO2 were determined as a function of the acid concentration and temperature. During the dissolution of MgO/CeO2 pellets the MgO dissolves completely, while CeO2 (>99%) remains undissolved. This study intends to provide a profound understanding of the chemical performance of magnesia based IMF containing fissile material. The feasibility of the dissolution of magnesia based IMF with nitric acid is discussed.

Selectivity in Ligand Binding to Uranyl Compounds: A Synthetic, Structural, Thermodynamic and Computational Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arnold, John

The uranyl cation (UO 2 2+) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due tomore » the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. We believe that the goal of developing a practical system for uranium separation from seawater will not be attained without new insights into our existing fundamental knowledge of actinide chemistry. We posit that detailed studies of the kinetic and thermodynamic factors that influence interactions between f-elements and ligands with a range of donor atoms is essential to any major advance in this important area. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. We anticipate that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials.« less

PREPARATION OF ACTINIDE-ALUMINUM ALLOYS

DOEpatents

Moore, R.H.

1962-09-01

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

Transmutation of actinides in power reactors.

PubMed

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

2005-01-01

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

PRODUCTION OF ACTINIDE METAL

DOEpatents

Knighton, J.B.

1963-11-01

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

Actinide geochemistry: from the molecular level to the real system.

PubMed

Geckeis, Horst; Rabung, Thomas

2008-12-12

Geochemical processes leading to either mobilization or retention of radionuclides in an aquifer system are significantly influenced by their interaction with rock, sediment and colloid surfaces. Therefore, a sound safety assessment of nuclear waste disposal requires the elucidation and quantification of those processes. State-of-the-art analytical techniques as e.g. laser- and X-ray spectroscopy are increasingly applied to study solid-liquid interface reactions to obtain molecular level speciation insight. We have studied the sorption of trivalent lanthanides and actinides onto aluminium oxides, hydroxides and purified clay minerals by the time-resolved laser fluorescence spectroscopy and X-ray-absorption spectroscopy. Chemical constitution and structure of surface bound actinides are proposed based on spectroscopic information. Open questions still remain with regard to the exact nature of mineral surface ligands and the mineral/water interface. Similarities of spectroscopic data obtained for M(III) sorbed onto gamma-alumina, and clay minerals suggest the formation of very comparable inner-sphere surface complexes such as S-O-An(III)(OH)x(2-x)(H2O)5-x at pH > 5. Those speciation data are found consistent with those predicted by surface complexation modelling. The applicability of data obtained for pure mineral phases to actinide sorption onto heterogeneously composed natural clay rock is examined by experiments and by geochemical modelling. Good agreement of experiment and model calculations is found for U(VI) and trivalent actinide/lanthanide sorption to natural clay rock. The agreement of spectroscopy, geochemical modelling and batch experiments with natural rock samples and purified minerals increases the reliability in model predictions. The assessment of colloid borne actinide migration observed in various laboratory and field studies calls for detailed information on actinide-colloid interaction. Kinetic stabilization of colloid bound actinides can be due to inclusion into inorganic colloid matrix or by macromolecular rearrangement in case of organic, humic/fulvic like colloids. Only a combination of spectroscopy, microscopy and classical batch sorption experiments can help to elucidate the actinide-colloid interaction mechanisms and thus contribute to the assessment of colloids for radionuclide migration.

New cubic structure compounds as actinide host phases

NASA Astrophysics Data System (ADS)

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

2010-03-01

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

Relaxation of Actinide Surfaces: An All Electron Study

NASA Astrophysics Data System (ADS)

Atta-Fynn, Raymond; Dholabhai, Pratik; Ray, Asok

2006-10-01

Fully relativistic full potential density functional calculations with a linearized augmented plane wave plus local orbitals basis (LAPW + lo) have been performed to investigate the relaxations of heavy actinide surfaces, namely the (111) surface of fcc δ-Pu and the (0001) surface of dhcp Am using WIEN2k. This code uses the LAPW + lo method with the unit cell divided into non-overlapping atom-centered spheres and an interstitial region. The APW+lo basis is used to describe all s, p, d, and f states and LAPW basis to describe all higher angular momentum states. Each surface was modeled by a three-layer periodic slab separated by 60 Bohr vacuum with four atoms per surface unit cell. In general, we have found a contraction of the interlayer separations for both Pu and Am. We will report, in detail, the electronic and geometric structures of the relaxed surfaces and comparisons with the respective non-relaxed surfaces.

Oxygen potentials of mixed oxide fuels for fast reactors

NASA Astrophysics Data System (ADS)

Kato, M.; Tamura, T.; Konashi, K.

2009-03-01

Oxygen potentials of homogenous (Pu0.2U0.8)O2-x and (Am0.02Pu0.30Np0.02U0.66)O2-x which have been developed as fuels for fast breeder reactors were measured at temperatures of 1473-1623 K by a gas equilibrium method using an (Ar, H2, H2O) gas mixture. The measured oxygen potentials of (Pu0.2U0.8)O2-x were about 25 kJ mol-1 lower than those of (Pu0.3U0.7)O2-x measured previously and were consistent with the values calculated by Besmann and Lindemer's model. The measured oxygen potentials of (Am0.02Pu0.30Np0.02U0.66)O2-x were slightly higher than those of MOX without minor actinides. No fuel-cladding chemical interaction is affected significantly by adding their minor actinides.

Effect of the size of experimental channels of the lead slowing-down spectrometer SVZ-100 (Institute for Nuclear Research, Moscow) on the moderation constant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Latysheva, L. N.; Bergman, A. A.; Sobolevsky, N. M., E-mail: sobolevs@inr.ru

Lead slowing-down (LSD) spectrometers have a low energy resolution (about 30%), but their luminosity is 10{sup 3} to 10{sup 4} times higher than that of time-of-flight (TOF) spectrometers. A high luminosity of LSD spectrometers makes it possible to use them to measure neutron cross section for samples of mass about several micrograms. These features specify a niche for the application of LSD spectrometers in measuring neutron cross sections for elements hardly available in macroscopic amounts-in particular, for actinides. A mathematical simulation of the parameters of SVZ-100 LSD spectrometer of the Institute for Nuclear Research (INR, Moscow) is performed in themore » present study on the basis of the MCNPX code. It is found that the moderation constant, which is the main parameter of LSD spectrometers, is highly sensitive to the size and shape of detecting volumes in calculations and, hence, to the real size of experimental channels of the LSD spectrometer.« less

Experimental status of the nuclear spin scissors mode

NASA Astrophysics Data System (ADS)

Balbutsev, E. B.; Molodtsova, I. V.; Schuck, P.

2018-04-01

With the Wigner function moments (WFM) method the scissors mode of the actinides and rare earth nuclei are investigated. The unexplained experimental fact that in 232Th a double hump structure is found finds a natural explanation within WFM. It is predicted that the lower peak corresponds to an isovector spin scissors mode whereas the higher-lying states corresponds to the conventional isovector orbital scissors mode. The experimental situation is scrutinized in this respect concerning practically all results of M 1 excitations.

Colloid-borne forms of tetravalent actinides: A brief review

NASA Astrophysics Data System (ADS)

Zänker, Harald; Hennig, Christoph

2014-02-01

Tetravalent actinides, An(IV), are usually assumed to be little mobile in near-neutral environmental waters because of their low solubility. However, there are certain geochemical scenarios during which mobilization of An(IV) in a colloid-borne (waterborne) form cannot be ruled out. A compilation of colloid-borne forms of tetravalent actinides described so far for laboratory experiments together with several examples of An(IV) colloids observed in field experiments and real-world scenarios are given. They are intended to be a knowledge base and a tool for those who have to interpret actinide behavior under environmental conditions. Synthetic colloids containing structural An(IV) and synthetic colloids carrying adsorbed An(IV) are considered. Their behavior is compared with the behavior of An(IV) colloids observed after the intentional or unintentional release of actinides into the environment. A list of knowledge gaps as to the behavior of An(IV) colloids is provided and items which need further research are highlighted.

A Screened Hybrid DFT Study of Actinide Oxides, Nitrides, and Carbides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wen, Xiaodong; Martin, Richard L.; Scuseria, Gustavo E.

2013-06-27

A systematic study of the structural, electronic, and magnetic properties of actinide oxides, nitrides, and carbides (AnX1–2 with X = C, N, O) is performed using the Heyd–Scuseria–Ernzerhof (HSE) hybrid functional. Our computed results show that the screened hybrid HSE functional gives a good description of the electronic and structural properties of actinide dioxides (strongly correlated insulators) when compared with available experimental data. However, there are still some problems reproducing the electronic properties of actinide nitrides and carbides (strongly correlated metals). In addition, in order to compare with the results by HSE, the structures, electronic, and magnetic properties of thesemore » actinide compounds are also investigated in the PBE and PBE+U approximation. Interestingly, the density of states of UN obtained with PBE compares well with the experimental photoemission spectra, in contrast to the hybrid approximation. This is presumably related to the need of additional screening in the Hartree–Fock exchange term of the metallic phases.« less

Ceramicrete stabilization of U-and Pu-bearing materials

DOEpatents

Wagh, Arun S.; Maloney, M. David; Thompson, Gary H.

2007-11-13

A method of stabilizing nuclear material is disclosed. Oxides or halides of actinides and/or transuranics (TRUs) and/or hydrocarbons and/or acids contaminated with actinides and/or TRUs are treated by adjusting the pH of the nuclear material to not less than about 5 and adding sufficient MgO to convert fluorides present to MgF.sub.2; alumina is added in an amount sufficient to absorb substantially all hydrocarbon liquid present, after which a binder including MgO and KH.sub.2PO.sub.4 is added to the treated nuclear material to form a slurry. Additional MgO may be added. A crystalline radioactive material is also disclosed having a binder of the reaction product of calcined MgO and KH.sub.2PO.sub.4 and a radioactive material of the oxides and/or halides of actinides and/or transuranics (TRUs). Acids contaminated with actinides and/or TRUs, and/or actinides and/or TRUs with or without oils and/or greases may be encapsulated and stabilized by the binder.

Matrix infrared spectra and electronic structure calculations of the first actinide borylene: FB=ThF(2).

PubMed

Wang, Xuefeng; Roos, Björn O; Andrews, Lester

2010-03-14

Laser-ablated Th atoms react with BF(3) during condensation in excess argon at 6 K to form the first actinide borylene (FB=ThF(2)) and actinide-boron multiple bond. Three new product absorptions in the B-F and Th-F stretching regions of matrix infrared spectra are assigned to FB=ThF(2) from comparison to theoretically predicted vibrational frequencies.

CHARACTERIZATION OF ACTINIDES IN SIMULATED ALKALINE TANK WASTE SLUDGES AND LEACHATES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash, Kenneth L.

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 actinidesmore » 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.« less

Correlation consistent basis sets for actinides. II. The atoms Ac and Np-Lr

NASA Astrophysics Data System (ADS)

Feng, Rulin; Peterson, Kirk A.

2017-08-01

New correlation consistent basis sets optimized using the all-electron third-order Douglas-Kroll-Hess (DKH3) scalar relativistic Hamiltonian are reported for the actinide elements Ac and Np through Lr. These complete the series of sets reported previously for Th-U [K. A. Peterson, J. Chem. Phys. 142, 074105 (2015); M. Vasiliu et al., J. Phys. Chem. A 119, 11422 (2015)]. The new sets range in size from double- to quadruple-zeta and encompass both those optimized for valence (6s6p5f7s6d) and outer-core electron correlations (valence + 5s5p5d). The final sets have been contracted for both the DKH3 and eXact 2-component (X2C) Hamiltonians, yielding cc-pVnZ-DK3/cc-pVnZ-X2C sets for valence correlation and cc-pwCVnZ-DK3/cc-pwCVnZ-X2C sets for outer-core correlation (n = D, T, Q in each case). In order to test the effectiveness of the new basis sets, both atomic and molecular benchmark calculations have been carried out. In the first case, the first three atomic ionization potentials (IPs) of all the actinide elements Ac-Lr have been calculated using the Feller-Peterson-Dixon (FPD) composite approach, primarily with the multireference configuration interaction (MRCI) method. Excellent convergence towards the respective complete basis set (CBS) limits is achieved with the new sets, leading to good agreement with experiment, where these exist, after accurately accounting for spin-orbit effects using the 4-component Dirac-Hartree-Fock method. For a molecular test, the IP and atomization energy (AE) of PuO2 have been calculated also using the FPD method but using a coupled cluster approach with spin-orbit coupling accounted for using the 4-component MRCI. The present calculations yield an IP0 for PuO2 of 159.8 kcal/mol, which is in excellent agreement with the experimental electron transfer bracketing value of 162 ± 3 kcal/mol. Likewise, the calculated 0 K AE of 305.6 kcal/mol is in very good agreement with the currently accepted experimental value of 303.1 ± 5 kcal/mol. The ground state of PuO2 is predicted to be the 0 g +5Σ state.

Correlation consistent basis sets for actinides. II. The atoms Ac and Np-Lr.

PubMed

Feng, Rulin; Peterson, Kirk A

2017-08-28

New correlation consistent basis sets optimized using the all-electron third-order Douglas-Kroll-Hess (DKH3) scalar relativistic Hamiltonian are reported for the actinide elements Ac and Np through Lr. These complete the series of sets reported previously for Th-U [K. A. Peterson, J. Chem. Phys. 142, 074105 (2015); M. Vasiliu et al., J. Phys. Chem. A 119, 11422 (2015)]. The new sets range in size from double- to quadruple-zeta and encompass both those optimized for valence (6s6p5f7s6d) and outer-core electron correlations (valence + 5s5p5d). The final sets have been contracted for both the DKH3 and eXact 2-component (X2C) Hamiltonians, yielding cc-pVnZ-DK3/cc-pVnZ-X2C sets for valence correlation and cc-pwCVnZ-DK3/cc-pwCVnZ-X2C sets for outer-core correlation (n = D, T, Q in each case). In order to test the effectiveness of the new basis sets, both atomic and molecular benchmark calculations have been carried out. In the first case, the first three atomic ionization potentials (IPs) of all the actinide elements Ac-Lr have been calculated using the Feller-Peterson-Dixon (FPD) composite approach, primarily with the multireference configuration interaction (MRCI) method. Excellent convergence towards the respective complete basis set (CBS) limits is achieved with the new sets, leading to good agreement with experiment, where these exist, after accurately accounting for spin-orbit effects using the 4-component Dirac-Hartree-Fock method. For a molecular test, the IP and atomization energy (AE) of PuO 2 have been calculated also using the FPD method but using a coupled cluster approach with spin-orbit coupling accounted for using the 4-component MRCI. The present calculations yield an IP 0 for PuO 2 of 159.8 kcal/mol, which is in excellent agreement with the experimental electron transfer bracketing value of 162 ± 3 kcal/mol. Likewise, the calculated 0 K AE of 305.6 kcal/mol is in very good agreement with the currently accepted experimental value of 303.1 ± 5 kcal/mol. The ground state of PuO 2 is predicted to be the Σ0g+5 state.

Ground-state configurations and theoretical soft-x-ray emission of highly charged actinide ions

NASA Astrophysics Data System (ADS)

Sheil, J.; Kilbane, D.; O'Sullivan, G.; Liu, L.; Suzuki, C.

2017-12-01

It is well known that the lanthanide and actinide elements are formed by the filling of 4 f and 5 f subshells which occurs after the filling of 5 d and 6 d subshells, respectively, has begun. With increasing ionization one expects the energy levels to eventually regroup to their hydrogenic ordering, i.e., in terms of principal quantum number. In the lanthanides, the 4 f electron binding energy overtakes that of 5 p near the 6th or 7th ion stage and 5 s near the 14th or 15th ion stage, leading to dramatic rearrangements of ground-state configurations. In this paper we report on the results of a study to explore the effects of increasing ionization on the ground-state configurations of actinide ions as a result of 5 f and 6 p or 6 s level crossings. It is seen that the effects generally occur later and are more strongly influenced by spin-orbit splitting than in the lanthanides. The near degeneracies of 5 f and 6 l energies in these stages lead to configuration interaction (CI) amongst configurations with variable numbers of 5 f and 6 p electrons. The effects of CI on the level complexity are explored for ions along the Rn I sequence and are found to lead to the formation of "compound states" as predicted for the lanthanides. The extreme ultraviolet and soft x-ray spectra of medium and highly charged lanthanides are dominated by emission from unresolved transition arrays (UTAs) of the type Δ n =0 , 4 p64 dN +1-4 p54 dN +2+4 p64 dN4 f , which, in general, overlap in adjacent ion stages of a particular element. Here, the corresponding Δ n =0 , 5 p65 dN +1-5 p55 dN +2+5 p65 dN5 f UTAs have been studied theoretically with the aid of Hartree-Fock with configuration interaction calculations. As well as predicting the wavelengths and spectral details of the anticipated features, the calculations show that the effects of configuration interaction are quite different for the two different families of Δ n =0 transitions and, once more, spin-orbit interactions play a major role.

A review on solid phase extraction of actinides and lanthanides with amide based extractants.

PubMed

Ansari, Seraj A; Mohapatra, Prasanta K

2017-05-26

Solid phase extraction is gaining attention from separation scientists due to its high chromatographic utility. Though both grafted and impregnated forms of solid phase extraction resins are popular, the later is easy to make by impregnating a given organic extractant on to an inert solid support. Solid phase extraction on an impregnated support, also known as extraction chromatography, combines the advantages of liquid-liquid extraction and the ion exchange chromatography methods. On the flip side, the impregnated extraction chromatographic resins are less stable against leaching out of the organic extractant from the pores of the support material. Grafted resins, on the other hand, have a higher stability, which allows their prolong use. The goal of this article is a brief literature review on reported actinide and lanthanide separation methods based on solid phase extractants of both the types, i.e., (i) ligand impregnation on the solid support or (ii) ligand functionalized polymers (chemically bonded resins). Though the literature survey reveals an enormous volume of studies on the extraction chromatographic separation of actinides and lanthanides using several extractants, the focus of the present article is limited to the work carried out with amide based ligands, viz. monoamides, diamides and diglycolamides. The emphasis will be on reported applied experimental results rather than on data pertaining fundamental metal complexation. Copyright © 2017 Elsevier B.V. All rights reserved.

Metal-metal bonds in f-element chemistry.

PubMed

Liddle, Stephen T; Mills, David P

2009-08-07

The molecular chemistry of the f-elements is traditionally dominated by the use of carbon-, nitrogen-, oxygen-, or halide-ligands. However, the use of metal-based fragments as ligands is underdeveloped, which contrasts to the fields of d- and p-block metal-metal complexes that have developed extensively over the last fifty years. This perspective outlines the development of compounds, which possess polarised covalent or donor-acceptor f-element-metal bonds. For this review, the f-element is defined as (i) a group 3 or lanthanide metal: scandium, yttrium, lanthanum to lutetium, or (ii) an actinide metal: thorium, or uranium, and the metal is defined as a d-block transition metal, or a group 13 (aluminium or gallium), a group 14 (silicon, germanium, or tin), or a group 15 (antimony, or bismuth) metal. Silicon, germanium, and antimony are traditionally classified as metalloids but they are included for completeness. This review focuses mainly on complexes that have been structurally authenticated by single-crystal X-ray diffraction studies and we highlight novel aspects of their syntheses, properties, and reactivities.

The Heavy Nuclei eXplorer (HNX) Mission

NASA Astrophysics Data System (ADS)

Krizmanic, John; Mitchell, John; Binns, W. Robert; Hams, Thomas; Israel, Martin; Link, Jason; Rauch, Brian; Sakai, Kenichi; Sasaki, Makoto; Westphal, Andrew; Wiedenbeck, Mark; Heavy Nuclei eXplorer Collaboration

2016-03-01

The Heavy Nuclei eXplorer (HNX) will use two large high-precision instruments, the Extremely-heavy Cosmic-ray Composition Observer (ECCO) and the Cosmic-ray Trans-Iron Galactic Element Recorder (CosmicTIGER), designed to fly in a SpaceX DragonLab Capsule, to measure the cosmic-ray abundance of every individual element in the periodic table from carbon through curium, providing the first measurement of many of these elements. These measurements provide an investigation on the nature of the source material of cosmic rays, the processes that inject them into cosmic accelerators, and the acceleration mechanisms. HNX will measure several thousand ultra-heavy galactic cosmic ray (UHGCR) nuclei with Z >= 30 , including about 50 actinides (Z >= 79). These data allow for a measurement of the mix of new and old material that is accelerated to GCRs, determine their age, measure the mix of nucleosynthesis processes responsible for the UHGCRs, determine how UHGCR elements are selected for acceleration, and measure the mean integrated pathlength traversed by UHGCRs before observation. The scientific motivation and instrumentation of HNX will be discussed as well as recent beam test results.

A relativistic density functional study of the role of 5f electrons in atomic and molecular adsorptions on actinide surfaces

NASA Astrophysics Data System (ADS)

Huda, Muhammad Nurul

Atomic and molecular adsorptions of oxygen and hydrogen on actinide surfaces have been studied within the generalized gradient approximations to density functional theory (GGA-DFT). The primary goal of this work is to understand the details of the adsorption processes, such as chemisorption sites, energies, adsorption configurations and activation energies for dissociation of molecules; and the signature role of the plutonium 5f electrons. The localization of the 5f electrons remains one of central questions in actinides and one objective here is to understand the extent to which localizations plays a role in adsorption on actinide surfaces. We also investigated the magnetism of the plutonium surfaces, given the fact that magnetism in bulk plutonium is a highly controversial issue, and the surface magnetism of it is not a well explored territory. Both the non-spin-polarized and spin-polarized calculations have been performed to arrive at our conclusions. We have studied both the atomic and molecular hydrogen and oxygen adsorptions on plutonium (100) and (111) surfaces. We have also investigated the oxygen molecule adsorptions on uranium (100) surface. Comparing the adsorption on uranium and plutonium (100) surfaces, we have seen that O2 chemisorption energy for the most favorable adsorption site on uranium surface has higher chemisorption energy, 9.492 eV, than the corresponding plutonium site, 8.787 eV. Also degree of localization of 5f electrons is less for uranium surface. In almost all of the cases, the most favorable adsorption sites are found where the coordination numbers are higher. For example, we found center sites are the most favorable sites for atomic adsorptions. In general oxygen reacts more strongly with plutonium surface than hydrogen. We found that atomic oxygen adsorption energy on (100) surface is 3.613 eV more than that of the hydrogen adsorptions, considering only the most favorable site. This is also true for molecular adsorptions, as the oxygen molecules on both (100) and (111) plutonium surfaces dissociate almost spontaneously, whereas hydrogen needs some activation energy to dissociate. From spin-polarized calculations we found both (100) and (111) surfaces have the layer by layer alternating spin-magnetic behavior. In general adsorption of H2 and O2 do not change this behavior.

Titanite petrochronology in the Fish Canyon Tuff

NASA Astrophysics Data System (ADS)

Schmitz, M. D.; Crowley, J. L.

2014-12-01

The petrologic complexity of the archtypical 'monotonous intermediate' Fish Canyon Tuff (FCT) has been previously established by a variety of mineralogical and geochemical proxies [1-2], and the unusual storage and eruptive dynamics of the FCT have been delineated by several geochronological studies [3-5]. Titanite is an apparent equilibrium phase in the penultimate FCT magma, and can be linked petrographically to hornblende crystals that preserve up-temperature core-to-rim zoning profiles. As a reactive, trace element-rich phase, we hypothesized that titanite may record an intracrystalline record of magma chamber dynamics. Titanite crystals from the same separate analyzed in [4] were oriented and doubly-polished to yield characteristic wedge-shaped cross-sectional wafers approximately 300 µm in thickness. BSE imaging guided LA-ICPMS analyses of a full suite of trace elements using a 25 µm beam diameter and crater depth on multiple locations across both sides of the wafer. Most titanite crystals are characterized by large variations in trace elements, including at least two generations of REE-enriched, actinide-poor, low Sr, large Eu anomaly cores overgrown by REE-depleted, actinide-rich, high Sr domains with small Eu anomalies and distinctive concave-up middle to heavy REE patterns. Trace element contents and patterns correlate strongly with Eu anomaly; intermediate compositions are abundant and spatially correlated to reaction zones between core and rim domains. Within the context of the batholithic rejuvenation model for the FCT magma [1-2], these trace element variations are interpreted to record the partial melting of a differentiated crystalline FCT precursor and its hybridization with a more 'mafic' flux. ID-TIMS dating of end-member titanites confirm older ages (ca 28.4 to 29.0 Ma) for cores and define a younger age for rejuvenation of ca 28.2 Ma, consistent with recent U-Pb zircon and 40Ar/39Ar studies [5-7]. [1] Bachmann & Dungan (2002) Am Mineral 87, 1062-1076. [2] Bachmann et al (2002) J Petrology 43, 1469-1503. [3] Bachmann et al (2007) Chem Geol 236, 134-166. [4] Schmitz & Bowring (2001) GCA 65, 2571-2587. [5] Wotzlaw et al (2013) Geology 41, 867-870. [6] Rivera et al. (2011) EPSL 311, 420-426. [7] Kuiper et al (2008) Science 320, 500-504.

Controlling Actinide Hydration in Mixed Solvent Systems: Towards Tunable Solvent Systems to Close the Fuel Cycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, Sue B.

2016-10-31

The goal of this project has been to define the extent of hydration the f-elements and other cations in mixed solvent electrolyte systems. Methanol-water and other mixed solvent systems have been studied, where the solvent dielectric constant was varied systematically. Thermodynamic and spectroscopic studies provide details concerning the energetics of complexation and other reactions of these cations. This information has also been used to advance new understanding of the behavior of these cations in a variety of systems, ranging from environmental studies, chromatographic approaches, and ionization processes for mass spectrometry.

Crystal Growth and Characterization of THO2 and UxTh1-xO2

DTIC Science & Technology

2013-03-01

bulk actinide crystals would open up new possibilities for the detection of weapons of mass destruction, the study of the effect of aging on...way of growing bulk actinide materials of optical quality. These refractory oxide single crystals offer potential applications in thorium nuclear...fuel technology, wide-band-gap uranium-based direct-conversion solid state neutron detectors, and understanding how actinide fuels age with time. ThO2

TPE/REE separation with the use of zirconium salt of HDBP

NASA Astrophysics Data System (ADS)

Glekov, R. G.; Shmidt, O. V.; Palenik, Yu. V.; Goletsky, N. D.; Sukhareva, S. Yu.; Fedorov, Yu. S.; Zilberman, B. Ya.

2003-01-01

Partitioning of long-lived radionuclides (minor actinides, fission products) is considered as TBP-compatible ZEALEX-process for extraction separation of transplutonium elements (TPE) and rare-earth elements (REE), as well as Y, Mo, Fe and residual amounts of Np, Pu, U. Zirconium salt of dibutyl phosphoric acid (ZS-HDBP) dissolved in 30 % TBP is used as a solvent. The process was tested in multistage centrifugal contactors. Lanthanides, Y and TPE, as well as Mo, Fe were extracted from high-level Purex raffinate, Am and ceric subgroup of REE being separated from the polyvalent elements by stripping with HNO3. TPE/REE partitioning was achieved in the second cycle of the ZEALEX-process using DTPA in formic acid media. The integral decontamination factor of Am from La and Ce after both cycles is >200, from Pr and Nd 20-30 and from Sm and Eu 3.6; REE strips in both cycles contained <0,1% of the initial amount of TPE.

The effects of rare earth elements on an anaerobic hydrogen producing microorganism

NASA Astrophysics Data System (ADS)

Fujita, Y.; St Jeor, J. D.; Reed, D. W.

2016-12-01

Rapid growth of new energy technologies and consumer electronics is leading to increased fluxes of rare earth elements (REE), during the phases of resource extraction, product usage, recycling, and disposal. However, little is known about the impacts of these increased REE fluxes on environmental ecosystems, whether natural or engineered (e.g., biological waste treatment systems). We have been evaluating the effects of europium and yttrium on hydrogen production by an anaerobic fermenting microorganism, Sporacetigenium mesophilum, originally isolated from an anaerobic digester at a wastewater treatment plant.1 Europium and yttrium are important components of phosphors used in fluorescent lighting, and are expected to be recycled in larger quantities in the future. Also tested was the compound tributyl phosphate (TBP), a widely used complexing agent in lanthanide and actinide separations. TBP and related compounds may be used in recycling processes for REE. S. mesophilumcultures were amended with Eu at 100 ppb, 1 ppm and 10 ppm and hydrogen production was measured. While the lowest Eu concentration had minimal effect on hydrogen production compared to the no Eu control, the two higher Eu amendment levels appeared to enhance hydrogen production. TBP at 0.1 g/L completely inhibited hydrogen production. Measurements of aqueous Eu concentrations indicated that >85% of the added Eu remained soluble at all three of the Eu addition levels tested. Experiments to ascertain whether enhancement (or inhibition) occurs at even higher Eu concentrations are underway, as are corresponding experiments with yttrium. This work contributes to the assessment of the potential impacts of increased REE recycling and processing on ecosystems, and supports decision making with respect to disposal of wastewaters generated during these industrial practices. 1Chen, S., Song, L. and X. Dong. Int J. Syst. Evol. Microbiol. 56, 721-725, doi: 10.1099/ijs.0.63686-0 (2006).

Decomposition of diverse solid inorganic matrices with molten ammonium bifluoride salt for constituent elemental analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

O'Hara, Matthew J.; Kellogg, Cyndi M.; Parker, Cyrena M.

Ammonium bifluoride (ABF, NH4F·HF) is a well-known reagent for converting metal oxides to fluorides and for its applications in breaking down minerals and ores in order to extract useful components. It has been more recently applied to the decomposition of inorganic matrices prior to elemental analysis. Herein, a sample decomposition method that employs molten ABF sample treatment in the initial step is systematically evaluated across a range of inorganic sample types: glass, quartz, zircon, soil, and pitchblende ore. Method performance is evaluated across the two variables: duration of molten ABF treatment and ABF reagent mass to sample mass ratio. Themore » degree of solubilization of these sample classes are compared to the fluoride stoichiometry that is theoretically necessary to enact complete fluorination of the sample types. Finally, the sample decomposition method is performed on several soil and pitchblende ore standard reference materials, after which elemental constituent analysis is performed by ICP-OES and ICP-MS. Elemental recoveries are compared to the certified values; results indicate good to excellent recoveries across a range of alkaline earth, rare earth, transition metal, and actinide elements.« less

Nano-Scale Structure of Twin Boundaries in Shocked Zircon from the Vredefort Impact Structure.

NASA Astrophysics Data System (ADS)

Sharp, T. G.; Cavosie, A. J.

2017-12-01

Shock deformation of zircon produces distinct microstructures that can be used as evidence of shock in natural samples. These deformation features include {112} twins that have been observed in naturally shocked samples from Vredefort and elsewhere [1-3]. Electron backscatter diffraction (EBSD) has shown that these twins are polysynthetic, generally < 1µm wide and have a 65°/<110> crystallographic relation to the host zircon [2]. The structure and composition of these twin boundaries, and their effects on element mobility have not been explored previously. Here we use high-resolution TEM to investigate the nano-structure of a {112} twin in a shocked zircon crystal from the 2.0 Ga Vredefort impact structure [3]. Focused-ion-beam lift-out techniques were used to prepare a TEM foil with a 1 µm wide {112}-twin lamella. The foil was characterized by TEM imaging and electron diffraction using a FEI CM200-FEG transmission electron microscope. Selected area diffraction from the {112}-twin boundary, along a <111> zone, showed no apparent evidence of twining. However, the domain boundaries displayed weak diffraction contrast in this orientation. High-resolution images show a 50-nm wide zone of heterogeneous structural disorder and locally amorphous domains along the twin boundaries that is inferred to be a localized metamict zone. The detailed lattice structure of the interface was not discernable because of this structural disorder. Diffraction and imaging along <021> confirms that the {112}-twin composition plane is a mirror plane. The crystallographic relations observed along <110> and <021> are consistent with the 65°/<110> twin structure previously determined from EBSD [2]. Enhanced metamict disorder suggests a higher concentration of actinides along the twin boundaries and implies actinide mobility near twin boundaries. [1] Moser et al, 2011 Can J Earth Sci. [2] Erickson et al. 2013 Am Min. [3] Cavosie et al. 2015 Geol.

Nuclear waste disposal—pyrochlore (A2B2O7): Nuclear waste form for the immobilization of plutonium and "minor" actinides

NASA Astrophysics Data System (ADS)

Ewing, Rodney C.; Weber, William J.; Lian, Jie

2004-06-01

During the past half-century, the nuclear fuel cycle has generated approximately 1400 metric tons of plutonium and substantial quantities of the "minor" actinides, such as Np, Am, and Cm. The successful disposition of these actinides has an important impact on the strategy for developing advanced nuclear fuel cycles, weapons proliferation, and the geologic disposal of high-level radioactive waste. During the last decade, there has been substantial interest in the use of the isometric pyrochlore structure-type, A2B2O7, for the immobilization of actinides. Most of the interest has focused on titanate-pyrochlore because of its chemical durability; however, these compositions experience a radiation-induced transition from the crystalline-to-aperiodic state due to radiation damage from the alpha-decay of actinides. Depending on the actinide concentration, the titanate pyrochlore will become amorphous in less than 1000 years of storage. Recently, systematic ion beam irradiations of a variety of pyrochlore compositions has revealed that many zirconate pyrochlores do not become amorphous, but remain crystalline as a defect fluorite structure-type due to disordering of the A- and B-site cations. The zirconate pyrochlores will remain crystalline even to very high doses, greater than 100 displacements per atom. Systematic experimental studies of actinide-doped and ion beam-irradiated pyrochlore, analyses of natural U- and Th-bearing pyrochlore, and simulations of the energetics of the disordering process now provide a rather detailed understanding of the structural and chemical controls on the response of pyrochlore to radiation. These results provide a solid basis for predicting the behavior and durability of pyrochlore used to immobilize plutonium.

Predictive Modeling in Actinide Chemistry and Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ping

2016-05-16

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

Georgia Institute of Technology research on the Gas Core Actinide Transmutation Reactor (GCATR)

NASA Technical Reports Server (NTRS)

Clement, J. D.; Rust, J. H.; Schneider, A.; Hohl, F.

1976-01-01

The program reviewed is a study of the feasibility, design, and optimization of the GCATR. The program is designed to take advantage of initial results and to continue work carried out on the Gas Core Breeder Reactor. The program complements NASA's program of developing UF6 fueled cavity reactors for power, nuclear pumped lasers, and other advanced technology applications. The program comprises: (1) General Studies--Parametric survey calculations performed to examine the effects of reactor spectrum and flux level on the actinide transmutation for GCATR conditions. The sensitivity of the results to neutron cross sections are to be assessed. Specifically, the parametric calculations of the actinide transmutation are to include the mass, isotope composition, fission and capture rates, reactivity effects, and neutron activity of recycled actinides. (2) GCATR Design Studies--This task is a major thrust of the proposed research program. Several subtasks are considered: optimization criteria studies of the blanket and fuel reprocessing, the actinide insertion and recirculation system, and the system integration. A brief review of the background of the GCATR and ongoing research is presented.

Rapid determination of actinides in asphalt samples

DOE PAGES

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

2014-01-12

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

Selective Separation of Trivalent Actinides from Lanthanides by Aqueous Processing with Introduction of Soft Donor Atoms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kenneth L. Nash

2009-09-22

Implementation of a closed loop nuclear fuel cycle requires the utilization of Pu-containing MOX fuels with the important side effect of increased production of the transplutonium actinides, most importantly isotopes of Am and Cm. Because the presence of these isotopes significantly impacts the long-term radiotoxicity of high level waste, it is important that effective methods for their isolation and/or transmutation be developed. Furthermore, since transmutation is most efficiently done in the absence of lanthanide fission products (high yield species with large thermal neutron absorption cross sections) it is important to have efficient procedures for the mutual separation of Am andmore » Cm from the lanthanides. The chemistries of these elements are nearly identical, differing only in the slightly stronger strength of interaction of trivalent actinides with ligand donor atoms softer than O (N, Cl-, S). Research being conducted around the world has led to the development of new reagents and processes with considerable potential for this task. However, pilot scale testing of these reagents and processes has demonstrated the susceptibility of the new classes of reagents to radiolytic and hydrolytic degradation. In this project, separations of trivalent actinides from fission product lanthanides have been investigated in studies of 1) the extraction and chemical stability properties of a class of soft-donor extractants that are adapted from water-soluble analogs, 2) the application of water soluble soft-donor complexing agents in tandem with conventional extractant molecules emphasizing fundamental studies of the TALSPEAK Process. This research was conducted principally in radiochemistry laboratories at Washington State University. Collaborators at the Radiological Processing Laboratory (RPL) at the Pacific Northwest National Laboratory (PNNL) have contributed their unique facilities and capabilities, and have supported student internships at PNNL to broaden their academic experience. New information has been developed to qualify the extraction potential of a class of pyridine-functionalized tetraaza complexants indicating potential single contact Am-Nd separation factors of about 40. The methodology developed for characterization will find further application in our continuing efforts to synthesize and characterize new reagents for this separation. Significant new insights into the performance envelope and supporting information on the TALSPEAK process has also been developed.« less

Macrophages as key elements of Mixed-oxide [U-Pu(O2)] distribution and pulmonary damage after inhalation?

PubMed

Van der Meeren, Anne; Moureau, Agnes; Griffiths, Nina M

2014-11-01

Abstract Purpose: To investigate the consequences of alveolar macrophage (AM) depletion on Mixed OXide fuel (MOX: U, Pu oxide) distribution and clearance, as well as lung damage following MOX inhalation. Rats were exposed to MOX by nose only inhalation. AM were depleted with intratracheal administration of liposomal clodronate at 6 weeks. Lung changes, macrophage activation, as well as local and systemic actinide distribution were studied up to 3 months post-inhalation. Clodronate administration modified excretion/retention patterns of α activity. At 3 months post-inhalation lung retention was higher in clodronate-treated rats compared to Phosphate Buffered Saline (PBS)-treated rats, and AM-associated α activity was also increased. Retention in liver was higher in clodronate-treated rats and fecal and urinary excretions were lower. Three months after inhalation, rats exhibited lung fibrotic lesions and alveolitis, with no marked differences between the two groups. Foamy macrophages of M2 subtype [inducible Nitric Oxide Synthase (iNOS) negative but galectin-3 positive] were frequently observed, in correlation with the accumulation of MOX particles. AM from all MOX-exposed rats showed increased chemokine levels as compared to sham controls. Despite the transient reduced AM numbers in clodronate-treated animals no major differences on lung damage were observed as compared to non-treated rats after MOX inhalation. The higher lung activity retention in rats receiving clodronate seems to be part of a general inflammatory response and needs further investigation.

From carbon to actinides: A new universal 1MV accelerator mass spectrometer at ANSTO

NASA Astrophysics Data System (ADS)

Wilcken, K. M.; Hotchkis, M.; Levchenko, V.; Fink, D.; Hauser, T.; Kitchen, R.

2015-10-01

A new 1 MV NEC pelletron AMS system at ANSTO is presented. The spectrometer comprises large radius magnets for actinide measurements. A novel feature of the system is fast switching between isotopes both at low and high energy sections allowing measurements of up to 8 isotopes within a single sequence. Technical details and layout of the spectrometer is presented. Performance data for 14C, 10Be, 26Al and actinides demonstrate the system is ready for routine AMS measurements.

Magnetic susceptibilities of actinide 3d-metal intermetallic compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muniz, R.B.; d'Albuquerque e Castro, J.; Troper, A.

1988-04-15

We have numerically calculated the magnetic susceptibilities which appear in the Hartree--Fock instability criterion for actinide 3d transition-metal intermetallic compounds. This calculation is based on a previous tight-binding description of these actinide-based compounds (A. Troper and A. A. Gomes, Phys. Rev. B 34, 6487 (1986)). The parameters of the calculation, which starts from simple tight-binding d and f bands are (i) occupation numbers, (ii) ratio of d-f hybridization to d bandwidth, and (iii) electron-electron Coulomb-type interactions.

Pocket formula for nuclear deformations of actinides

NASA Astrophysics Data System (ADS)

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

2018-06-01

We have formulated a pocket formula for quadrupole (β2), octupole (β3), hexadecapole (β4) and hexacontatetrapole (β6) deformation of the nuclear ground state of all isotopes of actinide nuclei (89 < Z < 103). This formula is first of its kind and produces a nuclear deformation of all isotopes actinide nuclei 89 < Z < 103 with simple inputs of Z and A. Hence, this formula is useful in the fields of nuclear physics to study the structure and interaction of nuclei.

Method for extracting lanthanides and actinides from acid solutions

DOEpatents

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

1985-01-01

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

RAPID DETERMINATION OF ACTINIDES IN URINE BY INDUCTIVELY-COUPLED PLASMA MASS SPECTROMETRY AND ALPHA SPECTROMETRY: A HYBRID APPROACH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maxwell, S.; Jones, V.

2009-05-27

A new rapid separation method that allows separation and preconcentration of actinides in urine samples was developed for the measurement of longer lived actinides by inductively coupled plasma mass spectrometry (ICP-MS) and short-lived actinides by alpha spectrometry; a hybrid approach. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration, if required, is performed using a streamlined calcium phosphate precipitation. Similar technology has been applied to separate actinides prior to measurement by alpha spectrometry, but this new method has been developed with elution reagents now compatible with ICP-MS as well. Purified solutions are splitmore » between ICP-MS and alpha spectrometry so that long- and short-lived actinide isotopes can be measured successfully. The method allows for simultaneous extraction of 24 samples (including QC samples) in less than 3 h. Simultaneous sample preparation can offer significant time savings over sequential sample preparation. For example, sequential sample preparation of 24 samples taking just 15 min each requires 6 h to complete. The simplicity and speed of this new method makes it attractive for radiological emergency response. If preconcentration is applied, the method is applicable to larger sample aliquots for occupational exposures as well. The chemical recoveries are typically greater than 90%, in contrast to other reported methods using flow injection separation techniques for urine samples where plutonium yields were 70-80%. This method allows measurement of both long-lived and short-lived actinide isotopes. 239Pu, 242Pu, 237Np, 243Am, 234U, 235U and 238U were measured by ICP-MS, while 236Pu, 238Pu, 239Pu, 241Am, 243Am and 244Cm were measured by alpha spectrometry. The method can also be adapted so that the separation of uranium isotopes for assay is not required, if uranium assay by direct dilution of the urine sample is preferred instead. Multiple vacuum box locations may be set-up to supply several ICP-MS units with purified sample fractions such that a high sample throughput may be achieved, while still allowing for rapid measurement of short-lived actinides by alpha spectrometry.« less

Reactor-based management of used nuclear fuel: assessment of major options.

PubMed

Finck, Phillip J; Wigeland, Roald A; Hill, Robert N

2011-01-01

This paper discusses the current status of the ongoing Advanced Fuel Cycle Initiative (AFCI) program in the U.S. Department of Energy that is investigating the potential for using the processing and recycling of used nuclear fuel to improve radioactive waste management, including used fuel. A key element of the strategies is to use nuclear reactors for further irradiation of recovered chemical elements to transmute certain long-lived highly-radioactive isotopes into less hazardous isotopes. Both thermal and fast neutron spectrum reactors are being studied as part of integrated nuclear energy systems where separations, transmutation, and disposal are considered. Radiotoxicity is being used as one of the metrics for estimating the hazard of used fuel and the processing of wastes resulting from separations and recycle-fuel fabrication. Decay heat from the used fuel and/or wastes destined for disposal is used as a metric for use of a geologic repository. Results to date indicate that the most promising options appear to be those using fast reactors in a repeated recycle mode to limit buildup of higher actinides, since the transuranic elements are a key contributor to the radiotoxicity and decay heat. Using such an approach, there could be much lower environmental impact from the high-level waste as compared to direct disposal of the used fuel, but there would likely be greater generation of low-level wastes that will also require disposal. An additional potential waste management benefit is having the ability to tailor waste forms and contents to one or more targeted disposal environments (i.e., to be able to put waste in environments best-suited for the waste contents and forms). Copyright © 2010 Health Physics Society

Fusion barrier characteristics of actinides

NASA Astrophysics Data System (ADS)

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

2018-03-01

We have studied fusion barrier characteristics of actinide compound nuclei with atomic number range 89 ≤ Z ≤ 103 for all projectile target combinations. After the calculation of fusion barrier heights and positions, we have searched for their parameterization. We have achieved the empirical formula for fusion barrier heights (VB), positions (RB), curvature of the inverted parabola (ħω) of actinide compound nuclei with atomic number range 89 ≤ Z ≤ 103 for all projectile target combinations (6

Electronic structure of free and doped actinides: N and Z dependences of energy levels and electronic structure parameters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kulagin, N.

2005-02-15

Theoretical study of electronic structure of antinide ions and its dependence on N and Z are presented in this paper. The main 5f{sup N} and excited 5f{sup N}n'l'{sup N'} configurations of actinides have been studied using Hartree-Fock-Pauli approximation. Results of calculations of radial integrals and the energy of X-ray lines for all 5f ions with electronic state AC{sup +1}-AC{sup +4} show approximate dependence on N and Z. A square of N and cubic of Z are ewalized for the primary electronic parameters of the actinides. Theoretical values of radial integrals for free actinides and for ions in a cluster AC{supmore » +n}:[L]{sub k} are compared, too.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kersting, Annie B.; Zavarin, Mavrik

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) ismore » 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).« less

The use of MOX caramel fuel mixed with 241Am, 242mAm and 243Am as burnable absorber actinides for the MTR research reactors.

PubMed

Shaaban, Ismail; Albarhoum, Mohamad

2017-07-01

The MOX (UO 2 &PuO 2 ) caramel fuel mixed with 241 Am, 242m Am and 243 Am as burnable absorber actinides was proposed as a fuel of the MTR-22MW reactor. The MCNP4C code was used to simulate the MTR-22MW reactor and estimate the criticality and the neutronic parameters, and the power peaking factors before and after replacing its original fuel (U 3 O 8 -Al) by the MOX caramel fuel mixed with 241 Am, 242m Am and 243 Am actinides. The obtained results of the criticality, the neutronic parameters, and the power peaking factors for the MOX caramel fuel mixed with 241 Am, 242m Am and 243 Am actinides were compared with the same parameters of the U 3 O 8 -Al original fuel and a maximum difference is -6.18% was found. Additionally, by recycling 2.65% and 2.71% plutonium and 241 Am, 242m Am and 243 Am actinides in the MTR-22MW reactor, the level of 235 U enrichment is reduced from 4.48% to 3% and 2.8%, respectively. This also results in the reduction of the 235 U loading by 32.75% and 37.22% for the 2.65%, the 2.71% plutonium and 241 Am, 242m Am and 243 Am actinides, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Measurement of Irradiated Pyroprocessing Samples via Laser Induced Breakdown Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phongikaroon, Supathorn

The primary objective of this research is to develop an applied technology and provide an assessment to remotely measure and analyze the real time or near real time concentrations of used nuclear fuel (UNF) dissolute in electrorefiners. Here, Laser-Induced Breakdown Spectroscopy (LIBS), in UNF pyroprocessing facilities will be investigated. LIBS is an elemental analysis method, which is based on the emission from plasma generated by focusing a laser beam into the medium. This technology has been reported to be applicable in the media of solids, liquids (includes molten metals), and gases for detecting elements of special nuclear materials. The advantagesmore » of applying the technology for pyroprocessing facilities are: (i) Rapid real-time elemental analysis|one measurement/laser pulse, or average spectra from multiple laser pulses for greater accuracy in < 2 minutes; (ii) Direct detection of elements and impurities in the system with low detection limits|element specific, ranging from 2-1000 ppm for most elements; and (iii) Near non-destructive elemental analysis method (about 1 g material). One important challenge to overcome is achieving high-resolution spectral analysis to quantitatively analyze all important fission products and actinides. Another important challenge is related to accessibility of molten salt, which is heated in a heavily insulated, remotely operated furnace in a high radiation environment with an argon atmosphere.« less

Modelos estereoquimicos na quimica de coordenacao e organometalica de lantanideos e actinideos: aplicacoes a complexos de torio (iv) com boratos de polipirazolilo (Stereochemical models in lanthanide and actinide coordination and organometallic chemistry: Applications to thorium (IV) complexes with polypyrazolylborates). Doctoral thesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

de Almeida, J.C.M.

1990-01-01

A detailed analysis is made of two stereochemical models commonly used in lanthanide and actinide coordination and organometallic chemistry. Li Xing-fu's Cone Packing Model and K. N. Raymond's Ionic Model. Corrections are introduced in the first model as a basis to discuss the stability and structure of known complexes. A Steric Coordination Number is defined for the second model, based on the solid angle to correlate metal-ligand distances in complexes with the ionic radii of the elements and to assign effective radii to the ligands, related to the donating power of the coordinating atoms. As an application of the models,more » the syntheses and characterizations of thorium(IV) complexes with polypyrazolylborates. (HBPz3) {sup -1} and (HB(3.5-Me2Pz)3) {sup -1}, and alkoxides, aryloxides, carboxylates, amides, thiolates, alkyls and cyclopentadienyl are described and their stabilities discussed. The geometries of the complexes in the solid and in solution are discussed and a mechanism is proposed to explain the fluxionality in solution of the complexes with (HBPz3) {sup -1}.« less

Back-end of the fuel cycle - Indian scenario

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wattal, P.K.

Nuclear power has a key role in meeting the energy demands of India. This can be sustained by ensuring robust technology for the back end of the fuel cycle. Considering the modest indigenous resources of U and a huge Th reserve, India has adopted a three stage Nuclear Power Programme (NPP) based on 'closed fuel cycle' approach. This option on 'Recovery and Recycle' serves twin objectives of ensuring adequate supply of nuclear fuel and also reducing the long term radio-toxicity of the wastes. Reprocessing of the spent fuel by Purex process is currently employed. High Level Liquid Waste (HLW) generatedmore » during reprocessing is vitrified and undergoes interim storage. Back-end technologies are constantly modified to address waste volume minimization and radio-toxicity reduction. Long-term management of HLW in Indian context would involve partitioning of long lived minor actinides and recovery of valuable fission products specifically cesium. Recovery of minor actinides from HLW and its recycle is highly desirable for the sustained growth of India's NPPs. In this context, programme for developing and deploying partitioning technologies on industrial scale is pursued. The partitioned elements could be either transmuted in Fast Reactors (FRs)/Accelerated Driven Systems (ADS) as an integral part of sustainable Indian NPP. (authors)« less

U(IV) chalcogenolates synthesized via oxidation of uranium metal by dichalcogenides.

PubMed

Gaunt, Andrew J; Scott, Brian L; Neu, Mary P

2006-09-04

Treatment of uranium metal with dichalcogenides in the presence of a catalytic amount of iodine in pyridine affords molecular U(IV) chalcogenolates that do not require stabilizing ancillary ligands. Oxidation of U(0) by PhEEPh yields monomeric seven-coordinate U(EPh)4(py)3 (E = S(1), Se(2)). The dimeric eight-coordinate complexes [U(EPh)2(mu2-EPh)2(CH3CN)2]2 (E = S(3), Se(4)) are obtained by crystallization from solutions of 1 and 2 dissolved in acetonitrile. Oxidation of U(0) by pySSpy and crystallization from thf yields nine-coordinate U(Spy)4(thf) (5). Incorporation of elemental selenium into the oxidation of U(0) by PhSeSePh results in the isolation of [U(py)2(SePh)(mu3-Se)(mu2-SePh)]4.4py (6), a tetrameric cluster in which each U(IV) ion is eight-coordinate and the U4Se4 core forms a distorted cube. The compounds were analyzed spectroscopically and the single-crystal X-ray structures of 1 and 3-6 were determined. The isolation of 1-6 represents six new examples of actinide chalcogenolates and allows insight into the nature of "hard" actinide ion-"soft" chalcogen donor interactions.

M3FT-15OR0202212: SUBMIT SUMMARY REPORT ON THERMODYNAMIC EXPERIMENT AND MODELING

DOE Office of Scientific and Technical Information (OSTI.GOV)

McMurray, Jake W.; Brese, Robert G.; Silva, Chinthaka M.

2015-09-01

Modeling the behavior of nuclear fuel with a physics-based approach uses thermodynamics for key inputs such as chemical potentials and thermal properties for phase transformation, microstructure evolution, and continuum transport simulations. Many of the lanthanide (Ln) elements and Y are high-yield fission products. The U-Y-O and U-Ln-O ternaries are therefore key subsystems of multi-component high-burnup fuel. These elements dissolve in the dominant urania fluorite phase affecting many of its properties. This work reports on an effort to assess the thermodynamics of the U-Pr-O and U-Y-O systems using the CALPHAD (CALculation of PHase Diagrams) method. The models developed within this frameworkmore » are capable of being combined and extended to include additional actinides and fission products allowing calculation of the phase equilibria, thermochemical and material properties of multicomponent fuel with burnup.« less

Trek and ECCO: Abundance measurements of ultraheavy galactic cosmic rays

NASA Astrophysics Data System (ADS)

Westphal, Andrew J.

2000-06-01

Using the Trek detector, we have measured the abundances of the heaviest elements (with Z>70) in the galactic cosmic rays with sufficient charge resolution to resolve the even-Z elements. We find that the abundance of Pb compared to Pt is ~3 times lower than the value expected from the most widely-held class of models of the origin of galactic cosmic ray nuclei, that is, origination in a partially ionized medium with solar-like composition. The low abundance of Pb is, however, consistent with the interstellar gas and dust model of Meyer, Drury and Ellison, and with a source enriched in r-process material, proposed by Binns et al. A high-resolution, high-statistics measurement of the abundances of the individual actinides would distinguish between these models. This is the goal of ECCO, the Extremely Heavy Cosmic-ray Composition Observer, which we plan to deploy on the International Space Station. .

Actinide Sputtering Induced by Fission with Ultra-cold Neutrons

NASA Astrophysics Data System (ADS)

Venuti, Michael; Shi, Tan; Fellers, Deion; Morris, Christopher; Makela, Mark

2017-09-01

Understanding the effects of actinide sputtering due to nuclear fission is important for a wide range of applications, including nuclear fuel storage, space science, and national defense. A new program at the Los Alamos Neutron Science Center uses ultracold neutrons (UCN) to induce fission in actinides such as uranium and plutonium. By controlling the energy of UCN, it is possible to induce fission at the sample surface within a well-defined depth. It is therefore an ideal tool for studying the effects of fission-induced sputtering as a function of interaction depth. Since the mechanism for fission-induced surface damage is not well understood, especially for samples with a surface oxide layer, this work has the potential to separate the various damage mechanisms proposed in previous works. During the irradiation with UCN, fission events are monitored by coincidence counting between prompt gamma rays using NaI detectors. Alpha spectroscopy of the ejected actinide material is performed in a custom-built ionization chamber to determine the amount of sputtered material. Actinide samples with various sample properties and surface conditions are irradiated and analyzed. In this presentation, we will discuss our experimental setup and present the preliminary results.

Electrochemical reduction of CerMet fuels for transmutation using surrogate CeO2-Mo pellets

NASA Astrophysics Data System (ADS)

Claux, B.; Souček, P.; Malmbeck, R.; Rodrigues, A.; Glatz, J.-P.

2017-08-01

One of the concepts chosen for the transmutation of minor actinides in Accelerator Driven Systems or fast reactors proposes the use of fuels and targets containing minor actinides oxides embedded in an inert matrix either composed of molybdenum metal (CerMet fuel) or of ceramic magnesium oxide (CerCer fuel). Since the sufficient transmutation cannot be achieved in a single step, it requires multi-recycling of the fuel including recovery of the not transmuted minor actinides. In the present work, a pyrochemical process for treatment of Mo metal inert matrix based CerMet fuels is studied, particularly the electroreduction in molten chloride salt as a head-end step required prior the main separation process. At the initial stage, different inactive pellets simulating the fuel containing CeO2 as minor actinide surrogates were examined. The main studied parameters of the process efficiency were the porosity and composition of the pellets and the process parameters as current density and passed charge. The results indicated the feasibility of the process, gave insight into its limiting parameters and defined the parameters for the future experiment on minor actinide containing material.

Local Symmetry Effects in Actinide 4f X-ray Absorption in Oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Butorin, Sergei M.; Modin, Anders; Vegelius, Johan R.

2016-03-23

A systematic X-ray absorption study at actinide N 6,7 (4f → 6d transitions) edges was performed for light-actinide oxides including data obtained for the first time for NpO 2, PuO 2, and UO 3. The measurements were supported by ab initio calculations based on local-density-approximation with added 5f-5f Coulomb interaction (LDA+U). Improved energy resolution compared to common experiments at actinide L 2,3 (2p → 6d transitions) edges allowed us to resolve the major structures of the unoccupied 6d density of states (DOS) and estimate the crystal-field splittings in the 6d shell directly from the spectra of light-actinide dioxides. The measurementsmore » demonstrated an enhanced sensitivity of the N 6,7 spectral shape to changes in the compound crystal structure. Finally, for nonstoichiometric NpO 2-x, the filling of the entire band gap with Np 6d states was observed thus supporting a phase coexistence of Np metal and stoichiometric NpO 2 which is in agreement with the tentative Np-O phase diagram.« less

Joint Actinide Shock Physics Experimental Research - JASPER

ScienceCinema

None

2018-01-16

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

Rapid method to determine actinides and 89/90Sr in limestone and marble samples

DOE PAGES

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

2016-04-12

A new method for the determination of actinides and radiostrontium in limestone and marble samples has been developed that utilizes a rapid sodium hydroxide fusion to digest the sample. Following rapid pre-concentration steps to remove sample matrix interferences, the actinides and 89/90Sr are separated using extraction chromatographic resins and measured radiometrically. The advantages of sodium hydroxide fusion versus other fusion techniques will be discussed. Lastly, this approach has a sample preparation time for limestone and marble samples of <4 hours.

SOLVENT EXTRACTION PROCESS FOR THE RECOVERY OF METALS FROM PHOSPHORIC ACID

DOEpatents

Bailes, R.H.; Long, R.S.

1958-11-01

> A solvent extraction process is presented for recovering metal values including uranium, thorium, and other lanthanide and actinide elements from crude industrial phosphoric acid solutions. The process conslsts of contacting said solution with an immisclble organic solvent extractant containing a diluent and a material selected from the group consisting of mono and di alkyl phosphates, alkyl phosphonates and alkyl phosphites. The uranlum enters the extractant phase and is subsequently recovered by any of the methods known to the art. Recovery is improved if the phosphate solution is treated with a reducing agent such as iron or aluminum powder prior to the extraction step.

Advancing the scientific basis of trivalent actinide-lanthanide separations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash, K.L.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarta, Jose A.; Castiblanco, Luis A

With cooperation of the International Atomic Energy Agency (IAEA) and the Department of Energy (DOE) of the United States, several calculations and tasks related to the waste disposal of spent MTR fuel enriched nominally to 93% were carried out for the conversion of the IAN-R1 Research Reactor from MTR-HEU fuel to TRIGA-LEU fuel. In order to remove the spent MTR-HEU fuel of the core and store it safely a program was established at the Instituto de Ciencias Nucleares y Energias Alternativas (INEA). This program included training, acquisition of hardware and software, design and construction of a decay pool, transfer ofmore » the spent HEU fuel elements into the decay pool and his final transport to Savannah River in United States. In this paper are presented data of activities calculated for each relevant radionuclide present in spent MTR-HEU fuel elements of the IAN-R1 Research Reactor and the total activity. The total activity calculated takes in consideration contributions of fission, activation and actinides products. The data obtained were the base for shielding calculations for the decay pool concerning the storage of spent MTR-HEU fuel elements and the respective dosimetric evaluations in the transferring operations of fuel elements into the decay pool.« less

Chemistry of berkelium: A review

NASA Astrophysics Data System (ADS)

Hobart, D. E.; Peterson, J. R.

Element 97 was first produced in December 1949, by the bombardment of americium-241 with accelerated alpha particles. This new element was named berkelium (Bk) after Berkeley, California, the city of its discovery. In the 36 years since the discovery of Bk, a substantial amount of knowledge concerning the physicochemical properties of this relatively scarce transplutonium element was acquired. All of the Bk isotopes of mass numbers 240 and 242 through 251 are presently known, but only berkelium-249 is available in sufficient quantities for bulk chemical studies. About 0.7 gram of this isotope was isolated at the HFIR/TRU Complex in Oak Ridge, Tennessee in the last 18 years. Over the same time period, the scale of experimental work using berkelium-249 has increased from the tracer level to bulk studies at the microgram level to solution and solid state investigations with milligram quantities. Extended knowledge of the physicochemical behavior of berkelium is important in its own right, because Bk is the first member of the second half of the actinide series. In addition, such information should enable more accurate extrapolations to the predicted behavior of heavier elements for which experimental studies are severely limited by lack of material and/or by intense radioactivity.

Sigma Team for Advanced Actinide Recycle FY2015 Accomplishments and Directions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moyer, Bruce A.

The Sigma Team for Minor Actinide Recycle (STAAR) has made notable progress in FY 2015 toward the overarching goal to develop more efficient separation methods for actinides in support of the United States Department of Energy (USDOE) objective of sustainable fuel cycles. Research in STAAR has been emphasizing the separation of americium and other minor actinides (MAs) to enable closed nuclear fuel recycle options, mainly within the paradigm of aqueous reprocessing of used oxide nuclear fuel dissolved in nitric acid. Its major scientific challenge concerns achieving selectivity for trivalent actinides vs lanthanides. Not only is this challenge yielding to researchmore » advances, but technology concepts such as ALSEP (Actinide Lanthanide Separation) are maturing toward demonstration readiness. Efforts are organized in five task areas: 1) combining bifunctional neutral extractants with an acidic extractant to form a single process solvent, developing a process flowsheet, and demonstrating it at bench scale; 2) oxidation of Am(III) to Am(VI) and subsequent separation with other multivalent actinides; 3) developing an effective soft-donor solvent system for An(III) selective extraction using mixed N,O-donor or all-N donor extractants such as triazinyl pyridine compounds; 4) testing of inorganic and hybrid-type ion exchange materials for MA separations; and 5) computer-aided molecular design to identify altogether new extractants and complexants and theory-based experimental data interpretation. Within these tasks, two strategies are employed, one involving oxidation of americium to its pentavalent or hexavalent state and one that seeks to selectively complex trivalent americium either in the aqueous phase or the solvent phase. Solvent extraction represents the primary separation method employed, though ion exchange and crystallization play an important role. Highlights of accomplishments include: Confirmation of the first-ever electrolytic oxidation of Am(III) in a noncomplexing aqueous solution and submission of this scientific breakthrough as a paper in Science; The first-ever co-crystallization of Am(VI) with UO 2(NO 3) 2 ∙ 6H 2O, opening the door to a new approach for separating hexavalent actinides as a group; Results showing that three potentially problematic metals will not present risk in ALSEP; Improvement in ALSEP contactor stripping kinetics to acceptable performance; A comparison of centrifugal contactors vs mixer-settlers showing the former performs better in ALSEP stripping; Synthesis of new mixed N,O-donor extractants with enhanced solubility and strength for selective trivalent actinide extraction; Development of computational methods showing promise in prediction of the selectivity of new extractants for trivalent actinides vs lanthanides; An order-of-magnitude improvement in aqueous Am/Eu complexation selectivity of an alternative macrocyclic stripping agent for ALSEP, potentially enabling an option for an Am product stream free from both Ln and Cm. An alternative aqueous combination of dipicolinate complexant and malonate buffer that may present options for ALSEP and TALSPEAK (Trivalent Actinide-Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Komplexes) type separations. The ALSEP concept is advancing toward a benchtop flowsheet demonstration planned for FY 2016, and a bench-scale test bed at Idaho National Laboratory (INL) will be employed to demonstrate at least one tandem Am oxidation and separation concept. This report outlines the goals of the STAAR, significance of achieving these goals, STAAR organization around the above aims and questions, recent highlights, and future directions. The report also includes a listing of publications, reports, patents, and dissertations.« less

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA-); Synthesis and Structure of MIVTTA4 (MIV = Zr, Hf, Ce, Th, U, Np, Pu) and MIII(TTA)4- (MIII = Ce, Nd, Sm, Yb).

PubMed

Cary, Samantha K; Livshits, Maksim; Cross, Justin N; Ferrier, Maryline G; Mocko, Veronika; Stein, Benjamin W; Kozimor, Stosh A; Scott, Brian L; Rack, Jeffrey J

2018-04-02

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction-or find alternatives-because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report here advances in fundamental understanding of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV (TTA) 4 . Meanwhile, +3 metals formed anionic M III (TTA) 4 - species. Characterization of these M(TTA) 4 x- ( x = 0, 1) compounds by UV-vis-NIR, IR, 1 H and 19 F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV (TTA) 4 and Pu IV (TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV (TTA) 4 and M III (TTA) 4 - are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV , Hf IV , and Zr IV .

FCRD Transmutation Fuels Handbook 2015

DOE Office of Scientific and Technical Information (OSTI.GOV)

Janney, Dawn Elizabeth; Papesch, Cynthia Ann

2015-09-01

Transmutation of minor actinides such as Np, Am, and Cm in spent nuclear fuel is of international interest because of its potential for reducing the long-term health and safety hazards caused by the radioactivity of the spent fuel. One important approach to transmutation (currently being pursued by the DOE Fuel Cycle Research & Development Advanced Fuels Campaign) involves incorporating the minor actinides into U-Pu-Zr alloys, which can be used as fuel in fast reactors. It is, therefore, important to understand the properties of U-Pu-Zr alloys, both with and without minor actinide additions. In addition to requiring extensive safety precautions, alloysmore » containing U and Pu are difficult to study for numerous reasons, including their complex phase transformations, characteristically sluggish phase-transformation kinetics, tendency to produce experimental results that vary depending on the histories of individual samples, and sensitivity to contaminants such as oxygen in concentrations below a hundred parts per million. Many of the experimental measurements were made before 1980, and the level of documentation for experimental methods and results varies widely. It is, therefore, not surprising that little is known with certainty about U-Pu-Zr alloys, and that general acceptance of results sometimes indicates that there is only a single measurement for a particular property. This handbook summarizes currently available information about U, Pu, Zr, and alloys of two or three of these elements. It contains information about phase diagrams and related information (including phases and phase transformations); heat capacity, entropy, and enthalpy; thermal expansion; and thermal conductivity and diffusivity. In addition to presenting information about materials properties, it attempts to provide information about how well the property is known and how much variation exists between measurements. Although the handbook includes some references to publications about modeling, its primary focus is experimental data. Most of the data has been published elsewhere (although scattered throughout numerous references, some quite obscure); however, some data is presented here for the first time.« less

The behaviour of transuranic mixed oxide fuel in a Candu-900 reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morreale, A. C.; Ball, M. R.; Novog, D. R.

2012-07-01

The production of transuranic actinide fuels for use in current thermal reactors provides a useful intermediary step in closing the nuclear fuel cycle. Extraction of actinides reduces the longevity, radiation and heat loads of spent material. The burning of transuranic fuels in current reactors for a limited amount of cycles reduces the infrastructure demand for fast reactors and provides an effective synergy that can result in a reduction of as much as 95% of spent fuel waste while reducing the fast reactor infrastructure needed by a factor of almost 13.5 [1]. This paper examines the features of actinide mixed oxidemore » fuel, TRUMOX, in a CANDU{sup R}* nuclear reactor. The actinide concentrations used were based on extraction from 30 year cooled spent fuel and mixed with natural uranium in 3.1 wt% actinide MOX fuel. Full lattice cell modeling was performed using the WIMS-AECL code, super-cell calculations were analyzed in DRAGON and full core analysis was executed in the RFSP 2-group diffusion code. A time-average full core model was produced and analyzed for reactor coefficients, reactivity device worth and online fuelling impacts. The standard CANDU operational limits were maintained throughout operations. The TRUMOX fuel design achieved a burnup of 27.36 MWd/kg HE. A full TRUMOX fuelled CANDU was shown to operate within acceptable limits and provided a viable intermediary step for burning actinides. The recycling, reprocessing and reuse of spent fuels produces a much more sustainable and efficient nuclear fuel cycle. (authors)« less

The chemical behavior of the transuranic elements and the barrier function in natural aquifer systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jewett, J.R.

1997-09-17

In a geological repository for long-lived radioactive wastes, such as actinides and certain fission products, most of the stored radionuclides remain immobile in the particular geological formation. If any of these could possibly become mobile, only trace concentrations of a few radionuclides would result. Nevertheless, with an inventory in the repository of many tonnes of transuranic elements, the amounts that could disperse cannot be neglected. A critical assessment of the chemical behavior of these nuclides, especially their migration properties in the aquifer system around the repository site, is mandatory for analysis of the long-term safety. The chemistry requited for thismore » includes many geochemical multicomponent reactions that are so far only partially understood and [which] therefore can be quantified only incompletely. A few of these reactions have been discussed in this paper based on present knowledge. If a comprehensive discussion of the subject is impossible because of this [lack of information], then an attempt to emphasize the importance of the predominant geochemical reactions of the transuranic elements in various aquifer systems should be made.« less

Microanalysis (micro-XRF, micro-XANES, and micro-XRD) of a tertiary sediment using microfocused synchrotron radiation.

PubMed

Denecke, Melissa A; Somogyi, Andrea; Janssens, Koen; Simon, Rolf; Dardenne, Kathy; Noseck, Ulrich

2007-06-01

Micro-focused synchrotron radiation techniques to investigate actinide elements in geological samples are becoming an increasingly used tool in nuclear waste disposal research. In this article, results using mu-focus techniques are presented from a bore core section of a U-rich tertiary sediment collected from Ruprechtov, Czech Republic, a natural analog to nuclear waste repository scenarios in deep geological formations. Different methods are applied to obtain various, complementary information. Elemental and element chemical state distributions are obtained from micro-XRF measurements, oxidation states of As determined from micro-XANES, and the crystalline structure of selected regions are studied by means of micro-XRD. We find that preparation of the thin section created an As oxidation state artifact; it apparently changed the As valence in some regions of the sample. Results support our previously proposed hypothesis of the mechanism for U-enrichment in the sediment. AsFeS coating on framboid Fe nodules in the sediment reduced mobile groundwater-dissolved U(VI) to less-soluble U(IV), thereby immobilizing the uranium in the sediment.

A GREEN'S FUNCTION APPROACH FOR DETERMINING DOSE RATES FOR SMALL GRAM QUANTITIES IN SHIPPING PACKAGINGS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nathan, S.

The Small Gram Quantity (SGQ) concept is based on the understanding that small amounts of hazardous materials, in this case radioactive materials (RAM), are significantly less hazardous than large amounts of the same materials. This paper describes a methodology designed to estimate an SGQ for several neutron and gamma emitting isotopes that can be shipped in a package in compliance with 10 CFR Part 71 external radiation level limits regulations. The neutron and photon sources were calculated using both ORIGEN-S and RASTA. The response from a unit source in each neutron and photon group was calculated using MCNP5 with eachmore » unshielded and shielded container configuration. Effects of self-shielding on both neutron and photon response were evaluated by including either plutonium oxide or iron in the source region for the case with no shielded container. For the cases of actinides mixed with light elements, beryllium is the bounding light element. The added beryllium (10 to 90 percent of the actinide mass) in the cases studied represents between 9 and 47 percent concentration of the total mixture mass. For beryllium concentrations larger than 50 percent, the increase in the neutron source term and dose rate tend to increase at a much lower rate than at concentrations lower than 50%. The intimately mixed actinide-beryllium form used in these models is very conservative and thus the limits presented in this report are practical bounds on the mass that can be safely shipped. The calculated dose rate from one gram of each isotope was then used to determin the maximum amount of a single isotope that could be shipped in the Model 9977 Package (or packagings having the same or larger external dimensions as well as similar structural materials) and have the external radiation level within the regulatory dose limits at the surface of the package. The estimates of the mass limits presented would also serve as conservative limits for both the Models 9975 and 9978 packages. If a package contains a mixture of isotopes, the acceptability for shipment can be determined by a sum of fractions approach. It should be noted that the SGQ masses presented in this report represent limits that would comply with the external radiation limits under 10CFR Part 71. They do not necessarily bound lower limits that may be required to comply with other factors such as heat load of the package.« less

Analogue Study of Actinide Transport at Sites in Russia

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2003-02-12

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

Method for extracting lanthanides and actinides from acid solutions by modification of Purex solvent

DOEpatents

Horwitz, E.P.; Kalina, D.G.

1984-05-21

A process has been developed for the extraction of multivalent lanthanide and actinide values from acidic waste solutions, and for the separation of these values from fission product and other values, which utilizes a new series of neutral bi-functional extractants, the alkyl(phenyl)-N, N-dialkylcarbamoylmethylphosphine oxides, in combination with a phase modifier to form an extraction solution. The addition of the extractant to the Purex process extractant, tri-n-butylphosphate in normal paraffin hydrocarbon diluent, will permit the extraction of multivalent lanthanide and actinide values from 0.1 to 12.0 molar acid solutions.

SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES

DOEpatents

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

1962-08-14

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

Effect of oxidation state and ionic strength on sorption of actinides (Th, U, Np, Am) to geologic media [Abstract and References Only

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dittrich, Timothy M.; Richmann, Michael K.; Reed, Donald T.

2015-10-30

The degree of conservatism in the estimated sorption partition coefficients (K ds) used in a performance assessment model is being evaluated based on a complementary batch and column method. The main focus of this work is to investigate the role of ionic strength, solution chemistry, and oxidation state (III-VI) in actinide sorption to dolomite rock. Based on redox conditions and solution chemistry expected at the WIPP, possible actinide species include Pu(III), Pu(IV), U(IV), U(VI), Np(IV), Np(V), Am(III), and Th(IV).

Actinide Sputtering Induced by Fission with Ultra-cold Neutrons

NASA Astrophysics Data System (ADS)

Shi, Tan; Venuti, Michael; Fellers, Deion; Martin, Sean; Morris, Chris; Makela, Mark

2017-09-01

Understanding the effects of actinide sputtering due to nuclear fission is important for a wide range of applications, including nuclear fuel storage, space science, and national defense. A new program at the Los Alamos Neutron Science Center uses ultracold neutrons (UCN) to induce fission in actinides such as uranium and plutonium. By controlling the UCN energy, it is possible to induce fission at the sample surface within a well-defined depth. It is therefore an ideal tool for studying the effects of fission-induced sputtering as a function of interaction depth. Since the mechanism for fission-induced surface damage is not well understood, this work has the potential to deconvolve the various damage mechanisms. During the irradiation with UCN, NaI detectors are used to monitor the fission events and were calibrated by monitoring fission fragments with an organic scintillator. Alpha spectroscopy of the ejected actinide material is performed in an ion chamber to determine the amount of sputtered material. Actinide samples with various sample properties and surface conditions are irradiated and analyzed. In this talk, I will discuss our experimental setup and present the preliminary results from the testing of multiple samples. This work has been supported by Los Alamos National Laboratory and Seaborg Summer Research Fellowship.

Ceramification: A plutonium immobilization process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rask, W.C.; Phillips, A.G.

1996-05-01

This paper describes a low temperature technique for stabilizing and immobilizing actinide compounds using a combination process/storage vessel of stainless steel, in which measured amounts of actinide nitrate solutions and actinide oxides (and/or residues) are systematically treated to yield a solid article. The chemical ceramic process is based on a coating technology that produces rare earth oxide coatings for defense applications involving plutonium. The final product of this application is a solid, coherent actinide oxide with process-generated encapsulation that has long-term environmental stability. Actinide compounds can be stabilized as pure materials for ease of re-use or as intimate mixtures withmore » additives such as rare earth oxides to increase their degree of proliferation resistance. Starting materials for the process can include nitrate solutions, powders, aggregates, sludges, incinerator ashes, and others. Agents such as cerium oxide or zirconium oxide may be added as powders or precursors to enhance the properties of the resulting solid product. Additives may be included to produce a final product suitable for use in nuclear fuel pellet production. The process is simple and reduces the time and expense for stabilizing plutonium compounds. It requires a very low equipment expenditure and can be readily implemented into existing gloveboxes. The process is easily conducted with less associated risk than proposed alternative technologies.« less

Photochemical route to actinide-transition metal bonds: synthesis, characterization and reactivity of a series of thorium and uranium heterobimetallic complexes.

PubMed

Ward, Ashleigh L; Lukens, Wayne W; Lu, Connie C; Arnold, John

2014-03-05

A series of actinide-transition metal heterobimetallics has been prepared, featuring thorium, uranium, and cobalt. Complexes incorporating the binucleating ligand N[ο-(NHCH2P(i)Pr2)C6H4]3 with either Th(IV) (4) or U(IV) (5) and a carbonyl bridged [Co(CO)4](-) unit were synthesized from the corresponding actinide chlorides (Th: 2; U: 3) and Na[Co(CO)4]. Irradiation of the resulting isocarbonyls with ultraviolet light resulted in the formation of new species containing actinide-metal bonds in good yields (Th: 6; U: 7); this photolysis method provides a new approach to a relatively unusual class of complexes. Characterization by single-crystal X-ray diffraction revealed that elimination of the bridging carbonyl and formation of the metal-metal bond is accompanied by coordination of a phosphine arm from the N4P3 ligand to the cobalt center. Additionally, actinide-cobalt bonds of 3.0771(5) Å and 3.0319(7) Å for the thorium and uranium complexes, respectively, were observed. The solution-state behavior of the thorium complexes was evaluated using (1)H, (1)H-(1)H COSY, (31)P, and variable-temperature NMR spectroscopy. IR, UV-vis/NIR, and variable-temperature magnetic susceptibility measurements are also reported.

Photochemical route to actinide-transition metal bonds: synthesis, characterization and reactivity of a series of thorium and uranium heterobimetallic complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Ashleigh; Lukens, Wayne; Lu, Connie

2014-04-01

A series of actinide-transition metal heterobimetallics has been prepared, featuring thorium, uranium and cobalt. Complexes incorporating the binucleating ligand N[-(NHCH2PiPr2)C6H4]3 and Th(IV) (4) or U(IV) (5) with a carbonyl bridged [Co(CO)4]- unit were synthesized from the corresponding actinide chlorides (Th: 2; U: 3) and Na[Co(CO)4]. Irradiation of the isocarbonyls with ultraviolet light resulted in the formation of new species containing actinide-metal bonds in good yields (Th: 6; U: 7); this photolysis method provides a new approach to a relatively rare class of complexes. Characterization by single-crystal X-ray diffraction revealed that elimination of the bridging carbonyl is accompanied by coordination ofmore » a phosphine arm from the N4P3 ligand to the cobalt center. Additionally, actinide-cobalt bonds of 3.0771(5) and 3.0319(7) for the thorium and uranium complexes, respectively, were observed. The solution state behavior of the thorium complexes was evaluated using 1H, 1H-1H COSY, 31P and variable-temperature NMR spectroscopy. IR, UV-Vis/NIR, and variable-temperature magnetic susceptibility measurements are also reported.« less

Aqueous Electrochemical Mechanisms in Actinide Residue Processing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morris, David E.; Burns, Carol J.; Smith, Wayne H.

2000-12-31

Plutonium and uranium residues (e.g., incinerator ash, combustibles, and sand/slag/crucibles) resulting from the purification and processing of nuclear materials constitute an enormous volume of ''lean'' processing waste and represent a significant fraction of the U. S. Department of Energy's (DOE) legacy waste from fifty years of nuclear weapons production activities. Much of this material is presently in storage at sites throughout the DOE weapons production complex (most notably Rocky Flats, Savannah River and Hanford) awaiting further processing and/or final disposition. The chemical and physical stability of much of this material has been called into question recently by the Defense Nuclearmore » Facility Safety Board (DNFSB) and resulted in the issuance of a mandate by the DNFSB to undertake a program to stabilize these materials [1]. The ultimate disposition for much of these materials is anticipated to be geologic repositories such as the proposed Waste Isolation Pilot Plant in New Mexico. However, in light of the mandate to stabilize existing residues and the probable concomitant increase in the volume of material to be disposed as a result of stabilization (e.g., from repackaging at lower residue densities), the projected storage volume for these wastes within anticipated geologic repositories will likely be exceeded simply to handle existing wastes. Additional processing of some of these residue waste streams to reduce radionuclide activity levels, matrix volume, or both is a potentially important strategy to achieve both stabilization and volume reduction so that the anticipated geologic repositories will provide adequate storage volume. In general, the plutonium and uranium that remains in solid residue materials exists in a very stable chemical form (e.g., as binary oxides), and the options available to remove the actinides are limited. However, there have been some demonstrated successes in this vain using aqueous phase electrochemical methods such as the Catalyzed Electrochemical Plutonium Oxide Dissolution (CEPOD) process pioneered by workers at Pacific Northwest National Laboratory in the mid-1970s [2]. The basis for most of these mediated electrochemical oxidation/reduction (MEO/R) processes is the generation of a dissolved electrochemical catalyst, such as Ag2+, which is capable of oxidizing or reducing solid-phase actinide species or actinide sorbates via 7 heterogeneous electron transfer to oxidation states that have significantly greater solubilities (e.g., PuO2(s) to PuO2 2+ (dissolved)). The solubilized actinide can then be recovered by ion exchange or other mechanisms. These aqueous electrochemical methods for residue treatment have been considered in many of the ''trade studies'' to evaluate options for stabilization of the various categories of residue materials. While some concerns generally arise (e.g., large secondary waste volumes could results since the process stream normally goes th rough anion exchange or precipitation steps to remove the actinide), the real utility and versatility of these methods should not be overlooked. They are low temperature, ambient pressure processes that operate in a non-corrosive environment. In principle, they can be designed to be highly selective for the actinides (i.e., no substrate degradation occurs), they can be utilized for many categories of residue materials with little or no modification in hardware or operating conditions, and they can conceivably be engineered to minimize secondary waste stream volume. However, some fundamental questions remain concerning the mechanisms through which these processes act, and how the processes might be optimized to maximize efficiency while minimizing secondary waste. In addition, given the success achieved to date on the limited set of residues, further research is merited to extend the range of applicability of these electrochemical methods to other residue and waste streams. The principal goal of the work described here is to develop a fundamental understanding of the heterogeneous electron transfer thermodynamics and kinetics that lie at the heart of the MEO/R processes for actinide solids and actinide species entrained in or surface-bound to residue substrates. This has been accomplished as described in detail below through spectroscopic characterization of actinide-bearing substrates and electrochemical investigations of electron transfer reactions between uranium- and plutonium- (or surrogates) bearing solids (dispersed actinide solid phases and actinides sorbed to inorganic and organic colloids) and polarizable electrode materials. In general, the actinide solids or substrate-supported species were chosen to represent relevant residue materials (e.g., incinerator ash, sand/slag/crucible, and combustibles).« less

Interaction of rare earth elements and components of the Horonobe deep groundwater.

PubMed

Kirishima, Akira; Kuno, Atsushi; Amamiya, Hiroshi; Kubota, Takumi; Kimuro, Shingo; Amano, Yuki; Miyakawa, Kazuya; Iwatsuki, Teruki; Mizuno, Takashi; Sasaki, Takayuki; Sato, Nobuaki

2017-02-01

To better understand the migration behavior of minor actinides in deep groundwater, the interactions between doped rare earth elements (REEs) and components of Horonobe deep groundwater were investigated. Approximately 10 ppb of the REEs, i.e. Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, and Yb were doped into a groundwater sample collected from a packed section in a borehole drilled at 140 m depth in the experiment drift of Horonobe Underground Research Laboratory in Hokkaido, Japan. The groundwater sample was sequentially filtered with a 0.2 μm pore filter, and 10 kDa, 3 kDa and 1 kDa nominal molecular weight limit (NMWL) ultrafilters with conditions kept inert. Next, the filtrate solutions were analyzed with inductively coupled plasma mass spectrometry (ICP-MS) to determine the concentrations of the REEs retained in solution at each filtration step, while the used filters were analyzed through neutron activation analysis (NAA) and TOF-SIMS element mapping to determine the amounts and chemical species of the trapped fractions of REEs on each filter. A strong relationship between the ratios of REEs retained in the filtrate solutions and the ionic radii of the associated REEs was observed; i.e. smaller REEs occur in larger proportions dissolved in the solution phase under the conditions of the Horonobe groundwater. The NAA and TOF-SIMS analyses revealed that portions of the REEs were trapped by the 0.2 μm pore filter as REE phosphates, which correspond to the species predicted to be predominant by chemical equilibrium calculations for the conditions of the Horonobe groundwater. Additionally, small portions of colloidal REEs were trapped by the 10 kDa and 3 kDa NMWL ultrafilters. These results suggest that phosphate anions play an important role in the chemical behavior of REEs in saline (seawater-based) groundwater, which may be useful for predicting the migration behavior of trivalent actinides released from radioactive waste repositories in the far future. Copyright © 2016 Elsevier Ltd. All rights reserved.

Analysis and optimization of minor actinides transmutation blankets with regards to neutron and gamma sources

NASA Astrophysics Data System (ADS)

Kooymana, Timothée; Buiron, Laurent; Rimpault, Gérald

2017-09-01

Heterogeneous loading of minor actinides in radial blankets is a potential solution to implement minor actinides transmutation in fast reactors. However, to compensate for the lower flux level experienced by the blankets, the fraction of minor actinides to be loaded in the blankets must be increased to maintain acceptable performances. This severely increases the decay heat and neutron source of the blanket assemblies, both before and after irradiation, by more than an order of magnitude in the case of neutron source for instance. We propose here to implement an optimization methodology of the blankets design with regards to various parameters such as the local spectrum or the mass to be loaded, with the objective of minimizing the final neutron source of the spent assembly while maximizing the transmutation performances of the blankets. In a first stage, an analysis of the various contributors to long and short term neutron and gamma source is carried out while in a second stage, relevant estimators are designed for use in the effective optimization process, which is done in the last step. A comparison with core calculations is finally done for completeness and validation purposes. It is found that the use of a moderated spectrum in the blankets can be beneficial in terms of final neutron and gamma source without impacting minor actinides transmutation performances compared to more energetic spectrum that could be achieved using metallic fuel for instance. It is also confirmed that, if possible, the use of hydrides as moderating material in the blankets is a promising option to limit the total minor actinides inventory in the fuel cycle. If not, it appears that focus should be put upon an increased residence time for the blankets rather than an increase in the acceptable neutron source for handling and reprocessing.

Liquid-liquid extraction of actinides, lanthanides, and fission products by use of ionic liquids: from discovery to understanding.

PubMed

Billard, Isabelle; Ouadi, Ali; Gaillard, Clotilde

2011-06-01

Liquid-liquid extraction of actinides and lanthanides by use of ionic liquids is reviewed, considering, first, phenomenological aspects, then looking more deeply at the various mechanisms. Future trends in this developing field are presented.

Development of ion beam sputtering techniques for actinide target preparation

NASA Astrophysics Data System (ADS)

Aaron, W. S.; Zevenbergen, L. A.; Adair, H. L.

1985-06-01

Ion beam sputtering is a routine method for the preparation of thin films used as targets because it allows the use of a minimum quantity of starting material, and losses are much lower than most other vacuum deposition techniques. Work is underway in the Isotope Research Materials Laboratory (IRML) at ORNL to develop the techniques that will make the preparation of actinide targets up to 100 μg/cm 2 by ion beam sputtering a routinely available service from IRML. The preparation of the actinide material in a form suitable for sputtering is a key to this technique, as is designing a sputtering system that allows the flexibility required for custom-ordered target production. At present, development work is being conducted on low-activity actinides in a bench-top system. The system will then be installed in a hood or glove box approved for radioactive materials handling where processing of radium, actinium, and plutonium isotopes among others will be performed.

Supercritical Fluid Extraction and Separation of Uranium from Other Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donna L. Quach; Bruce J. Mincher; Chien M. Wai

2014-06-01

This paper investigates the feasibility of separating uranium from other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of an extraction and counter current stripping technique, which would be a more efficient and environmentally benign technology for used nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U(VI), Np(VI), Pu(IV), and Am(III)) were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, the separation of uraniummore » from plutonium in sc-CO2 modified with TBP was successful at nitric acid concentrations of less than 3 M in the presence of acetohydroxamic acid or oxalic acid, and the separation of uranium from neptunium was successful at nitric acid concentrations of less than 1 M in the presence of acetohydroxamic acid, oxalic acid, or sodium nitrite.« less

Centrifugal Tensioned Metastable Fluid Detectors for Trace Radiation Sources: Experimental Verification and Military Employment

DTIC Science & Technology

2016-06-01

used in both CTMFD and Beckman LS 6500 Scintillation System. Actinide   Mass  of  Nalgene  (g)  Mass  of  Cap (g)  Mass  of  Nalgene,  Cap, 50 mL...both CTMFD and Beckman LS 6500 Scintillation System. Actinide   Mass  of  Nalgene  and Cap  (g)  Mass  of  Nalgene, Cap,  50 mL Acetone  (g)  Mass  of...testing comparing the CTMFD’s capabilities of actinide spectroscopy and neutron detection against other detection systems with similar capabilities. The

Vaporisation of candidate nuclear fuels and targets for transmutation of minor actinides

NASA Astrophysics Data System (ADS)

Gotcu-Freis, P.; Hiernaut, J.-P.; Colle, J.-Y.; Nästrén, C.; Carretero, A. Fernandez; Konings, R. J. M.

2011-04-01

The thermal stability and high temperature behaviour of candidate fuels and targets for transmutation of minor actinides has been investigated. Zirconia-based solid solution, MgO-based CERCER and molybdenum-based CERMET fuels containing Am and/or Pu in various concentrations were heated up to 2700 K in a Knudsen cell coupled with a quadrupole mass spectrometer, to measure their vapour pressure and vapour composition. The results reveal that the vaporisation of the actinides from the samples is not only determined by the thermodynamics of the system but is also related to the dynamic evolution of multi-component mixtures with complex composition or microstructure.

Method for reprocessing and separating spent nuclear fuels. [Patent application

DOEpatents

Krikorian, O.H.; Grens, J.Z.; Parrish, W.H. Sr.

1982-01-19

Spent nuclear fuels, including actinide fuels, volatile and nonvolatile fission products, are reprocessed and separated in a molten metal solvent housed in a separation vessel made of a carbon-containing material. A first catalyst, which promotes the solubility and permeability of carbon in the metal solvent, is included. By increasing the solubility and permeability of the carbon in the solvent, the rate at which actinide oxides are reduced (carbothermic reduction) is greatly increased. A second catalyst, included to increase the affinity for nitrogen in the metal solvent, is added to increase the rate at which actinide nitrides form after carbothermic reduction is complete.

Cryogenic gamma detectors enable direct detection of 236U and minor actinides for non-destructive assay [Cryogenic gamma detectors enable direct detection of minor actinides for non-destructive assay

DOE Office of Scientific and Technical Information (OSTI.GOV)

Velazquez, Miguel; Dreyer, Jonathan; Drury, Owen B.

2015-09-05

Here, we demonstrate the utility of a superconducting transition edge sensor (TES) γ-ray detector with high energy resolution and low Compton background for non-destructive assay (NDA) of a uranium sample from reprocessed nuclear fuel. We show that TES γ-detectors can separate low energy actinide γ-emissions from the background and nearby lines, even from minor isotopes whose signals are often obscured in NDA with conventional Ge detectors. Superconducting γ detectors may therefore bridge the gap between high-accuracy destructive assay (DA) and easier to-use NDA.

United States Transuranium and Uranium Registries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kathren, R.L.; Filipy, R.E.; Dietert, S.E.

1991-06-01

This report summarizes the primary scientific activities of the United States Transuranium and Uranium Registries for the period October 1, 1989 through September 30, 1990. The Registries are parallel human tissue research programs devoted to the study of the actinide elements in humans. To date there have been 261 autopsy or surgical specimen donations, which include 11 whole bodies. The emphasis of the Registry was directed towards quality improvement and the development of a fully computerized data base that would incorporate not only the results of postmortem radiochemical analysis, but also medical and monitoring information obtained during life. Human subjectsmore » reviews were also completed. A three compartment biokinetic model for plutonium distribution is proposed. 2 tabs.« less

Selective uptake of uranium and thorium by some vegetables

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yusof, A.M.; Ghazali, Z.; Rahman, S.A.

1996-12-31

Uranium and thorium are trace elements in the actinide series found naturally in the atmosphere and can enter the human body through ingestion of food or by drinking. To establish baseline information for current and future environmental assessment due to pollution, especially in foodstuff, by heavy and trace metals, biological samples such as locally grown vegetables were analyzed for uranium and thorium contents. The terrain in most parts of the Malaysian peninsula consists of monazite-bearing rocks or soil that can be found extensively in areas related to tin-mining operations. Abandoned mining areas provide suitable sites for vegetable cultivation where mostmore » vegetables in the lowlands are grown.« less

LIBS Spectral Data for a Mixed Actinide Fuel Pellet Containing Uranium, Plutonium, Neptunium and Americium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Judge, Elizabeth J.; Berg, John M.; Le, Loan A.

2012-06-18

Laser-induced breakdown spectroscopy (LIBS) was used to analyze a mixed actinide fuel pellet containing 75% UO{sub 2}/20% PuO{sub 2}/3% AmO{sub 2}/2% NpO{sub 2}. The preliminary data shown here is the first report of LIBS analysis of a mixed actinide fuel pellet, to the authors knowledge. The LIBS spectral data was acquired in a plutonium facility at Los Alamos National Laboratory where the sample was contained within a glove box. The initial installation of the glove box was not intended for complete ultraviolet (UV), visible (VIS) and near infrared (NIR) transmission, therefore the LIBS spectrum is truncated in the UV andmore » NIR regions due to the optical transmission of the window port and filters that were installed. The optical collection of the emission from the LIBS plasma will be optimized in the future. However, the preliminary LIBS data acquired is worth reporting due to the uniqueness of the sample and spectral data. The analysis of several actinides in the presence of each other is an important feature of this analysis since traditional methods must chemically separate uranium, plutonium, neptunium, and americium prior to analysis. Due to the historic nature of the sample fuel pellet analyzed, the provided sample composition of 75% UO{sub 2}/20% PuO{sub 2}/3% AmO{sub 2}/2% NpO{sub 2} cannot be confirm without further analytical processing. Uranium, plutonium, and americium emission lines were abundant and easily assigned while neptunium was more difficult to identify. There may be several reasons for this observation, other than knowing the exact sample composition of the fuel pellet. First, the atomic emission wavelength resources for neptunium are limited and such techniques as hollow cathode discharge lamp have different dynamics than the plasma used in LIBS which results in different emission spectra. Secondly, due to the complex sample of four actinide elements, which all have very dense electronic energy levels, there may be reactions and interactions occurring within the plasma, such as collisional energy transfer, that might be a factor in the reduction in neptunium emission lines. Neptunium has to be analyzed alone using LIBS to further understand the dynamics that may be occurring in the plasma of the mixed actinide fuel pellet sample. The LIBS data suggests that the emission spectrum for the mixed actinide fuel pellet is not simply the sum of the emission spectra of the pure samples but is dependent on the species present in the plasma and the interactions and reactions that occur within the plasma. Finally, many of the neptunium lines are in the near infrared region which is drastically reduced in intensity by the current optical setup and possibly the sensitivity of the emission detector in the spectral region. Once the optics are replaced and the optical collection system is modified and optimized, the probability of observing emission lines for neptunium might be increased significantly. The mixed actinide fuel pellet was analyzed under the experimental conditions listed in Table 1. The LIBS spectra of the fuel pellet are shown in Figures 1-49. The spectra are labeled with the observed wavelength and atomic species (both neutral (I) and ionic (II)). Table 2 is a complete list of the observed and literature based emission wavelengths. The literature wavelengths have references including NIST Atomic Spectra Database (NIST), B.A. Palmer et al. 'An Atlas of Uranium Emission Intensities in a Hollow Cathode Discharge' taken at the Kitt Peak National Observatory (KPNO), R.L. Kurucz 1995 Atomic Line Data from the Smithsonian Astrophysical Observatory (SAO), J. Blaise et al. 'The Atomic Spectrum of Plutonium' from Argonne National Laboratory (BFG), and M. Fred and F.S. Tomkins, 'Preliminary Term Analysis of Am I and Am II Spectra' (FT). The dash (-) shown under Ionic State indicates that the ionic state of the transition was not available. In the spectra, the dash (-) is replaced with a question mark (?). Peaks that are not assigned are most likely real features and not noise but cannot be confidently assigned to a transition without further investigation. Several peaks have multiple assignments due to limited resolution of the spectrometer used (20,000, {lambda}/{Delta}{lambda}) and without the availability, at this point in time, of pure PuO{sub 2}, AmO{sub 2}, and NpO{sub 2} to confirm the identity of the peaks. A different spectrometer was used in the plutonium facility to collect the mixed actinide fuel pellet data (Echelle 3000) than the DUO{sub 2}, ThO{sub 2} and uranium ore previously reported [6-8] (Echelle 4000) which accounts for the slight shift in the observed wavelength of the uranium emission lines.« less

First-principles study of the Kondo physics of a single Pu impurity in a Th host

DOE PAGES

Zhu, Jian -Xin; Albers, R. C.; Haule, K.; ...

2015-04-23

Based on its condensed-matter properties, crystal structure, and metallurgy, which includes a phase diagram with six allotropic phases, plutonium is one of the most complicated pure elements in its solid state. Its anomalous properties, which are indicative of a very strongly correlated state, are related to its special position in the periodic table, which is at the boundary between the light actinides that have itinerant 5f electrons and the heavy actinides that have localized 5f electrons. As a foundational study to probe the role of local electronic correlations in Pu, we use the local-density approximation together with a continuous-time quantummore » Monte Carlo simulation to investigate the electronic structure of a single Pu atom that is either substitutionally embedded in the bulk and or adsorbed on the surface of a Th host. This is a simpler case than the solid phases of Pu metal. With the Pu impurity atom we have found a Kondo resonance peak, which is an important signature of electronic correlations, in the local density of states around the Fermi energy. We show that the peak width of this resonance is narrower for Pu atoms at the surface of Th than for those in the bulk due to a weakened Pu - 5f hybridization with the ligands at the surface.« less

Complexation of Nd(III) with tetraborate ion and its effect on actinide (III) solubility in WIPP brine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borkowski, Marian; Richmann, Michael K; Reed, Donald T

2010-01-01

The potential importance of tetraborate complexation on lanthanide(III) and actinide(III) solubility is recognized in the literature but a systematic study of f-element complexation has not been performed. In neodymium solubility studies in WIPP brines, the carbonate complexation effect is not observed since tetraborate ions form a moderately strong complex with neodymium(III). The existence of these tetraborate complexes was established for low and high ionic strength solutions. Changes in neodymium(III) concentrations in undersaturation experiments were used to determine the neodymium with tetraborate stability constants as a function of NaCl ionic strength. As very low Nd(III) concentrations have to be measured, itmore » was necessary to use an extraction pre-concentration step combined with ICP-MS analysis to extend the detection limit by a factor of 50. The determined Nd(III) with borate stability constants at infinite dilution and 25 C are equal to log {beta}{sub 1} = 4.55 {+-} 0.06 using the SIT approach, equal to log {beta}{sub 1} = 4.99 {+-} 0.30 using the Pitzer approach, with an apparent log {beta}{sub 1} = 4.06 {+-} 0.15 (in molal units) at I = 5.6 m NaCl. Pitzer ion-interaction parameters for neodymium with tetraborate and SIT interaction coefficients were also determined and reported.« less

Skull counting in late stages after internal contamination by actinides.

PubMed

Tani, Kotaro; Shutt, Arron; Kurihara, Osamu; Kosako, Toshiso

2015-02-01

Monitoring preparation for internal contamination with actinides (e.g. Pu and Am) is required to assess internal doses at nuclear fuel cycle-related facilities. In this paper, the authors focus on skull counting in case of single-incident inhalation of (241)Am and propose an effective procedure for skull counting with an existing system, taking into account the biokinetic behaviour of (241)Am in the human body. The predicted response of the system to skull counting under a certain counting geometry was found to be only ∼1.0 × 10(-5) cps Bq(-1) 1y after intake. However, this disadvantage could be remedied by repeated measurements of the skull during the late stage of the intake due to the predicted response reaching a plateau at about the 1000th day after exposure and exceeding that in the lung counting. Further studies are needed for the development of a new detection system with higher sensitivity to perform reliable internal dose estimations based on direct measurements. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

The generator coordinate Dirac-Fock method for open-shell atomic systems

NASA Astrophysics Data System (ADS)

Malli, Gulzari L.; Ishikawa, Yasuyuki

1998-11-01

Recently we developed generator coordinate Dirac-Fock and Dirac-Fock-Breit methods for closed-shell systems assuming finite nucleus and have reported Dirac-Fock and Dirac-Fock-Breit energies for the atoms He through Nobelium (Z=102) [see Refs. Reference 10Reference 11Reference 12Reference 13]. In this paper, we generalize our earlier work on closed-shell systems and develop a generator coordinate Dirac-Fock method for open-shell systems. We present results for a number of representative open-shell heavy atoms (with nuclear charge Z>80) including the actinide and superheavy transactinide (with Z>103) atomic systems: Fr (Z=87), Ac (Z=89), and Lr (Z=103) to E113 (eka-thallium, Z=113). The high accuracy obtained in our open-shell Dirac-Fock calculations is similar to that of our closed-shell calculations, and we attribute it to the fact that the representation of the relativistic dynamics of an electron in a spherical ball finite nucleus near the origin in terms of our universal Gaussian basis set is as accurate as that provided by the numerical finite difference method. The DF SCF energies calculated by Desclaux [At. Data. Nucl. Data Tables 12, 311 (1973)] (apart from a typographic error for Fr pointed out here) are higher than those reported here for atoms of some of the superheavy transactinide elements by as much as 5 hartrees (136 eV). We believe that this is due to the use by Desclaux of much larger atomic masses than the currently accepted values for these elements.

Managing the Nuclear Fuel Cycle: Policy Implications of Expanding Global Access to Nuclear Power

DTIC Science & Technology

2010-03-05

However, the case of Iran raises perhaps the most critical question in this decade for strengthening the nuclear nonproliferation regime: How can...enrichment process can take advantage of the slight difference in atomic mass between 235U and 238U. The typical enrichment process requires about 10 lbs of...neutrons but can induce fission in all actinides , including all plutonium isotopes. Therefore, nuclear fuel for a fast reactor must have a higher

Chronopotentiometry of Refractory Metals, Actinides and Oxyanions in Molten Salts: A Review

DTIC Science & Technology

1992-09-01

disappaared. No new wave appeared which could be attributed to the nitrosonium , NO+, ion . The nitronium ion , N02+, could not be detected in the melt...electrodeposit- ion of coherent deposits of refractory metals from solutions in fused electrolytes. 2.1. Titanium. The electrochemical oxidation of Ti(II...the higher valent niobium ions were found to be electroactive. The reduction process was a reversible, one electron step with the product soluble in the

DOE Office of Scientific and Technical Information (OSTI.GOV)

Capote, R.; Chen, Y. -J.; Hambsch, F. -J.

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

Theory of Photoemission in Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Svane, Axel

2008-07-01

A theory is presented which describes the photoemission spectra of actinide compounds starting from the atomic limit of isolated actinide ions. The multiplets of the ion are calculated and an additional term is introduced to describe the interaction with the sea of conduction electrons. This leads to complex mixed-valent ground states, which describes well the rich spectrum observed for PuSe. In particular, the three-peak feature, which is often seen in Pu and Pu compounds in the vicinity of the Fermi level originates from f{sup 6} {yields} f{sup 5} emission. The theory is further applied to PuSb, PuCoGa{sub 5} and Am.more » (author)« less

Method for extracting lanthanides and actinides from acid solutions by modification of purex solvent

DOEpatents

Horwitz, E. Philip; Kalina, Dale G.

1986-01-01

A process for the recovery of actinide and lanthanide values from aqueous solutions with an extraction solution containing an organic extractant having the formula: ##STR1## where .phi. is phenyl, R.sup.1 is a straight or branched alkyl or alkoxyalkyl containing from 6 to 12 carbon atoms and R.sup.2 is an alkyl containing from 3 to 6 carbon atoms and phase modifiers in a water-immiscible hydrocarbon diluent. The addition of the extractant to the Purex process extractant, tri-n-butylphosphate in normal paraffin hydrocarbon diluent, will permit the extraction of multivalent lanthanide and actinide values from 0.1 to 12.0 molar acid solutions.

Ultra-heavy cosmic rays: Theoretical implications of recent observations

NASA Technical Reports Server (NTRS)

Blake, J. B.; Hainebach, K. L.; Schramm, D. N.; Anglin, J. D.

1977-01-01

Extreme ultraheavy cosmic ray observations (Z greater or equal 70) are compared with r-process models. A detailed cosmic ray propagation calculation is used to transform the calculated source distributions to those observed at the earth. The r-process production abundances are calculated using different mass formulae and beta-rate formulae; an empirical estimate based on the observed solar system abundances is used also. There is the continued strong indication of an r-process dominance in the extreme ultra-heavy cosmic rays. However it is shown that the observed high actinide/Pt ratio in the cosmic rays cannot be fit with the same r-process calculation which also fits the solar system material. This result suggests that the cosmic rays probably undergo some preferential acceleration in addition to the apparent general enrichment in heavy (r-process) material. As estimate also is made of the expected relative abundance of superheavy elements in the cosmic rays if the anomalous heavy xenon in carbonaceous chondrites is due to a fissioning superheavy element.

Fractionation in the solar nebula. II - Condensation of Th, U, Pu and Cm

NASA Technical Reports Server (NTRS)

Boynton, W. V.

1978-01-01

Reasonable assumptions concerning activity coefficients allow the calculation of the relative volatility of the actinide elements under conditions expected during the early history of the solar system. Several of the light rare earths have volatilities similar to Pu and Cm and can be used as indicators of the degree of fractionation of these extinct elements. Uranium is considerably more volatile than either Pu or Cm, leading to fractionations of about a factor of 50 and 90 in the Pu/U and Cm/U ratio in the earliest condensates from the solar nebula. Ca,Al-rich inclusions from the Allende meteorite, including the coarse-grained inclusions, have a depletion of U relative to La of about a factor of three, suggesting that these inclusions may have been isolated from the nebular gas before condensation of U was complete. The inclusions, however, can be used to determine solar Pu/U and Cm/U ratios if the rare earth patterns are determined in addition to the other normal measurements.

Separation science and technology. Semiannual progress report, October 1993--March 1994

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vandegrift, G.F.; Aase, S.B.; Buchholz, B.

1997-12-01

This document reports on the work done by the Separations Science and Technology Programs of the Chemical Technology Division, Argonne National Laboratory (ANL), in the period October 1993-March 1994. This effort is mainly concerned with developing the TRUEX process for removing and concentrating actinides from acidic waste streams contaminated with transuranic (TRU) elements. The objectives of TRUEX processing are to recover valuable TRU elements and to lower disposal costs for the nonTRU waste product of the process. Other projects are underway with the objective of developing (1) evaporation technology for concentrating radioactive waste and product streams such as those generatedmore » by the TRUEX process, (2) treatment schemes for liquid wastes stored are being generated at ANL, (3) a process based on sorbing modified TRUEX solvent on magnetic beads to be used for separation of contaminants from radioactive and hazardous waste streams, and (4) a process that uses low-enriched uranium targets for production of {sup 99}Mo for nuclear medicine uses.« less

Plutonium Story

DOE R&D Accomplishments Database

Seaborg, G. T.

1981-09-01

The first nuclear synthesis and identification (i.e., the discovery) of the synthetic transuranium element plutonium (isotope /sup 238/Pu) and the demonstration of its fissionability with slow neutrons (isotope /sup 239/Pu) took place at the University of California, Berkeley, through the use of the 60-inch and 37-inch cyclotrons, in late 1940 and early 1941. This led to the development of industrial scale methods in secret work centered at the University of Chicago's Metallurgical Laboratory and the application of these methods to industrial scale production, at manufacturing plants in Tennessee and Washington, during the World War II years 1942 to 1945. The chemical properties of plutonium, needed to devise the procedures for its industrial scale production, were studied by tracer and ultramicrochemical methods during this period on an extraordinarily urgent basis. This work, and subsequent investigations on a worldwide basis, have made the properties of plutonium very well known. Its well studied electronic structure and chemical properties give it a very interesting position in the actinide series of inner transition elements.

Covalency in the f element-chalcogen bond. computational studies of M[N(EPR2)2]3 (M = La, Ce, Pr, Pm, Eu, U, Np, Pu, Am, Cm; E = O, S, Se, Te; R = H, (i)Pr, Ph).

PubMed

Ingram, Kieran I M; Tassell, Matthew J; Gaunt, Andrew J; Kaltsoyannis, Nikolas

2008-09-01

The geometric and electronic structures of the title complexes have been studied using scalar relativistic, gradient-corrected density functional theory. Extension of our previous work on six-coordinate M[N(EPH 2) 2] 3 (M = La, Ce, U, Pu; E = O, S, Se, Te), models for the experimentally characterized M[N(EP (i)Pr 2) 2] 3, yields converged geometries for all of the other 4f and 5f metals studied and for all four group 16 elements. By contrast, converged geometries for nine-coordinate M[N(EPPh 2) 2] 3 are obtained only for E = S and Se. Comparison of the electronic structures of six- and nine-coordinate M[N(EPH 2) 2] 3 suggests that coordination of the N atoms produces only minor changes in the metal-chalcogen interactions. Six-coordinate Eu[N(EPH 2) 2] 3 and Am[N(EPH 2) 2] 3 with the heavier group 16 donors display geometric and electronic properties rather different from those of the other members of the 4f and 5f series, in particular, longer than expected Eu-E and Am-E bond lengths, smaller reductions in charge difference between M and E down group 16, and larger f populations. The latter are interpreted not as evidence of f-based metal-ligand covalency but rather as being indicative of ionic metal centers closer to M (II) than M (III). The Cm complexes are found to be very ionic, with very metal-localized f orbitals and Cm (III) centers. The implications of the results for the separation of the minor actinides from nuclear wastes are discussed, as is the validity of using La (III)/U (III) comparisons as models for minor actinide/Eu systems.

Extending FEAST-METAL for analysis of low content minor actinide bearing and zirconium rich metallic fuels for sodium fast reactors

NASA Astrophysics Data System (ADS)

Karahan, Aydın

2011-07-01

Computational models in FEAST-METAL fuel behaviour code have been upgraded to simulate minor actinide bearing zirconium rich metallic fuels for use in sodium fast reactors. Increasing the zirconium content to 20-40 wt.% causes significant changes in fuel slug microstructure affecting thermal, mechanical, chemical, and fission gas behaviour. Inclusion of zirconium rich phase reduces the fission gas swelling rate significantly in early irradiation. Above the threshold fission gas swelling, formation of micro-cracks, and open pores increase material compliancy enhance diffusivity, leading to rapid fuel gas swelling, interconnected porosity development and release of the fission gases and helium. Production and release of helium was modelled empirically as a function of americium content and fission gas production, consistent with previous Idaho National Laboratory studies. Predicted fuel constituent redistribution is much smaller compared to typical U-Pu-10Zr fuel operated at EBR-II. Material properties such as fuel thermal conductivity, modulus of elasticity, and thermal expansion coefficient have been approximated using the available database. Creep rate and fission gas diffusivity of high zirconium fuel is lowered by an order of magnitude with respect to the reference low zirconium fuel based on limited database and in order to match experimental observations. The new code is benchmarked against the AFC-1F fuel assembly post irradiation examination results. Satisfactory match was obtained for fission gas release and swelling behaviour. Finally, the study considers a comparison of fuel behaviour between high zirconium content minor actinide bearing fuel and typical U-15Pu-6Zr fuel pins with 75% smear density. The new fuel has much higher fissile content, allowing for operating at lower neutron flux level compared to fuel with lower fissile density. This feature allows the designer to reach a much higher burnup before reaching the cladding dose limit. On the other hand, in order to accommodate solid fission product swelling and to control fuel clad mechanical interaction of the stiffer fuel, the fuel smear density is reduced to 70%. In addition, plenum height is increased to accommodate for fission gases.

Redox and complexation interactions of neptunium(V) with quinonoid-enriched humic derivatives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shcherbina, Natalia S.; Perminova, Irina V.; Kalmykov, Stephan N.

2007-01-01

Actinides in their higher valence states (e.g., MO{sub 2}{sup +} and MO{sub 2}{sup 2+}, where M can be Np, Pu, etc) possess a higher potential for migration and in turn pose a substantial environmental threat. To minimize this potential for migration, reducing them to lower oxidation states (e.g., their tetravalent state) can be an attractive and efficient remedial process. These lower oxidation states are often much less soluble in natural aqueous media and are, therefore, less mobile in the environment. The research presented here focuses on assessing the performance of quinonoid-enriched humic derivatives with regards to complexing and/or reducing Np(V)more » present in solution. These 'designer' humics are essentially derived reducing agents that can serve as reactive components of a novel humic-based remediation technology. The derivatives are obtained by incorporating different quinonoid-moieties into leonardite humic acids. Five quinonoid-derivatives are tested in this work and all five prove more effective as reducing agents for selected actinides than the parent leonardite humic acid, and the hydroquinone derivatives are better than the catechol derivatives. The reduction kinetics and the Np(V) species formed with the different derivatives are studied via a batch mode using near-infrared (NIR)-spectroscopy. Np(V) reduction by the humic derivatives under anoxic conditions at 293 K and at pH 4.7 obeys first-order kinetics. Rate constants range from 1.70 x 10{sup -6} (parent humic acid) to 1.06 x 10{sup -5} sec{sup -1} (derivative with maximum hydroquinone content). Stability constants for Np(V)-humic complexes calculated from spectroscopic data produce corresponding Log{beta} values of 2.3 for parent humic acid and values ranging from 2.5 to 3.2 at pH 4.7 and from 3.3 to 3.7 at pH 7.4 for humic derivatives. Maximum constants are observed for hydroquinone-enriched derivatives. It is concluded that among the humic derivatives tested, the hydroquinone-enriched ones are the most useful for addressing remedial needs of actinide-contaminated aquifers.« less

Actinide Corroles: Synthesis and Characterization of Thorium(IV) and Uranium(IV) bis(-chloride) Dimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Ashleigh L.; Buckley, Heather L.; Gryko, Daniel T.

2013-12-01

The first synthesis and structural characterization of actinide corroles is presented. Thorium(IV) and uranium(IV) macrocycles of Mes2(p-OMePh)corrole were synthesised and characterized by single-crystal X-ray diffraction, UV-Visible spectroscopy, variable-temperature 1H NMR, ESI mass spectrometry and cyclic voltammetry.

Assessment for advanced fuel cycle options in CANDU

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morreale, A.C.; Luxat, J.C.; Friedlander, Y.

2013-07-01

The possible options for advanced fuel cycles in CANDU reactors including actinide burning options and thorium cycles were explored and are feasible options to increase the efficiency of uranium utilization and help close the fuel cycle. The actinide burning TRUMOX approach uses a mixed oxide fuel of reprocessed transuranic actinides from PWR spent fuel blended with natural uranium in the CANDU-900 reactor. This system reduced actinide content by 35% and decreased natural uranium consumption by 24% over a PWR once through cycle. The thorium cycles evaluated used two CANDU-900 units, a generator and a burner unit along with a drivermore » fuel feedstock. The driver fuels included plutonium reprocessed from PWR, from CANDU and low enriched uranium (LEU). All three cycles were effective options and reduced natural uranium consumption over a PWR once through cycle. The LEU driven system saw the largest reduction with a 94% savings while the plutonium driven cycles achieved 75% savings for PWR and 87% for CANDU. The high neutron economy, online fuelling and flexible compact fuel make the CANDU system an ideal reactor platform for many advanced fuel cycles.« less

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

JOWOG 22/2 - Actinide Chemical Technology (July 9-13, 2012)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jackson, Jay M.; Lopez, Jacquelyn C.; Wayne, David M.

2012-07-05

The Plutonium Science and Manufacturing Directorate provides world-class, safe, secure, and reliable special nuclear material research, process development, technology demonstration, and manufacturing capabilities that support the nation's defense, energy, and environmental needs. We safely and efficiently process plutonium, uranium, and other actinide materials to meet national program requirements, while expanding the scientific and engineering basis of nuclear weapons-based manufacturing, and while producing the next generation of nuclear engineers and scientists. Actinide Process Chemistry (NCO-2) safely and efficiently processes plutonium and other actinide compounds to meet the nation's nuclear defense program needs. All of our processing activities are done in amore » world class and highly regulated nuclear facility. NCO-2's plutonium processing activities consist of direct oxide reduction, metal chlorination, americium extraction, and electrorefining. In addition, NCO-2 uses hydrochloric and nitric acid dissolutions for both plutonium processing and reduction of hazardous components in the waste streams. Finally, NCO-2 is a key team member in the processing of plutonium oxide from disassembled pits and the subsequent stabilization of plutonium oxide for safe and stable long-term storage.« less

Crystalline matrices for the immobilization of plutonium and actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, E.B.; Burakov, E.E.; Galkin, Ya.B.

1996-05-01

The management of weapon plutonium, disengaged as a result of conversion, is considered together with the problem of the actinide fraction of long-lived high level radioactive wastes. It is proposed to use polymineral ceramics based on crystalline host-phases: zircon ZrSiO{sub 4} and zirconium dioxide ZrO{sub 2}, for various variants of the management of plutonium and actinides (including the purposes of long-term safe storage or final disposal from the human activity sphere). It is shown that plutonium and actinides are able to form with these phases on ZrSiO{sub 4} and ZrO{sub 2} was done on laboratory level by the hot pressingmore » method, using the plasmochemical calcination technology. To incorporate simulators of plutonium into the structure of ZrSiO{sub 4} and ZrO{sub 2} in the course of synthesis, an original method developed by the authors as a result of studying the high-uranium zircon (Zr,U) SiO{sub 4} form Chernobyl {open_quotes}lavas{close_quotes} was used.« less

Properties of pure single crystals of actinide compounds

NASA Astrophysics Data System (ADS)

Vogt, O.

1989-07-01

Actinide research started with substances of poor quality and a multitude of "unexplainable" results mostly found on powder samples of doubtful quality exerted some pressure on the crystal growers. As an example we may mention the measurements on UP. Type I antiferromagnetism was found below 123 K by neutron diffraction experiments on powdered samples. At 23 K another transition becomes apparent in susceptibility measurements. The change of the magnetic moments associated with this transition remained unexplained. It was only after the discovery of multi k structures in other actinide compounds that the need was seen to perform even inelastic neutron diffraction experiments on single crystals so that finally the true nature of the transition in UP could be revealed. NpAs is another illustrative example for the fact that sometimes it takes decades to get a clear understanding for things even so simple as macroscopic magnetic properties. The main reason for the need of single crystals is certainly the anisotropy of the magnetic moment encountered in all actinide compounds. Self-heating effects may prevent research on big crystals or might call for isotopic purity of certain samples.

Lanthanide and actinide chemistry at high C/O ratios in the solar nebula

NASA Technical Reports Server (NTRS)

Lodders, Katharina; Fegley, Bruce, Jr.

1993-01-01

Chemical equilibrium calculations were performed to study the condensation chemistry of the REE and actinides under the highly reducing conditions which are necessary for the formation of the enstatite chondrites. Our calculations confirm that the REE and actinides condensed into oldhamite (CaS), the major REE and actinide host phase in enstatite chondrites, at a carbon-oxygen (C/O) ratio not less than 1 in an otherwise solar gas. Five basic types of REE abundance patterns, several of which are analogous to REE abundance patterns observed in the Ca, Al-rich inclusions in carbonaceous chondrites, are predicted to occur in meteoritic oldhamites. All of the reported REE patterns in oldhamites in enstatite chondrites can be interpreted in terms of our condensation calculations. The observed patterns fall into three of the five predicted categories. The reported Th and U enrichments and ratios in meteoritic oldhamites are also consistent with predictions of the condensation calculations. Pure REE sulfides are predicted to condense in the 10 exp -6 to 10 exp -9 bar range and may be found in enstatite chondrites if they formed in this pressure range.

JAERI R & D on accelerator-based transmutation under OMEGA program

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takizuka, T.; Nishida, T.; Mizumoto, M.

1995-10-01

The overview of the Japanese long-term research and development program on nuclide partitioning and transmutation, called {open_quotes}OMEGA,{close_quotes} is presented. Under this national program, major R&D activities are being carried out at JAERI, PNC, and CRIEPI. Accelerator-based transmutation study at JAERI is focused on a dedicated transmutor with a subcritical actinide-fueled subcritical core coupled with a spallation target driven by a high intensity proton accelerator. Two types of system concept, solid system and molten-salt system, are discussed. The solid system consists of sodium-cooled tungsten target and metallic actinide fuel. The molten-salt system is fueled with molten actinide chloride that acts alsomore » as a target material. The proposed plant transmutes about 250 kg of minor actinide per year, and generates enough electricity to power its own accelerator. JAERI is proposing the development of an intense proton linear accelerator ETA with 1.5 GeV-10 mA beam for engineering tests of accelerator-based transmutation. Recent achievements in the accelerator development are described.« less

Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal–Organic Frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dolgopolova, Ekaterina A.; Ejegbavwo, Otega A.; Martin, Corey R.

Growing necessity for efficient nuclear waste management is a driving force for development of alternative architectures towards fundamental understanding of mechanisms involved in actinide integration inside extended structures. In this manuscript, metal-organic frameworks (MOFs) were investigated as a model system for engineering radionuclide containing materials through utilization of unprecedented MOF modularity, which cannot be replicated in any other type of materials. Through the implementation of recent synthetic advances in the MOF field, hierarchical complexity of An-materials were built stepwise, which was only feasible due to preparation of the first examples of actinide-based frameworks with “unsaturated” metal nodes. The first successfulmore » attempts of solid-state metathesis and metal node extension in An-MOFs are reported, and the results of the former approach revealed drastic differences in chemical behavior of extended structures versus molecular species. Successful utilization of MOF modularity also allowed us to structurally characterize the first example of bimetallic An-An nodes. To the best of our knowledge, through combination of solid-state metathesis, guest incorporation, and capping linker installation, we were able to achieve the highest Th wt% in mono- and bi-actinide frameworks with minimal structural density. Overall, combination of a multistep synthetic approach with homogeneous actinide distribution and moderate solvothermal conditions could make MOFs an exceptionally powerful tool to address fundamental questions responsible for chemical behavior of An-based extended structures, and therefore, shed light on possible optimization of nuclear waste administration.« less

CMPO purity tests in the TRUEX solvent using americium-241

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brewer, K.N.; Herbst, R.S.; Tranter, T.J.

1993-12-01

The Transuranic Extraction (TRUEX) Process was developed by E.P. Horwitz and coworkers at Argonne National Laboratory (ANL) to separate the +4, +6, and +3 actinides from acidic aqueous solutions of nuclear wastes. Octyl (phenyl)-N-N-diisobutyl-carbamoylmethylphosphine oxide (CMPO) is the active actinide complexant used in the TRUEX solvent. CMPO is combined with tributyl phosphate (TBP) in an organic diluent, typically n-dodecane, to form the TRUEX solvent. Small quantities of impurities in the CMPO resulting from: (1) synthesis, (2) acid hydrolysis, or (3) radiolysis can result in actinide stripping problems from the solvent. The impurity, octylphenylphosphinic acid (POPPA), ia a powerful extractant atmore » low acid concentrations which may be formed during CMPO synthesis. Consequently, commercial CMPO may contain sufficient quantities of POPPA to significantly impact the stripping of actinides from the TRUEX solvent. The purpose of these tests was to (1) determine if commercially available CMPO is sufficiently pure to alleviate actinide stripping problems from the TRUEX process and (2) to determine if solvent cleanup methods are sufficient to purify the commercially purchased CMPO. Extraction and solvent cleanup methodologies used by Horwitz and coworkers at ANL were used to determine CMPO purity with {sup 241}Am. The improvement of the americium distribution coefficient in dilute nitric acid resulting from further purifying this CMPO is not significant enough to warrant additional CMPO purifying steps. The commercially purchased CMPO is found to be acceptable to use, as received, in a full-scale TRUEX process.« less

Applications of time-resolved laser fluorescence spectroscopy to the environmental biogeochemistry of actinides.

PubMed

Collins, Richard N; Saito, Takumi; Aoyagi, Noboru; Payne, Timothy E; Kimura, Takaumi; Waite, T David

2011-01-01

Time-resolved laser fluorescence spectroscopy (TRLFS) is a useful means of identifying certain actinide species resulting from various biogeochemical processes. In general, TRLFS differentiates chemical species of a fluorescent metal ion through analysis of different excitation and emission spectra and decay lifetimes. Although this spectroscopic technique has largely been applied to the analysis of actinide and lanthanide ions having fluorescence decay lifetimes on the order of microseconds, such as UO , Cm, and Eu, continuing development of ultra-fast and cryogenic TRLFS systems offers the possibility to obtain speciation information on metal ions having room-temperature fluorescence decay lifetimes on the order of nanoseconds to picoseconds. The main advantage of TRLFS over other advanced spectroscopic techniques is the ability to determine in situ metal speciation at environmentally relevant micromolar to picomolar concentrations. In the context of environmental biogeochemistry, TRLFS has principally been applied to studies of (i) metal speciation in aqueous and solid phases and (ii) the coordination environment of metal ions sorbed to mineral and bacterial surfaces. In this review, the principles of TRLFS are described, and the literature reporting the application of this methodology to the speciation of actinides in systems of biogeochemical interest is assessed. Significant developments in TRLFS methodology and advanced data analysis are highlighted, and we outline how these developments have the potential to further our mechanistic understanding of actinide biogeochemistry. American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.

Europium, uranyl, and thorium-phenanthroline amide complexes in acetonitrile solution: an ESI-MS and DFT combined investigation.

PubMed

Xiao, Cheng-Liang; Wang, Cong-Zhi; Mei, Lei; Zhang, Xin-Rui; Wall, Nathalie; Zhao, Yu-Liang; Chai, Zhi-Fang; Shi, Wei-Qun

2015-08-28

The tetradentate N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen) ligand with hard-soft donor atoms has been demonstrated to be promising for the group separation of actinides from highly acidic nuclear wastes. To identify the formed complexes of this ligand with actinides and lanthanides, electrospray ionization mass spectrometry (ESI-MS) combined with density functional theory (DFT) calculations was used to probe the possible complexation processes. The 1 : 2 Eu-L species ([EuL2(NO3)](2+)) can be observed in ESI-MS at low metal-to-ligand ([M]/[L]) ratios, whereas the 1 : 1 Eu-L species ([EuL(NO3)2](+)) can be observed when the [M]/[L] ratio is higher than 1.0. However, ([UO2L(NO3)](+)) is the only detected species for the uranyl complexes. The [ThL2(NO3)2](2+) species can be observed at low [M]/[L] ratios; the 1 : 2 species ([ThL2(NO3)](3+)) and a new 1 : 1 species ([ThL(NO3)3](+)) can be detected at high [M]/[L] ratios. Collision-induced dissociation (CID) results showed that Et-Tol-DAPhen ligands can coordinate strongly with metal ions, and the coordination moieties remain intact under CID conditions. Natural bond orbital (NBO), molecular electrostatic potential (MEP), electron localization function (ELF), atoms in molecules (AIM) and molecular orbital (MO) analyses indicated that the metal-ligand bonds of the actinide complexes exhibited more covalent character than those of the lanthanide complexes. In addition, according to thermodynamic analysis, the stable cationic M-L complexes in acetonitrile are found to be in good agreement with the ESI-MS results.

Analysis of incident-energy dependence of delayed neutron yields in actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nasir, Mohamad Nasrun bin Mohd, E-mail: monasr211@gmail.com; Metorima, Kouhei, E-mail: kohei.m2420@hotmail.co.jp; Ohsawa, Takaaki, E-mail: ohsawa@mvg.biglobe.ne.jp

The changes of delayed neutron yields (ν{sub d}) of Actinides have been analyzed for incident energy up to 20MeV using realized data of precursor after prompt neutron emission, from semi-empirical model, and delayed neutron emission probability data (P{sub n}) to carry out a summation method. The evaluated nuclear data of the delayed neutron yields of actinide nuclides are still uncertain at the present and the cause of the energy dependence has not been fully understood. In this study, the fission yields of precursor were calculated considering the change of the fission fragment mass yield based on the superposition of fivesmore » Gaussian distribution; and the change of the prompt neutrons number associated with the incident energy dependence. Thus, the incident energy dependent behavior of delayed neutron was analyzed.The total number of delayed neutron is expressed as ν{sub d}=∑Y{sub i} • P{sub ni} in the summation method, where Y{sub i} is the mass yields of precursor i and P{sub ni} is the delayed neutron emission probability of precursor i. The value of Y{sub i} is derived from calculation of post neutron emission mass distribution using 5 Gaussian equations with the consideration of large distribution of the fission fragments. The prompt neutron emission ν{sub p} increases at higher incident-energy but there are two different models; one model says that the fission fragment mass dependence that prompt neutron emission increases uniformly regardless of the fission fragments mass; and the other says that the major increases occur at heavy fission fragments area. In this study, the changes of delayed neutron yields by the two models have been investigated.« less

Comparison of actinide production in traveling wave and pressurized water reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osborne, A.G.; Smith, T.A.; Deinert, M.R.

The geopolitical problems associated with civilian nuclear energy production arise in part from the accumulation of transuranics in spent nuclear fuel. A traveling wave reactor is a type of breed-burn reactor that could, if feasible, reduce the overall production of transuranics. In one possible configuration, a cylinder of natural or depleted uranium would be subjected to a fast neutron flux at one end. The neutrons would transmute the uranium, producing plutonium and higher actinides. Under the right conditions, the reactor could become critical, at which point a self-stabilizing fission wave would form and propagate down the length of the reactormore » cylinder. The neutrons from the fission wave would burn the fissile nuclides and transmute uranium ahead of the wave to produce additional fuel. Fission waves in uranium are driven largely by the production and fission of {sup 239}Pu. Simulations have shown that the fuel burnup can reach values greater than 400 MWd/kgIHM, before fission products poison the reaction. In this work we compare the production of plutonium and minor actinides produced in a fission wave to that of a UOX fueled light water reactor, both on an energy normalized basis. The nuclide concentrations in the spent traveling wave reactor fuel are computed using a one-group diffusion model and are verified using Monte Carlo simulations. In the case of the pressurized water reactor, a multi-group collision probability model is used to generate the nuclide quantities. We find that the traveling wave reactor produces about 0.187 g/MWd/kgIHM of transuranics compared to 0.413 g/MWd/kgIHM for a pressurized water reactor running fuel enriched to 4.95 % and burned to 50 MWd/kgIHM. (authors)« less

Biogeochemical redox processes and their impact on contaminant dynamics

USGS Publications Warehouse

Borch, Thomas; Kretzschmar, Ruben; Kappler, Andreas; Van Cappellen, Philippe; Ginder-Vogel, Matthew; Campbell, Kate M.

2010-01-01

Life and element cycling on Earth is directly related to electron transfer (or redox) reactions. An understanding of biogeochemical redox processes is crucial for predicting and protecting environmental health and can provide new opportunities for engineered remediation strategies. Energy can be released and stored by means of redox reactions via the oxidation of labile organic carbon or inorganic compounds (electron donors) by microorganisms coupled to the reduction of electron acceptors including humic substances, iron-bearing minerals, transition metals, metalloids, and actinides. Environmental redox processes play key roles in the formation and dissolution of mineral phases. Redox cycling of naturally occurring trace elements and their host minerals often controls the release or sequestration of inorganic contaminants. Redox processes control the chemical speciation, bioavailability, toxicity, and mobility of many major and trace elements including Fe, Mn, C, P, N, S, Cr, Cu, Co, As, Sb, Se, Hg, Tc, and U. Redox-active humic substances and mineral surfaces can catalyze the redox transformation and degradation of organic contaminants. In this review article, we highlight recent advances in our understanding of biogeochemical redox processes and their impact on contaminant fate and transport, including future research needs.

AN EVALUATION OF POTENTIAL LINER MATERIALS FOR ELIMINATING FCCI IN IRRADIATED METALLIC NUCLEAR FUEL ELEMENTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

D. D. Keiser; J. I. Cole

2007-09-01

Metallic nuclear fuels are being looked at as part of the Global Nuclear Energy Program for transmuting longlive transuranic actinide isotopes contained in spent nuclear fuel into shorter-lived fission products. In order to optimize the performance of these fuels, the concept of using liners to eliminate the fuel/cladding chemical interactions that can occur during irradiation of a fuel element has been investigated. The potential liner materials Zr and V have been tested using solid-solid diffusion couples, consisting of liner materials butted against fuel alloys and against cladding materials. The couples were annealed at the relatively high temperature of 700°C. Thismore » temperature would be the absolute maximum temperature present at the fuel/cladding interface for a fuel element in-reactor. Analysis was performed using a scanning electron microscope equipped with energy-dispersive and wavelengthdispersive spectrometers (SEM/EDS/WDS) to evaluate any developed diffusion structures. At 700°C, minimal interaction was observed between the metallic fuels and either Zr or V. Similarly, limited interaction was observed between the Zr and V and the cladding materials. The best performing liner material appeared to be the V, based on amounts of interaction.« less

Development of a Plutonium Ceramic Target for the MASHA Separator

NASA Astrophysics Data System (ADS)

Shaughnessy, D. A.; Moody, K. J.; Kenneally, J. M.; Wild, J. F.; Stoyer, M. A.; Lougheed, R. W.; Yeremin, A. V.; Oganessian, Yu. Ts.

2004-04-01

We are participating in the development of the target for the MASHA (Mass Analyzer of Super Heavy Atoms) on-line mass separator in Dubna. Along with recent upgrades of the U400 cyclotron, MASHA will provide for at least a ten-fold increase in the production- and-detection rate for element 114 atoms, and will allow us to measure their atomic masses precisely. The MASHA separator will employ a thick Pu ceramic target capa- ble of tolerating temperatures in the vicinity of 2000 C without vaporizing the actinide compound. Reaction products will diffuse out of the target and will drift to an ECR ion source after which they will be transported through the separator and will impinge on a position-sensitive focal-plane detector array. Furthermore, operation of the MASHA hot target/ion source combination will provide chemical volatility information that will support our assignment of an atomic number of 114 to these nuclei. Taken together, these experiments on MASHA will allow us to make measurements that will cement our identification of element 114 and provide for future experiments in which the chemical properties of the heaviest elements are studied.

Method for forming an extraction agent for the separation of actinides from lanthanides

DOEpatents

Klaehn, John R.; Harrup, Mason K.; Law, Jack D.; Peterman, Dean R.

2010-04-27

An extraction agent for the separation of trivalent actinides from lanthanides in an acidic media and a method for forming same are described, and wherein the methodology produces a stable regiospecific and/or stereospecific dithiophosphinic acid that can operate in an acidic media having a pH of less than about 7.

Galvanic reduction of uranium(III) chloride from LiCl-KCl eutectic salt using gadolinium metal

NASA Astrophysics Data System (ADS)

Bagri, Prashant; Zhang, Chao; Simpson, Michael F.

2017-09-01

The drawdown of actinides is an important unit operation to enable the recycling of electrorefiner salt and minimization of waste. A new method for the drawdown of actinide chlorides from LiCl-KCl molten salt has been demonstrated here. Using the galvanic interaction between the Gd/Gd(III) and U/U(III) redox reactions, it is shown that UCl3 concentration in eutectic LiCl-KCl can be reduced from 8.06 wt.% (1.39 mol %) to 0.72 wt.% (0.12 mol %) in about an hour via plating U metal onto a steel basket. This is a simple process for returning actinides to the electrorefiner and minimizing their loss to the salt waste stream.

BAGHEERA: A new experimental facility at CEA / Valduc for actinides studies under high dynamic loading

NASA Astrophysics Data System (ADS)

Roy, G.; Llorca, F.; Lanier, G.; Lamalle, S.; Beaulieu, J.; Antoine, P.; Martinuzzi, P.

2006-08-01

This paper is a technical presentation about a new experimental facility recently developed at CEA/Valduc, BAGHEERA, a French acronym for “Hopkinson And High Speed Experiments Glove Box”. This facility is used since mid-2003 to characterize the physical and mechanical behaviour of actinides under high dynamic loadings. For this purpose, four basic experimental devices are confined inside a single glove box: a 50 mm bore diameter single stage light gas gun, two compression and torsion split Hopkinson bars (SHPB and TSHB respectively) and a Taylor test device (TTD). Design and technical data on the experimental equipment are addressed, with a particular emphasis on the gas gun specific features due to actinide applications.

Method for extracting lanthanides and actinides from acid solutions by modification of Purex solvent

DOEpatents

Horwitz, E.P.; Kalina, D.G.

1986-03-04

A process is described for the recovery of actinide and lanthanide values from aqueous solutions with an extraction solution containing an organic extractant having the formula as shown in a diagram where [phi] is phenyl, R[sup 1] is a straight or branched alkyl or alkoxyalkyl containing from 6 to 12 carbon atoms and R[sup 2] is an alkyl containing from 3 to 6 carbon atoms and phase modifiers in a water-immiscible hydrocarbon diluent. The addition of the extractant to the Purex process extractant, tri-n-butylphosphate in normal paraffin hydrocarbon diluent, will permit the extraction of multivalent lanthanide and actinide values from 0.1 to 12.0 molar acid solutions. 6 figs.

Uranium oxide fuel cycle analysis in VVER-1000 with VISTA simulation code

NASA Astrophysics Data System (ADS)

Mirekhtiary, Seyedeh Fatemeh; Abbasi, Akbar

2018-02-01

The VVER-1000 Nuclear power plant generates about 20-25 tons of spent fuel per year. In this research, the fuel transmutation of Uranium Oxide (UOX) fuel was calculated by using of nuclear fuel cycle simulation system (VISTA) code. In this simulation, we evaluated the back end components fuel cycle. The back end component calculations are Spent Fuel (SF), Actinide Inventory (AI) and Fission Product (FP) radioisotopes. The SF, AI and FP values were obtained 23.792178 ton/y, 22.811139 ton/y, 0.981039 ton/y, respectively. The obtained value of spent fuel, major actinide, and minor actinide and fission products were 23.8 ton/year, 22.795 ton/year, 0.024 ton/year and 0.981 ton/year, respectively.

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA –); Synthesis and Structure of M IVTTA 4 (M IV = Zr, Hf, Ce, Th, U, Np, Pu) and M III(TTA) 4 – (M III = Ce, Nd, Sm, Yb)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cary, Samantha K.; Livshits, Maksim; Cross, Justin N.

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction—or find alternatives—because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report in this paper advances in fundamental understandingmore » of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV(TTA) 4. Meanwhile, +3 metals formed anionic M III(TTA) 4 – species. Characterization of these M(TTA) 4 x– (x = 0, 1) compounds by UV–vis–NIR, IR, 1H and 19F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV(TTA) 4 and Pu IV(TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV(TTA) 4 and M III(TTA) 4 – are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Finally and moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV, Hf IV, and Zr IV.« less

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA –); Synthesis and Structure of M IVTTA 4 (M IV = Zr, Hf, Ce, Th, U, Np, Pu) and M III(TTA) 4 – (M III = Ce, Nd, Sm, Yb)

DOE PAGES

Cary, Samantha K.; Livshits, Maksim; Cross, Justin N.; ...

2018-03-21

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction—or find alternatives—because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report in this paper advances in fundamental understandingmore » of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV(TTA) 4. Meanwhile, +3 metals formed anionic M III(TTA) 4 – species. Characterization of these M(TTA) 4 x– (x = 0, 1) compounds by UV–vis–NIR, IR, 1H and 19F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV(TTA) 4 and Pu IV(TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV(TTA) 4 and M III(TTA) 4 – are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Finally and moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV, Hf IV, and Zr IV.« less

Characterization of Delayed-Particle Emission Signatures for Pyroprocessing. Part 1: ABTR Fuel Assembly.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durkee, Jr., Joe W.

A three-part study is conducted using the MCNP6 Monte Carlo radiation-transport code to calculate delayed-neutron (DN) and delayed-gamma (DG) emission signatures for nondestructive assay (NDA) metal-fuel pyroprocessing. In Part 1, MCNP6 is used to produce irradiation-induced used nuclear fuel (UNF) isotopic inventories for an Argonne National Laboratory (ANL) Advanced Burner Test Reactor (ABTR) preconceptual design fuel assembly (FA) model. The initial fuel inventory consists of uranium mixed with light-water-reactor transuranic (TRU) waste and 10 wt% zirconium (U-LWR-SFTRU-10%Zr). To facilitate understanding, parametric evaluation is done using models for 3% and 5% initial 235U a% enrichments, burnups of 5, 10, 15, 20,more » 30, …, 120 GWd/MTIHM, and 3-, 5-, 10-, 20-, and 30- year cooling times. Detailed delayed-particle radioisotope source terms for the irradiate FA are created using BAMF-DRT and SOURCES3A. Using simulation tallies, DG activity ratios (DGARs) are developed for 134Cs/ 137Cs 134Cs/ 154Eu, and 154Eu/ 137Cs markers as a function of (1) burnup and (2) actinide mass, including elemental uranium, neptunium, plutonium, americium, and curium. Spectral-integrated DN emission is also tallied. The study reveals a rich assortment of DGAR behavior as a function of DGAR type, enrichment, burnup, and cooling time. Similarly, DN emission plots show variation as a function of burnup and of actinide mass. Sensitivity of DGAR and DN signatures to initial 235U enrichment, burnup, and cooling time is evident. Comparisons of the ABTR radiation signatures and radiation signatures previously reported for a generic Westinghouse oxide-fuel assembly indicate that there are pronounced differences in the ABTR and Westinghouse oxide-fuel DN and DG signatures. These differences are largely attributable to the initial TRU inventory in the ABTR fuel. The actinide and nonactinide inventories for the FA models serve as source materials for the pre- and postelectrorefining models to be reported in Parts 2 and 3.« less

The apparent absence of chemical sensitivity in the 4d and 5d X-ray absorption spectroscopy of uranium compounds

DOE PAGES

Tobin, J. G.

2013-05-03

X-ray absorption spectroscopy (XAS) and related derivative measurements have been used to demonstrate that the Pu 5f states are strongly relativistic and have a 5f occupation number near 5. Owing to the success in this regime, it has been argued that the XAS measurements should be a powerful tool to probe 5f occupation variation, both as a function of elemental nature (actinide atomic number) and as a function of physical and chemical perturbation, e.g., oxidation state. We show that XAS and its related measurements fail in this latter aspect for a wide variety of uranium compounds and materials. Possible causesmore » will be discussed.« less

The Role of Chromohalobacter on Transport of Lanthanides and Cesium in the Dolomite Mineral System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zengotita, Frances; Emerson, Hilary Palmer; Dittrich, Timothy M.

2017-12-01

The chemical behavior of actinide series elements and fission products is a concern for the Waste Isolation Pilot Plant repository due to their uncertain mobility in the subsurface salt formation. In this work, we are observing the behavior of the halophilic bacterium, Chromohalobacter, and its effect on the mobility of lanthanides and cesium in the presence of dolomite. Batch and minicolumn experiments were conducted with Cs + and lanthanides (Nd 3+, Eu 3+) to quantify potential transport with bacteria. Preliminary results show that Cs does not interact strongly with dolomite or Chromohalobacter, while the lanthanides can interact strongly with bothmore » minerals and bacteria depending on which the Ln contacts first.« less

Metals, minerals and microbes: geomicrobiology and bioremediation.

PubMed

Gadd, Geoffrey Michael

2010-03-01

Microbes play key geoactive roles in the biosphere, particularly in the areas of element biotransformations and biogeochemical cycling, metal and mineral transformations, decomposition, bioweathering, and soil and sediment formation. All kinds of microbes, including prokaryotes and eukaryotes and their symbiotic associations with each other and 'higher organisms', can contribute actively to geological phenomena, and central to many such geomicrobial processes are transformations of metals and minerals. Microbes have a variety of properties that can effect changes in metal speciation, toxicity and mobility, as well as mineral formation or mineral dissolution or deterioration. Such mechanisms are important components of natural biogeochemical cycles for metals as well as associated elements in biomass, soil, rocks and minerals, e.g. sulfur and phosphorus, and metalloids, actinides and metal radionuclides. Apart from being important in natural biosphere processes, metal and mineral transformations can have beneficial or detrimental consequences in a human context. Bioremediation is the application of biological systems to the clean-up of organic and inorganic pollution, with bacteria and fungi being the most important organisms for reclamation, immobilization or detoxification of metallic and radionuclide pollutants. Some biominerals or metallic elements deposited by microbes have catalytic and other properties in nanoparticle, crystalline or colloidal forms, and these are relevant to the development of novel biomaterials for technological and antimicrobial purposes. On the negative side, metal and mineral transformations by microbes may result in spoilage and destruction of natural and synthetic materials, rock and mineral-based building materials (e.g. concrete), acid mine drainage and associated metal pollution, biocorrosion of metals, alloys and related substances, and adverse effects on radionuclide speciation, mobility and containment, all with immense social and economic consequences. The ubiquity and importance of microbes in biosphere processes make geomicrobiology one of the most important concepts within microbiology, and one requiring an interdisciplinary approach to define environmental and applied significance and underpin exploitation in biotechnology.

Brief overview of the long-lived radionuclide separation processes developed in france in connection with the spin program

NASA Astrophysics Data System (ADS)

Madic, Charles; Bourges, Jacques; Dozol, Jean-François

1995-09-01

To reduce the long-term potential hazards associated with the management of nuclear wastes generated by nuclear fuel reprocessing, one alternative is the transmutation of long-lived radionuclides into short-lived radionuclides by nuclear means (P & T strategy). In this context, according to the law passed by the French Parliament on 30 December 1991, the CEA launched the SPIN program for the design of long-lived radionuclide separation and nuclear incineration processes. The research in progress to define separation processes focused mainly on the minor actinides (neptunium, americium and curium) and some fission products, like cesium and technetium. To separate these long-lived radionuclides, two strategies were developed. The first involves research on new operating conditions for improving the PUREX fuel reprocessing technology. This approach concerns the elements neptunium and technetium (iodine and zirconium can also be considered). The second strategy involves the design of new processes; DIAMEX for the co-extraction of minor actinides from the high-level liquid waste leaving the PUREX process, An(III)/Ln(III) separation using tripyridyltriazine derivatives or picolinamide extracting agents; SESAME for the selective separation of americium after its oxidation to Am(IV) or Am(VI) in the presence of a heteropolytungstate ligand, and Cs extraction using a new class of extracting agents, calixarenes, which exhibit exceptional Cs separation properties, especially in the presence of sodium ion. This lecture focuses on the latest achievements in these research areas.

Economic Analysis of National Nuclear Security Administration (NNSA) Modernization Alternatives

DTIC Science & Technology

2007-11-01

without nuclear testing; works to reduce global danger from weapons of mass destruction; provides the U.S. Navy with safe and effective nuclear...SFE) covers the acquisition of glove boxes, long-lead facility, and actinide chemistry/materials characterization (AC/MC) equipment whose uniqueness...Hazard Category II AC/MC and actinide Research and Development operations, special nuclear 5 Babcock

Aqueous and pyrochemical reprocessing of actinide fuels

NASA Astrophysics Data System (ADS)

Toth, L. Mac; Bond, Walter D.; Avens, Larry R.

1993-02-01

Processing of the nuclear fuel actinides has developed in two independent directions—aqueous processing and pyroprocessing. Similarities in the two processes, their goals, and restraints are indicated in brief parallel descriptions along with distinguishing advantages and areas of future development. It is suggested that from a technical viewpoint, the ultimate process might be a hybrid which incorporates the best steps of each process.

GGA + U studies of the early actinide mononitrides and dinitrides

NASA Astrophysics Data System (ADS)

Obodo, K. O.; Chetty, N.

2013-11-01

We present a detailed comparative study of the electronic and mechanical properties of the early actinide mononitrides and dinitrides within the framework of the Perdew-Burke-Ernzerhof generalized gradient approximation (GGA [PBE]) and GGA + U implementations of density functional theory with the inclusion of spin-orbit coupling. The dependence of selected observables of these materials on the effective U-parameter is investigated in detail. The properties include the lattice constant, bulk modulus, charge density distribution, hybridization of the atomic orbitals, energy of formation and the lattice dynamics. The inclusion of the Hubbard U parameter results in a proper description of the 5f electrons, and is subsequently used in the determination of the structural and electronic properties of these compounds. The mononitrides and dinitrides of the early actinides are metallic except for UN2, which is a semiconductor. These actinide nitrides are non-magnetic with the exception of UN, NpN, PuN, NpN2 and PuN2 that are magnetic systems with orbital-dependent magnetic moments oriented in the z-axis. We observed that ThN2 is elastically unstable to isotropic pressure. We discovered that UN2 is thermodynamically unstable, but may be stabilized by N vacancy formation.

Complexation of lanthanides and actinides by acetohydroxamic acid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, R.J.; Sinkov, S.I.; Choppin, G.R.

2008-07-01

Acetohydroxamic acid (AHA) has been proposed as a suitable reagent for the complexant-based, as opposed to reductive, stripping of plutonium and neptunium ions from the tributylphosphate solvent phase in advanced PUREX or UREX processes designed for future nuclear-fuel reprocessing. Stripping is achieved by the formation of strong hydrophilic complexes with the tetravalent actinides in nitric acid solutions. To underpin such applications, knowledge of the complexation constants of AHA with all relevant actinide (5f) and lanthanide (4f) ions is therefore important. This paper reports the determination of stability constants of AHA with the heavier lanthanide ions (Dy-Yb) and also U(IV) andmore » Th(IV) ions. Comparisons with our previously published AHA stability-constant data for 4f and 5f ions are made. (authors)« less

Process for recovering actinide values

DOEpatents

Horwitz, E. Philip; Mason, George W.

1980-01-01

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

Magnetic separation - Advanced nanotechnology for future nuclear fuel recycle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaur, M.; Zhang, H.; Qiang, Y.

2013-07-01

The unique properties of magnetic nanoparticles (MNPs), such as their extremely small size and high surface area to volume ratio, provide better kinetics for the adsorption of metal ions from aqueous solutions. In this work, we demonstrated the separation of minor actinides using complex conjugates of MNPs with diethylenetriamine-pentaacetic acid (DTPA) chelator. The sorption results show the strong affinity of DTPA towards Am (III) and Pu (IV) by extracting 97% and 80% of actinides, respectively. It is shown that the extraction process is highly dependent on the pH of the solution. If these long-term heat generating actinides can be efficientlymore » removed from the used fuel raffinates, the volume of material that can be placed in a given amount of repository space can be significantly increased. (authors)« less

Updated and revised neutron reaction data for 237Np

NASA Astrophysics Data System (ADS)

Chen, Guochang; Wang, Jimin; Cao, Wentian; Tang, Guoyou; Yu, Baosheng

2017-09-01

Nuclear data with high accuracy for minor actinides play an important role in nuclear technology applications, including reactor design and operation, fuel cycle, estimation of the amount of minor actinides in high burn-up reactors and the minor actinides transmutation. Based on the evaluated experimental data, the updated and revised evaluation of a full set of n+237Np nuclear data from 10-5 eV ˜ 20 MeV are carried out and recommended. Mainly revised quantities are neutron multiplicities from fission reaction, inelastic, fission, (n, 2n) and (n, γ) reaction cross sections as well as angular distribution and so on. The promising results are obtained when the renewal evaluated data of 237Np will be used to instead of the evaluated data in CENDL-3.1 database.

Updated and revised neutron reaction data for 236,238Np

NASA Astrophysics Data System (ADS)

Chen, Guochang; Wang, Jimin; Cao, Wentian; Tang, Guoyou; Yu, Baosheng

2017-09-01

Nuclear data with high accuracy for minor actinides play an important role in nuclear technology applications, including reactor design and operation, fuel cycle, estimation of the amount of minor actinides in high burn-up reactors and the minor actinides transmutation. Based on a new set of neutron optical model parameter and the reaction cross section systematics of fissile isotopes, a full set of 236,238Np neutron reaction data from 10-5 eV ˜20 MeV are updated and improved through theoretical calculation. Mainly revised quantities include the total, elastic, inelastic, fission, (n, 2n) and (n, γ) reaction cross sections as well as angular distribution etc. The promising results are obtained when the renewal evaluated data of 236,238Np will replace the evaluated data in CENDL-3.1 database.

Electrodeposition of actinide compounds from an aqueous ammonium acetate matrix. Experimental development and optimization

DOE PAGES

Boll, Rose Ann; Matos, Milan; Torrico, Matthew N.

2015-03-27

Electrodeposition is a technique that is routinely employed in nuclear research for the preparation of thin solid films of actinide materials which can be used in accelerator beam bombardments, irradiation studies, or as radioactive sources. The present study investigates the deposition of both lanthanides and actinides from an aqueous ammonium acetate electrolyte matrix. Electrodepositions were performed primarily on stainless steel disks; with yield analysis evaluated using -spectroscopy. Experimental parameters were studied and modified in order to optimize the uniformity and adherence of the deposition while maximizing the yield. The initial development utilized samarium as the plating material, with and withoutmore » a radioactive tracer. As a result, surface characterization studies were performed by scanning electron microscopy, electron microprobe analysis, radiographic imaging, and x-ray diffraction.« less

Apparatus and method for reprocessing and separating spent nuclear fuels. [Patent application

DOEpatents

Krikorian, O.H.; Grens, J.Z.; Parrish, W.H. Sr.; Coops, M.S.

1982-01-19

A method and apparatus for separating and reprocessing spent nuclear fuels includes a separation vessel housing a molten metal solvent in a reaction region, a reflux region positioned above and adjacent to the reaction region, and a porous filter member defining the bottom of the separation vessel in a supporting relationship with the metal solvent. Spent fuels are added to the metal solvent. A nonoxidizing nitrogen-containing gas is introduced into the separation vessel, forming solid actinide nitrides in the metal solvent from actinide fuels, while leaving other fission products in solution. A pressure of about 1.1 to 1.2 atm is applied in the reflux region, forcing the molten metal solvent and soluble fission products out of the vessel, while leaving the solid actinide nitrides in the separation vessel.

Accuracy Improvement of Neutron Nuclear Data on Minor Actinides

NASA Astrophysics Data System (ADS)

Harada, Hideo; Iwamoto, Osamu; Iwamoto, Nobuyuki; Kimura, Atsushi; Terada, Kazushi; Nakao, Taro; Nakamura, Shoji; Mizuyama, Kazuhito; Igashira, Masayuki; Katabuchi, Tatsuya; Sano, Tadafumi; Takahashi, Yoshiyuki; Takamiya, Koichi; Pyeon, Cheol Ho; Fukutani, Satoshi; Fujii, Toshiyuki; Hori, Jun-ichi; Yagi, Takahiro; Yashima, Hiroshi

2015-05-01

Improvement of accuracy of neutron nuclear data for minor actinides (MAs) and long-lived fission products (LLFPs) is required for developing innovative nuclear system transmuting these nuclei. In order to meet the requirement, the project entitled as "Research and development for Accuracy Improvement of neutron nuclear data on Minor ACtinides (AIMAC)" has been started as one of the "Innovative Nuclear Research and Development Program" in Japan at October 2013. The AIMAC project team is composed of researchers in four different fields: differential nuclear data measurement, integral nuclear data measurement, nuclear chemistry, and nuclear data evaluation. By integrating all of the forefront knowledge and techniques in these fields, the team aims at improving the accuracy of the data. The background and research plan of the AIMAC project are presented.

A combined calorimetric and computational study of the energetics of rare earth substituted UO 2 systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Lei; Solomon, Jonathan M.; Asta, Mark

2015-09-01

The energetics of rare earth substituted UO2 solid solutions (U1-xLnxO2-0.5x+y, where Ln = La, Y, and Nd) are investigated employing a combination of calorimetric measurements and density functional theory based computations. Calculated and measured formation enthalpies agree within 10 kJ/mol for stoichiometric oxygen/metal compositions. To better understand the factors governing the stability and defect binding in rare earth substituted urania solid solutions, systematic trends in the energetics are investigated based on the present results and previous computational and experimental thermochemical studies of rare earth substituted fluorite oxides (A1-xLnxO2-0.5x, where A = Hf, Zr, Ce, and Th). A consistent trend towardsmore » increased energetic stability with larger size mismatch between the smaller host tetravalent cation and the larger rare earth trivalent cation is found for both actinide and non-actinide fluorite oxide systems where aliovalent substitution of Ln cations is compensated by oxygen vacancies. However, the large exothermic oxidation enthalpy in the UO2 based systems favors oxygen rich compositions where charge compensation occurs through the formation of uranium cations with higher oxidation states.« less

The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruce J. Mincher; Guiseppe Modolo; Strephen P. Mezyk

2009-01-01

Solvent extraction is the most commonly used process scale separation technique for nuclear applications and it benefits from more than 60 years of research and development and proven experience at the industrial scale. Advanced solvent extraction processes for the separation of actinides and fission products from dissolved nuclear fuel are now being investigated worldwide by numerous groups (US, Europe, Russia, Japan etc.) in order to decrease the radiotoxic inventories of nuclear waste. While none of the advanced processes have yet been implemented at the industrial scale their development studies have sometimes reached demonstration tests at the laboratory scale. Most ofmore » the partitioning strategies rely on the following four separations: 1. Partitioning of uranium and/or plutonium from spent fuel dissolution liquors. 2. Separation of the heat generating fission products such as strontium and cesium. 3. Coextraction of the trivalent actinides and lanthanides. 4. Separation of the trivalent actinides from the trivalent lanthanides. Tributylphosphate (TBP) in the first separation is the basis of the PUREX, UREX and COEX processes, developed in Europe and the US, whereas monoamides as alternatives for TBP are being developed in Japan and India. For the second separation, many processes were developed worldwide, including the use of crown-ether extractants, like the FPEX process developed in the USA, and the CCD-PEG process jointly developed in the USA and Russia for the partitioning of cesium and strontium. In the third separation, phosphine oxides (CMPOs), malonamides, and diglycolamides are used in the TRUEX, DIAMEX and the ARTIST processes, respectively developed in US, Europe and Japan. Trialkylphosphine oxide(TRPO) developed in China, or UNEX (a mixture of several extractants) jointly developed in Russia and the USA allow all actinides to be co-extracted from acidic radioactive liquid waste. For the final separation, soft donor atom-containing ligands such as the bistriazinylbipyridines (BTBPs) or dithiophosphinic acids have been developed in Europe and China to selectively extract the trivalent actinides. However, in the TALSPEAK process developed in the USA, the separation is based on the relatively high affinity of aminopolycarboxylic acid complexants such as DTPA for trivalent actinides over lanthanides. In the DIDPA, SETFICS and the GANEX processes, developed in Japan and France, the group separation is accomplished in a reverse TALSPEAK process. A typical scenario is shown in Figure 1 for the UREX1a (Uranium Extraction version 1a) process. The initial step is the TBP extraction for the separation of recyclable uranium. The second step partitions the short-lived, highly radioactive cesium and strontium to minimize heat loading in the high-level waste repository. The third step is a group separation of the trivalent actinides and lanthanides with the last step being partitioning of the trivalent lanthanides from the actinides.« less

Am phases in the matrix of a U–Pu–Zr alloy with Np, Am, and rare-earth elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Janney, Dawn E.; Kennedy, J. Rory; Madden, James W.

2015-01-01

Phases and microstructures in the matrix of an as-cast U-Pu-Zr alloy with 3 wt% Am, 2% Np, and 8% rare-earth elements were characterized by scanning and transmission electron microscopy. The matrix consists primarily of two phases, both of which contain Am: ζ-(U, Np, Pu, Am) (~70 at% U, 5% Np, 14% Pu, 1% Am, and 10% Zr) and δ-(U, Np, Pu, Am)Zr 2 (~25% U, 2% Np, 10-15% Pu, 1-2% Am, and 55-60 at% Zr). These phases are similar to those in U-Pu-Zr alloys, although the Zr content in ζ-(U, Np, Pu, Am) is higher than that in ζ-(U, Pu)more » and the Zr content in δ-(U, Np, Pu, Am)Zr 2 is lower than that in δ-UZr 2. Nanocrystalline actinide oxides with structures similar to UO2 occurred in some areas, but may have formed by reactions with the atmosphere during sample handling. Planar features consisting of a central zone of ζ-(U, Np, Pu, Am) bracketed by zones of δ-(U, Np, Pu, Am)Zr 2 bound irregular polygons ranging in size from a few micrometers to a few tens of micrometers across. The rest of the matrix consists of elongated domains of ζ-(U, Np, Pu, Am) and δ-(U, Np, Pu, Am)Zr 2. Each of these domains is a few tens of nanometers across and a few hundred nanometers long. The domains display strong preferred orientations involving areas a few hundred nanometers to a few micrometers across.« less

A low initial abundance of 247Cm in the early solar system and implications for r-process nucleosynthesis

NASA Astrophysics Data System (ADS)

Stirling, Claudine H.; Halliday, Alex N.; Potter, Emma-Kate; Andersen, Morten B.; Zanda, Brigitte

2006-11-01

The short-lived nuclide 247Cm is produced by r-process nucleosynthesis. When the presolar nebula formed, 247Cm became isolated from r-process production and its abundance diminished as a result of radioactive decay. Given its short half-life of only ˜ 16 million years, 247Cm is presently extinct, but its former presence should be detectable as small variations in 235U/ 238U in primitive meteoritic material, provided Cm was chemically fractionated from U at the time these solid objects formed. The magnitude of U isotopic anomalies in meteorites can thus be used to elucidate the timing and character of the last r-process nucleosynthetic event for input into models describing the formation and evolution of the early solar system. Here we report coupled U isotopic determinations and Nd/U proxy measurements for Cm/U in a series of acid-etched leachates and mineral assemblages extracted from meteorites containing primitive phases expected to show strong Cm-U fractionations. Using multiple-collector ICPMS, we are able to determine 235U/ 238U with 2 σ analytical uncertainties of ± 1 epsilon (1 epsilon = 1 part in 10,000) on sample sizes consisting of < 3 ng of 238U and < 20 pg of 235U. A double-spiking procedure using a mixed 236U- 233U spike was employed to allow instrumental mass fractionation to be reliably corrected internally and at high precision. Uranium isotopic results for almost 40 different phases show no resolvable deviations in 235U/ 238U from the chondritic value, at the ˜ 1-2 epsilon level. These data supplement our previous observations for a suite of bulk meteorite samples [C.H. Stirling, A.N. Halliday, D. Porcelli, In search of live 247Cm in the early solar system, Geochim. Cosmochim. Acta 69 (2005) 1059-1071] and provide evidence for a solar system initial 247Cm/ 235U of < 8 × 10 - 5 . Such a low value is difficult to explain without a long time-scale of ˜ 2.3 × 10 8 years between the last actinide producing r-process event and the formation of the solar system. As such it is difficult to reconcile with a model of actinide production in the same r-process forming event as 182Hf with a half-life of 8.9 My [G.J. Wasserburg, M. Busso, R. Gallino, Abundances of actinides and short-lived nonactinides in the interstellar medium: Diverse supernova sources for the r-processes, Astrophys. J. 466 (1996) L109-L113]. The alternative models of 182Hf production via a neutron-rich fast s-process, occurring, for example, in the helium burning shell in a 25 solar mass star during explosive nucleosynthesis [G.J. Wasserburg, M. Busso, R. Gallino, Abundances of actinides and short-lived nonactinides in the interstellar medium: Diverse supernova sources for the r-processes, Astrophys. J. 466 (1996) L109-L113], or via a distinct r-process event that is separate from actinide production [G.J. Wasserburg, M. Busso, R. Gallino, K.M. Nollet, Short-lived nuclei in the early solar system: Possible AGB sources, Nucl. Phys. A (in press)], may provide a viable explanation. However, further studies are also required to assess the veracity of Cm-U systematics, which are critically dependent on the suitability of using Nd and the light rare earth elements (LREEs) as a chemical proxy for Cm.

Rare earth elements concentration in mushroom cultivation substrates affects the production process and fruit-bodies content of Pleurotus ostreatus and Cyclocybe cylindracea.

PubMed

Koutrotsios, Georgios; Danezis, Georgios P; Georgiou, Constantinos A; Zervakis, Georgios I

2018-04-20

Concentrations of 16 rare earth elements (REEs) and two actinides were determined for the first time both in cultivated mushrooms and in their production substrates by inductively coupled plasma mass spectroscopy. Moreover, the effect of REEs on cultivation parameters and composition of the final product was assessed, together with their potential use for authentication purposes. The concentrations of REEs varied greatly among seven cultivation substrates and correlated with measurements in Cyclocybe cylindracea mushrooms; no such correlation was established in Pleurotus ostreatus. Reduction of hemicellulose, cellulose, and lignin in substrates during P. ostreatus cultivation was positively correlated with REE concentrations, which also affected the production performance depending on the species examined. In all cases, a negative correlation was established between bioconcentration factors (BCF) in mushrooms and REE content in substrates, while the effect of substrate composition on BCF values varied according to the element studied. The estimated daily intake values of REEs through mushroom consumption was at much lower levels than those reported as potentially harmful for human health. The content of REEs in cultivation substrates and in mushrooms revealed that the bioaccumulation of elements differed in each fungus. The nature/origin of substrates seemed to affect the concentration of REEs in mushrooms to a considerable extent. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

Diagnostic and Therapeutic Radiopharmaceutical Agents for Selective Discrimination of Prostate Cancer

DTIC Science & Technology

2009-10-01

Bottenus, Brienne N.∞; Fugate, Glenn A.†; Benny, Paul*. Actinides Separations, Conference Pacific Northwest National Lab 6/2006 In situ formation of...Bottenus, Brienne N.∞; Benny, Paul*. Actinides Separations, Conference Pacific Northwest National Lab 3/12/2006 S-functionalized cysteine ligands...cancer imaging. The successful preparation and radiolabeling of the first generation of compounds illustrates one the key critical objectives being

URANIUM SEPARATION PROCESS

DOEpatents

Lyon, W.L.

1962-04-17

A method of separating uranium oxides from PuO/sub 2/, ThO/sub 2/, and other actinide oxides is described. The oxide mixture is suspended in a fused salt melt and a chlorinating agent such as chlorine gas or phosgene is sparged through the suspension. Uranium oxides are selectively chlorinated and dissolve in the melt, which may then be filtered to remove the unchlorinated oxides of the other actinides. (AEC)

Alternate method of source preparation for alpha spectrometry: No electrodeposition, no hydrofluoric acid

DOE PAGES

Kurosaki, Hiromu; Mueller, Rebecca J.; Lambert, Susan B.; ...

2016-07-15

An alternate method of preparing actinide alpha counting sources was developed in place of electrodeposition or lanthanide fluoride micro-precipitation. The method uses lanthanide hydroxide micro-precipitation to avoid the use of hazardous hydrofluoric acid. Lastly, it provides a quicker, simpler, and safer way of preparing actinide alpha counting sources in routine, production-type laboratories that process many samples daily.

An Approach for Validating Actinide and Fission Product Burnup Credit Criticality Safety Analyses: Criticality (k eff) Predictions

DOE PAGES

Scaglione, John M.; Mueller, Don E.; Wagner, John C.

2014-12-01

One of the most important remaining challenges associated with expanded implementation of burnup credit in the United States is the validation of depletion and criticality calculations used in the safety evaluation—in particular, the availability and use of applicable measured data to support validation, especially for fission products (FPs). Applicants and regulatory reviewers have been constrained by both a scarcity of data and a lack of clear technical basis or approach for use of the data. In this study, this paper describes a validation approach for commercial spent nuclear fuel (SNF) criticality safety (k eff) evaluations based on best-available data andmore » methods and applies the approach for representative SNF storage and transport configurations/conditions to demonstrate its usage and applicability, as well as to provide reference bias results. The criticality validation approach utilizes not only available laboratory critical experiment (LCE) data from the International Handbook of Evaluated Criticality Safety Benchmark Experiments and the French Haut Taux de Combustion program to support validation of the principal actinides but also calculated sensitivities, nuclear data uncertainties, and limited available FP LCE data to predict and verify individual biases for relevant minor actinides and FPs. The results demonstrate that (a) sufficient critical experiment data exist to adequately validate k eff calculations via conventional validation approaches for the primary actinides, (b) sensitivity-based critical experiment selection is more appropriate for generating accurate application model bias and uncertainty, and (c) calculated sensitivities and nuclear data uncertainties can be used for generating conservative estimates of bias for minor actinides and FPs. Results based on the SCALE 6.1 and the ENDF/B-VII.0 cross-section libraries indicate that a conservative estimate of the bias for the minor actinides and FPs is 1.5% of their worth within the application model. Finally, this paper provides a detailed description of the approach and its technical bases, describes the application of the approach for representative pressurized water reactor and boiling water reactor safety analysis models, and provides reference bias results based on the prerelease SCALE 6.1 code package and ENDF/B-VII nuclear cross-section data.« less

Influence of a Heterocyclic Nitrogen-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by Aminopolycarboxylate Complexants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa

Here, the novel metal chelator N-2-(pyridylmethyl)diethylenetriamine- N,N',N",N"-tetraacetic acid (DTTA-PyM) was designed to replace a single oxygen-donor acetate group of the well-known aminopolycarboxylate complexant diethylenetriamine- N,N,N',N",N"-pentaacetic acid (DTPA) with a nitrogen-donor 2-pyridylmethyl. Potentiometric, spectroscopic, computational, and radioisotope distribution methods show distinct differences for the 4f and 5f coordination environments and enhanced actinide binding due to the nitrogen-bearing heterocyclic moiety. The Am 3+, Cm 3+, and Ln 3+ complexation studies for DTTA-PyM reveal an enhanced preference, relative to DTPA, for trivalent actinide binding. Fluorescence studies indicate no changes to the octadentate coordination of trivalent curium, while evidence of heptadentate complexation of trivalentmore » europium is found in mixtures containing EuHL (aq) complexes at the same aqueous acidity. The denticity change observed for Eu 3+ suggests that complex protonation occurs on the pyridyl nitrogen. Formation of the CmHL (aq) complex is likely due to the protonation of an available carboxylate group because the carbonyl oxygen can maintain octadentate coordination through a rotation. The observed suppressed protonation of the pyridyl nitrogen in the curium complexes may be attributed to stronger trivalent actinide binding by DTTA-PyM. Density functional theory calculations indicate that added stabilization of the actinide complexes with DTTA-PyM may originate from π-back-bonding interactions between singly occupied 5f orbitals of Am 3+ and the pyridyl nitrogen. The differences between the stabilities of trivalent actinide chelates (Am 3+, Cm 3+) and trivalent lanthanide chelates (La 3+–Lu 3+) are observed in liquid–liquid extraction systems, yielding unprecedented 4f/5f differentiation when using DTTA-PyM as an aqueous holdback reagent. In addition, the enhanced nitrogen-donor softness of the new DTTA-PyM chelator was perturbed by adding a fluorine onto the pyridine group. The comparative characterization of N-(3-fluoro-2-pyridylmethyl)diethylenetriamine- N,N',N",N"-tetraacetic acid (DTTA-3-F-PyM) showed subdued 4 f/5 f differentiation due to the presence of this electron-withdrawing group.« less

Towards Synthesis and Usage of Actinide-Bearing REE Phosphate age Standards: A Progress Report

NASA Astrophysics Data System (ADS)

Pyle, J. M.; Cherniak, D. J.

2006-05-01

Electron microprobe (EMP) dates result from a concentration-time unit conversion, so use of a concentration- based (rather than isotope-ratio based) fictive age standard is warranted. This observation has motivated our mineral synthesis program, aimed at producing actinide-doped REE phosphate EMP dating standards that meet the following criteria: 1) known concentrations of U, Th, and Pb; 2) homogeneous intragrain distribution of all components; 3) of suitable size, either as a single-crystal or polycrystalline sintered ceramic. Single-crystal synthesis of actinide-doped LaPO4 by flux-growth methods results in disproportionation of lanthanide and flux, alkali, and actinide components into phosphate and oxide phases, respectively, and flux- growth methods were abandoned. Actinide-doped La phosphate is successfully prepared by high-T annealing and hydrothermal processing of microcrystalline phosphate; both homogeneity and charge-balance of (Ca, Th, Pb)-bearing LaPO4 increase with increasing solvent acidity during cold-seal hydrothermal synthesis. A combination of pressing and high-T (1400° C) sintering transforms fine-grained (0.1-10 μm) run- products to ceramic pellets with 90-95% theoretical density. Our most recent runs focused on a target composition of La80(CaTh)17(CaU)2(PbTh)1PO4 processed with 6% 2M HCl at 820° C, 0.75 kbar for 1 week. The run products are 0.1-2 μm crystals identified by XRD as La-actinide phosphate solid solution. 2 μm grains (N=16) give a composition (mean±2 sd) of La79.77(1.26)(CaTh)17.87(1.00)(CaU)1.53(0.42)(PbTh)0.82(0.09)PO4. Th (8.07-9.13 wt. %) is homogeneous at the level of analytical precision, and the Pb concentration range (3500-4350 ppm) is restricted relative to untreated precipitate. Uranium concentration values are more variable (6500-10000 ppm). This run yields a fictive age of 702±4 Ma (mean±2 se), compared to the fictive age of 794 Ma for the target composition.

Comparative Photoemission Study of Actinide (Am, Pu, Np and U) Metals, Nitrides, and Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gouder, Thomas; Seibert, Alice; Rebizant, Jean

2007-07-01

Core-level and valence-band spectra of Pu and the other early actinide compounds show remarkable systematics, which can be understood in the framework of final state screening. We compare the early actinide (U, Np, Pu and Am) metals, nitrides and hydrides and a few other specific compounds (PuSe, PuS, PuCx, PuSix) prepared as thin films by sputter deposition. In choosing these systems, we combine inherent 5f band narrowing, due to 5f orbital contraction throughout the actinide series, with variations of the chemical environment in the compounds. Goal of this work was to learn more on the electronic structure of the earlymore » actinide systems and to achieve the correct interpretation of their photoemission spectra. The highly correlated nature of the 5f states in systems, which are on the verge to localization, makes this a challenging task, because of the peculiar interplay between ground state DOS and final-state effects. Their influence can be estimated by doing systematic studies on systems with different (5f) bandwidths. We conclude on the basis of such systematic experiments that final-state effects due to strong e-e correlations in narrow 5f-band systems lead to multiplet like structures, analogous to those observed in the case of systems with localized electron states. Such observations in essentially band-like 5f-systems was first surprising, but the astonishing similarity of photoemission spectra of very different chemical systems (e.g. PuSe, Pu{sub 2}C{sub 3}..) points to a common origin, relating them to atomic features rather than material dependent density of states (DOS) features. (authors)« less

Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 successfulmore » 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.« less

Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, Donald Timothy; Borkowski, Marian; Lucchini, Jean - Francois

2010-12-10

The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity.more » Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.« less

Seventeen-Coordinate Actinide Helium Complexes.

PubMed

Kaltsoyannis, Nikolas

2017-06-12

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

Alterations of thorium oxalate morphology by changing elementary precipitation conditions

NASA Astrophysics Data System (ADS)

Tyrpekl, V.; Beliš, M.; Wangle, T.; Vleugels, J.; Verwerft, M.

2017-09-01

Oxalates of actinide elements are widely used in research and industry mainly due to their low solubility in aqueous solution and easy conversion to oxide. Although thorium oxide is worldwide mostly produced by the oxalate precipitation and conversion route, the powder morphology obtained through this process is known to inhibit the packing and sintering step of the pellet production. The presented work investigates the effects of oxalate precipitation conditions on the final powder morphology. Among the precipitation conditions considered are: pH of the thorium feed solution, concentration, temperature and the order of addition (thorium solution in oxalic acid solution and vice versa) known as reverse/direct strike. Herein, we show that the morphology of the final oxalate depends significantly on the above mentioned precipitation parameters.

In-gas-cell laser ionization studies of plutonium isotopes at IGISOL

NASA Astrophysics Data System (ADS)

Pohjalainen, I.; Moore, I. D.; Kron, T.; Raeder, S.; Sonnenschein, V.; Tomita, H.; Trautmann, N.; Voss, A.; Wendt, K.

2016-06-01

In-gas-cell resonance laser ionization has been performed on long-lived isotopes of Pu at the IGISOL facility, Jyväskylä. This initiates a new programme of research towards high-resolution optical spectroscopy of heavy actinide elements which can be produced in sufficient quantities at research reactors and transported to facilities elsewhere. In this work a new gas cell has been constructed for fast extraction of laser-ionized elements. Samples of 238-240,242Pu and 244Pu have been evaporated from Ta filaments, laser ionized, mass separated and delivered to the collinear laser spectroscopy station. Here we report on the performance of the gas cell through studies of the mass spectra obtained in helium and argon, before and after the radiofrequency quadrupole cooler-buncher. This provides valuable insight into the gas phase chemistry exhibited by Pu, which has been additionally supported by measurements of ion time profiles. The resulting monoatomic yields are sufficient for collinear laser spectroscopy. A gamma-ray spectroscopic analysis of the Pu samples shows a good agreement with the assay provided by the Mainz Nuclear Chemistry department.

The Energetic Trans-Iron Nuclei Experiment (ENTICE)

NASA Technical Reports Server (NTRS)

Binns, W. R.; Israel, M. H.; Cummings, A. C.; Labrador, A. W.; Mewaldt, R. A.; Leske, R. A.; Stone, E. C.; Wiedenbeck, M. E.; Christian, E. R.; Denolfo, G. A.;

Determination of actinides in urine and fecal samples

DOEpatents

McKibbin, Terry T.

1993-01-01

A method of determining the radioactivity of specific actinides that are carried in urine or fecal sample material is disclosed. The samples are ashed in a muffle furnace, dissolved in an acid, and then treated in a series of steps of reduction, oxidation, dissolution, and precipitation, including a unique step of passing a solution through a chloride form anion exchange resin for separation of uranium and plutonium from americium.

Determination of actinides in urine and fecal samples

DOEpatents

McKibbin, T.T.

1993-03-02

A method of determining the radioactivity of specific actinides that are carried in urine or fecal sample material is disclosed. The samples are ashed in a muffle furnace, dissolved in an acid, and then treated in a series of steps of reduction, oxidation, dissolution, and precipitation, including a unique step of passing a solution through a chloride form anion exchange resin for separation of uranium and plutonium from americium.

Conjugates of magnetic nanoparticle-actinide specific chelator for radioactive waste separation.

PubMed

Kaur, Maninder; Zhang, Huijin; Martin, Leigh; Todd, Terry; Qiang, You

2013-01-01

A novel nanotechnology for the separation of radioactive waste that uses magnetic nanoparticles (MNPs) conjugated with actinide specific chelators (MNP-Che) is reviewed with a focus on design and process development. The MNP-Che separation process is an effective way of separating heat generating minor actinides (Np, Am, Cm) from spent nuclear fuel solution to reduce the radiological hazard. It utilizes coated MNPs to selectively adsorb the contaminants onto their surfaces, after which the loaded particles are collected using a magnetic field. The MNP-Che conjugates can be recycled by stripping contaminates into a separate, smaller volume of solution, and then become the final waste form for disposal after reusing number of times. Due to the highly selective chelators, this remediation method could be both simple and versatile while allowing the valuable actinides to be recovered and recycled. Key issues standing in the way of large-scale application are stability of the conjugates and their dispersion in solution to maintain their unique properties, especially large surface area, of MNPs. With substantial research progress made on MNPs and their surface functionalization, as well as development of environmentally benign chelators, this method could become very flexible and cost-effective for recycling used fuel. Finally, the development of this nanotechnology is summarized and its future direction is discussed.

Can-AMS: The New Accelerator Mass Spectrometry Facility At The University Of Ottawa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kieser, W. E.; Zhao, X.-L.; Clark, I. D.

2011-06-01

The Canadian Centre for Accelerator Mass Spectrometry (AMS) at the University of Ottawa will be equipped with a new, 3 MV tandem accelerator with peripheral equipment for the analysis of elements ranging from tritium to the actinides. This facility, along with a wide array of support instrumentation recently funded by the Canada Foundation for Innovation, will be located in a new science building on the downtown campus of the University of Ottawa. In addition to providing the standard AMS measurements on {sup 14}C, {sup 10}Be, {sup 26}Al, {sup 36}Cl and {sup 129}I for earth, environmental, cultural and biomedical sciences, thismore » facility will incorporate the new technologies of anion isobar separation at low energies using RFQ chemical reaction cells for {sup 36}Cl and new heavy element applications, integrated sample combustion and gas ion source for biomedical and environmental {sup 14}C analysis and the use of novel target matrices for expanding the range of applicable elements and simplifying sample preparation, all currently being developed at IsoTrace. This paper will outline the design goals for the new facility, present some details of the new AMS technologies, in particular the Isobar Separator for Anions and discuss the design of the AMS system resulting from these requirements.« less

Spectral analysis of rare earth elements using laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Martin, Madhavi Z.; Fox, Robert V.; Miziolek, Andrzej W.; DeLucia, Frank C.; André, Nicolas

2015-06-01

There is growing interest in rapid analysis of rare earth elements (REEs) both due to the need to find new natural sources to satisfy increased demand in their use in various electronic devices, as well as the fact that they are used to estimate actinide masses for nuclear safeguards and nonproliferation. Laser-Induced Breakdown Spectroscopy (LIBS) appears to be a particularly well-suited spectroscopy-based technology to rapidly and accurately analyze the REEs in various matrices at low concentration levels (parts-per-million). Although LIBS spectra of REEs have been reported for a number of years, further work is still necessary in order to be able to quantify the concentrations of various REEs in realworld complex samples. LIBS offers advantages over conventional solution-based radiochemistry in terms of cost, analytical turnaround, waste generation, personnel dose, and contamination risk. Rare earth elements of commercial interest are found in the following three matrix groups: 1) raw ores and unrefined materials, 2) as components in refined products such as magnets, lighting phosphors, consumer electronics (which are mostly magnets and phosphors), catalysts, batteries, etc., and 3) waste/recyclable materials (aka e-waste). LIBS spectra for REEs such as Gd, Nd, and Sm found in rare earth magnets are presented.

Spectral Analysis of Rare Earth Elements using Laser-Induced Breakdown Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martin, Madhavi Z; Fox, Dr. Richard V; Miziolek, Andrzej W

2015-01-01

There is growing interest in rapid analysis of rare earth elements (REEs) both due to the need to find new natural sources to satisfy increased demand in their use in various electronic devices, as well as the fact that they are used to estimate actinide masses for nuclear safeguards and nonproliferation. Laser-Induced Breakdown Spectroscopy (LIBS) appears to be a particularly well-suited spectroscopy-based technology to rapidly and accurately analyze the REEs in various matrices at low concentration levels (parts-per-million). Although LIBS spectra of REEs have been reported for a number of years, further work is still necessary in order to bemore » able to quantify the concentrations of various REEs in real-world complex samples. LIBS offers advantages over conventional solution-based radiochemistry in terms of cost, analytical turnaround, waste generation, personnel dose, and contamination risk. Rare earth elements of commercial interest are found in the following three matrix groups: 1) raw ores and unrefined materials, 2) as components in refined products such as magnets, lighting phosphors, consumer electronics (which are mostly magnets and phosphors), catalysts, batteries, etc., and 3) waste/recyclable materials (aka e-waste). LIBS spectra for REEs such as Gd, Nd, and Sm found in rare earth magnets are presented.« less

Spectral Analysis of Rare Earth Elements using Laser-Induced Breakdown Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martin, Madhavi Z; Fox, Dr. Richard V; Miziolek, Andrzej W

2015-01-01

There is growing interest in rapid analysis of rare earth elements (REEs) both due to the need to find new natural sources to satisfy increased demand in their use in various electronic devices, as well as the fact that they are used to estimate actinide masses for nuclear safeguards and nonproliferation. Laser-Induced Breakdown Spectroscopy (LIBS) appears to be a particularly well-suited spectroscopy-based technology to rapidly and accurately analyze the REEs in various matrices at low concentration levels (parts-per-million). Although LIBS spectra of REEs have been reported for a number of years, further work is still necessary in order to bemore » able to quantify the concentrations of various REEs in realworld complex samples. LIBS offers advantages over conventional solution-based radiochemistry in terms of cost, analytical turnaround, waste generation, personnel dose, and contamination risk. Rare earth elements of commercial interest are found in the following three matrix groups: 1) raw ores and unrefined materials, 2) as components in refined products such as magnets, lighting phosphors, consumer electronics (which are mostly magnets and phosphors), catalysts, batteries, etc., and 3) waste/recyclable materials (aka e-waste). LIBS spectra for REEs such as Gd, Nd, and Sm found in rare earth magnets are presented.« less

Spectral Analysis of Rare Earth Elements using Laser-Induced Breakdown Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Madhavi Z. Martin; Robert V. Fox; Andrzej W. Miziolek

2001-05-01

There is growing interest in rapid analysis of rare earth elements (REEs) both due to the need to find new natural sources to satisfy increased demand in their use in various electronic devices, as well as the fact that they are used to estimate actinide masses for nuclear safeguards and nonproliferation. Laser-Induced Breakdown Spectroscopy (LIBS) appears to be a particularly well-suited spectroscopy-based technology to rapidly and accurately analyze the REEs in various matrices at low concentration levels (parts-per-million). Although LIBS spectra of REEs have been reported for a number of years, further work is still necessary in order to bemore » able to quantify the concentrations of various REEs in realworld complex samples. LIBS offers advantages over conventional solution-based radiochemistry in terms of cost, analytical turnaround, waste generation, personnel dose, and contamination risk. Rare earth elements of commercial interest are found in the following three matrix groups: 1) raw ores and unrefined materials, 2) as components in refined products such as magnets, lighting phosphors, consumer electronics (which are mostly magnets and phosphors), catalysts, batteries, etc., and 3) waste/recyclable materials (aka e-waste). LIBS spectra for REEs such as Gd, Nd, and Sm found in rare earth magnets are presented.« less

Report on Initial Direct Soil Leaching Experiments Using Post-Detonation Debris

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gostic, R.; Knight, K. B.; Borg, L.

2011-08-01

A key challenge of nuclear forensics is reducing the time and manpower effort required to measure nuclear debris compositions. The overall motivation for this work is to explore development of a robust, automated system that can be used to concurrently analyze several elements/isotopes associated with the forensic signature of nuclear materials. The primary focus of this research has been to methodically investigate if rapid partial leaching of post-detonation debris can yield usable elemental and isotopic information for interpretation. The unique requirements of post-detonation nuclear forensics have not been fully adapted to or fully incorporated contemporary chemical separation techniques. Challenges includemore » addressing the range of material matrices or mixed fission product and actinide compositions and concentrations that might be encountered. These include, but are not limited to, puddle melt glass, urban debris, seawater, air filters, iron-rich urban debris, asphalt, and silica sand. Separation of these elements and their subsequent measurement is a key element of related laboratory analysis activity. Existing practices at LLNL rely on proven but time-consuming and labor intensive processes. Significant time and labor savings are possible in chemical separations, however, if rapid processing methods can be adapted to post-detonation debris. Development of a simple and reliable leaching technique could shorten analytical times and would be useful as a field deployable method for the preliminary characterization of actinide isotopic ratios in soils. Measurement of isotopic ratios in the field using modern mass spectrometry capabilities such as Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is desirable, taking advantage of the extended range of isotopic systems measureable using such instruments. Sample introduction to these types of mass spectrometry instruments requires partial leaching or full dissolution of a sample to remove isobaric (same mass) interferences, and, in some cases, to concentrate the elements(s) of interest. To develop a field-deployable mass spectrometry capability, therefore, automated and robust leaching of likely debris samples (ranging from silicates and oxides to metals and urban materials such as concrete and asphalt), followed by separation/purification through cation exchange column chemistry is necessary. In a post-detonation environment, analysis of melt glasses via rapid leaching and ICP-MS could be a viable route to the same goal. This report presents initial leaching experiments on ‘uncontaminated’ soils, as well as data from melt glass from a single nuclear weapons test. Samples were characterized by gamma spectrometry, then aliquoted for rapid leaching experiments. Experiments were conducted using two different rapid acid treatments to leach the soils. Following leaching, the leachate solutions were analyzed by ICP-MS to determine if U isotopic composition. We present these data to address the question as to whether or not rapid (~1 hr) leaching techniques have the potential to yield meaningful U isotopic compositions, without the need for a complete (time consuming) sample dissolution and separation.« less

β4 systematics in rare-earth and actinide nuclei: sdg interacting boson model description

NASA Astrophysics Data System (ADS)

Devi, Y. D.; Kota, V. K. B.

1992-07-01

The observed variation of hexadecupole deformation parameter β4 with mass number A in rare-earth and actinide nuclei is studied in the sdg interacting boson model (IBM) using single j-shell Otsuka-Arima-Iachello mapped and IBM-2 to IBM-1 projected hexadecupole transition operator together with SUsdg(3) and SUsdg(5) coherent states. The SUsdg(3) limit is found to provide a good description of data.

A calculation for radial expectation values of helium like actinide ions (Z=89-93)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ürer, G., E-mail: gurer@sakarya.edu.tr; Arslan, M., E-mail: murat.arslan4@ogr.sakarya.edu.tr; Balkaya, E., E-mail: eda.balkaya@ogr.sakarya.edu.tr

2016-03-25

Radial expectation values, , for helium like actinides (Z{sub Ac}=89, Z{sub Th}=90, Z{sub Pa}=91, Z{sub U}=92, and Z{sub Np}=93) are reported using the Multiconfiguration Hartree-Fock (MCHF) within the framework Breit-Pauli corrections. Atomic data as energy levels, wavelengths, weighted oscillator strengths, and transition probabilities for allowed and forbidden transitions need these calculations. The obtained results are compared available works.

Actinide halide complexes

DOEpatents

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

1992-01-01

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

Superabsorbing gel for actinide, lanthanide, and fission product decontamination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaminski, Michael D.; Mertz, Carol J.

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

Octupole deformation in neutron-rich actinides and superheavy nuclei and the role of nodal structure of single-particle wavefunctions in extremely deformed structures of light nuclei

NASA Astrophysics Data System (ADS)

Afanasjev, A. V.; Abusara, H.; Agbemava, S. E.

2018-03-01

Octupole deformed shapes in neutron-rich actinides and superheavy nuclei as well as extremely deformed shapes of the N∼ Z light nuclei have been investigated within the framework of covariant density functional theory. We confirmed the presence of new region of octupole deformation in neutron-rich actinides with the center around Z∼ 96,N∼ 196 but our calculations do not predict octupole deformation in the ground states of superheavy Z≥slant 108 nuclei. As exemplified by the study of 36Ar, the nodal structure of the wavefunction of occupied single-particle orbitals in extremely deformed structures allows to understand the formation of the α-clusters in very light nuclei, the suppression of the α-clusterization with the increase of mass number, the formation of ellipsoidal mean-field type structures and nuclear molecules.

Fission barriers from multidimensionally-constrained covariant density functional theories

NASA Astrophysics Data System (ADS)

Lu, Bing-Nan; Zhao, Jie; Zhao, En-Guang; Zhou, Shan-Gui

2017-11-01

In recent years, we have developed the multidimensionally-constrained covariant density functional theories (MDC-CDFTs) in which both axial and spatial reflection symmetries are broken and all shape degrees of freedom described by βλμ with even μ, such as β20, β22, β30, β32, β40, etc., are included self-consistently. The MDC-CDFTs have been applied to the investigation of potential energy surfaces and fission barriers of actinide nuclei, third minima in potential energy surfaces of light actinides, shapes and potential energy surfaces of superheavy nuclei, octupole correlations between multiple chiral doublet bands in 78Br, octupole correlations in Ba isotopes, the Y32 correlations in N = 150 isotones and Zr isotopes, the spontaneous fission of Fm isotopes, and shapes of hypernuclei. In this contribution we present the formalism of MDC-CDFTs and the application of these theories to the study of fission barriers and potential energy surfaces of actinide nuclei.

Actinide halide complexes

DOEpatents

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

1992-11-24

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

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

PubMed

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

2016-04-28

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

Thermodynamic constants for actinide oxides and oxyhydroxides relevant to actinide volatility calculations for thermal oxidation processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ebbinghaus, B.B.; Krikorian, O.H.

The purpose of this report is to provide input of thermodynamic data on actinide volatilities to EERC for use in their computer code for modeling of metal volatilities in incinerators. It is also anticipated that the data may be documented later in an EPA sponsored ``Metals Bible.`` It should be noted that only upper limits for the volatility of PuO{sub 2}(s) due to PuO{sub 3}(g) and PuO{sub 2}(OH){sub 2}(g) and the volatility of AmO{sub 2} in PuO{sub 2}(s) due to AmO{sub 3}(g) and AmO{sub 2}(OH){sub 2}(g) could be set. The data on the americium vapor species are intended for calculationsmore » where AmO{sub 2} is present as a solid solution in PuO{sub 2}(s).« less

Prediction of trivalent actinide amino(poly)carboxylate complex stability constants using linear free energy relationships with the lanthanide series

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uhnak, Nic E.

Prediction of Trivalent Actinide Amino(poly)carboxylate Complex Stability Constants Using Linear Free Energy Relationships with the Lanthanide Series Alternative title: LFER Based Prediction of An(III) APC Stability Constants There is a gap in the literature regarding the complexation of amino(poly)carboxylate (APC) ligands with trivalent actinides (An(III))). The chemistry of the An(III) is nearly identical to that of the trivalent lanthanides Lns, but the An(III) express a slight enhancement when binding APC ligands. Presented in this report is a simple method of predicting the stability constants of the An(III), Pu, Am, Cm, Bk and Cf by using linear free energy relationships (LFER)more » of the An and the lanthanide (Ln) series for 91 APCs. This method produced An stability constants within uncertainty to available literature values for most ligands.« less

Imaging the Formation of High-Energy Dispersion Anomalies in the Actinide UCoGa5

NASA Astrophysics Data System (ADS)

Das, Tanmoy; Durakiewicz, Tomasz; Zhu, Jian-Xin; Joyce, John J.; Sarrao, John L.; Graf, Matthias J.

2012-10-01

We use angle-resolved photoemission spectroscopy to image the emergence of substantial dispersion and spectral-weight anomalies in the electronic renormalization of the actinide compound UCoGa5 that was presumed to belong to a conventional Fermi-liquid family. Kinks or abrupt breaks in the slope of the quasiparticle dispersion are detected both at low (approximately 130 meV) and high (approximately 1 eV) binding energies below the Fermi energy, ruling out any significant contribution of phonons. We perform numerical calculations to demonstrate that the anomalies are adequately described by coupling between itinerant fermions and spin fluctuations arising from the particle-hole continuum of the spin-orbit-split 5f states of uranium. These anomalies resemble the “waterfall” phenomenon of the high-temperature copper-oxide superconductors, suggesting that spin fluctuations are a generic route toward multiform electronic phases in correlated materials as different as high-temperature superconductors and actinides.

A new incorporation mechanism for trivalent actinides into bioapatite: a TRLFS and EXAFS study.

PubMed

Holliday, Kiel; Handley-Sidhu, Stephanie; Dardenne, Kathy; Renshaw, Joanna; Macaskie, Lynne; Walther, Clemens; Stumpf, Thorsten

2012-02-28

One of the most toxic byproducts of nuclear power and weapons production is the transuranics, which have a high radiotoxicity and long biological half-life due to their tendency to accumulate in the skeletal system. This accumulation is inhomogeneous and has been associated with the chemical properties and structure of the bone material rather than its location or function. This suggests a chemical driving force to incorporation and requires an atomic scale mechanistic understanding of the incorporation process. Here we propose a new incorporation mechanism for trivalent actinides and lanthanides into synthetic and biologically produced hydroxyapatite. Time-resolved laser fluorescence spectroscopy and extended X-ray absorption fine structure have been used to demonstrate that trivalent actinides and lanthanides incorporate into the amorphous grain boundaries of apatite. This incorporation site can be used to explain patterns in uptake and distribution of radionuclides in the mammalian skeletal system. © 2012 American Chemical Society

Actinide abundances in ordinary chondrites

NASA Technical Reports Server (NTRS)

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

1990-01-01

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

Radionuclide Transport in Fracture-Granite Interface Zones

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Q; Mori, A

In situ radionuclide migration experiments, followed by excavation and sample characterization, were conducted in a water-conducting shear zone at the Grimsel Test Site (GTS) in Switzerland to study diffusion paths of radionuclides in fractured granite. In this work, we employed a micro-scale mapping technique that interfaces laser ablation sampling with inductively coupled plasma-mass spectrometry (LA/ICP-MS) to measure the fine-scale (micron-range) distribution of actinides ({sup 234}U, {sup 235}U, and {sup 237}Np) in the fracture-granite interface zones. Long-lived {sup 234}U, {sup 235}U, and {sup 237}Np were detected in flow channels, as well as in the adjacent rock matrix, using the sensitive, feature-basedmore » mapping of the LA/ICP-MS technique. The injected sorbing actinides are mainly located within the advective flowing fractures and the immediately adjacent regions. The water-conducting fracture studied in this work is bounded on one side by mylonite and the other by granitic matrix regions. These actinides did not penetrate into the mylonite side as much as the relatively higher-porosity granite matrix, most likely due to the low porosity, hydraulic conductivity, and diffusivity of the fracture wall (a thickness of about 0.4 mm separates the mylonite region from the fracture) and the mylonite region itself. Overall, the maximum penetration depth detected with this technique for the more diffusive {sup 237}Np over the field experimental time scale of about 60 days was about 10 mm in the granitic matrix, illustrating the importance of matrix diffusion in retarding radionuclide transport from the advective fractures. Laboratory tests and numerical modeling of radionuclide diffusion into granitic matrix was conducted to complement and help interpret the field results. Measured apparent diffusivity of multiple tracers in granite provided consistent predictions for radionuclide transport in the fractured granitic rock.« less

Solution thermodynamic stability of complexes formed with the octadentate hydroxypyridinonate ligand 3,4,3-LI(1,2-HOPO): A critical feature for efficient chelation of lanthanide(IV) and actinide(IV) ions

PubMed Central

Deblonde, Gauthier J-P.; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J.

2013-01-01

The solution thermodynamics of water soluble complexes formed between Ce(III), Ce(IV), Th(IV) and the octadentate chelating agent 3,4,3-LI(1,2-HOPO) were investigated. Several techniques including spectrofluorimetric and automated spectrophotometric titrations were used to overcome the slow spontaneous oxidation of Ce(III) complexes yielding to stability constants of log β110 = 17.4 ± 0.5, log β11-1 = 8.3 ± 0.4 and log β111 = 21.2 ± 0.4 for [Ce(III)(3,4,3-LI(1,2-HOPO))]−, [Ce(III)(3,4,3-LI(1,2-HOPO)(OH)]2− and [Ce(III)(3,4,3-LI(1,2-HOPO)H], respectively. Using the spectral properties of the hydroxypyridinonate chelator in ligand competition titrations against nitrilotriacetic acid, the stability constant log β110 = 41.5 ± 0.5 was determined for [Ce(IV)(3,4,3-LI(1,2-HOPO))]. Finally, the extraordinarily stable complex [Ce(IV)(3,4,3-LI(1,2-HOPO))] was used in Th(IV) competition titrations, resulting in a stability constant of log β110 = 40.1 ± 0.5 for [Th(IV)3,4,3-LI(1,2-HOPO))]. These experimental values are in excellent agreement with previous estimates, they are discussed with respect to the ionic radius and oxidation state of each cationic metal and allow predictions on the stability of other actinide complexes including [U(IV)(3,4,3-LI(1,2-HOPO))], [Np(IV)(3,4,3-LI(1,2-HOPO))] and [Pu(IV)(3,4,3-LI(1,2-HOPO))]. Comparisons with the standard ligand diethylenetriamine pentaacetic acid (DTPA) provide a thermodynamic basis for the observed significantly higher efficacy of 3,4,3-LI(1,2-HOPO) as an in vivo actinide decorporation agent. PMID:23855806

Plant Mounds as Concentration and Stabilization Agents for Actinide Soil Contaminants in Nevada

DOE Office of Scientific and Technical Information (OSTI.GOV)

D.S. Shafer; J. Gommes

Plant mounds or blow-sand mounds are accumulations of soil particles and plant debris around the base of shrubs and are common features in deserts in the southwestern United States. An important factor in their formation is that shrubs create surface roughness that causes wind-suspended particles to be deposited and resist further suspension. Shrub mounds occur in some plant communities on the Nevada Test Site, the Nevada Test and Training Range (NTTR), and Tonopah Test Range (TTR), including areas of surface soil contamination from past nuclear testing. In the 1970s as part of early studies to understand properties of actinides inmore » the environment, the Nevada Applied Ecology Group (NAEG) examined the accumulation of isotopes of Pu, 241Am, and U in plant mounds at safety experiment and storage-transportation test sites of nuclear devices. Although aerial concentrations of these contaminants were highest in the intershrub or desert pavement areas, the concentration in mounds were higher than in equal volumes of intershrub or desert pavement soil. The NAEG studies found the ratio of contaminant concentration of actinides in soil to be greater (1.6 to 2.0) in shrub mounds than in the surrounding areas of desert pavement. At Project 57 on the NTTR, 17 percent of the area was covered in mounds while at Clean Slate III on the TTR, 32 percent of the area was covered in mounds. If equivalent volumes of contaminated soil were compared between mounds and desert pavement areas at these sites, then the former might contain as much as 34 and 62 percent of the contaminant inventory, respectively. Not accounting for radionuclides associated with shrub mounds would cause the inventory of contaminants and potential exposure to be underestimated. In addition, preservation of shrub mounds could be important part of long-term stewardship if these sites are closed by fencing and posting with administrative controls.« less

Ion binding compounds, radionuclide complexes, methods of making radionuclide complexes, methods of extracting radionuclides, and methods of delivering radionuclides to target locations

DOEpatents

Chen, Xiaoyuan; Wai, Chien M.; Fisher, Darrell R.

2000-01-01

The invention pertains to compounds for binding lanthanide ions and actinide ions. The invention further pertains to compounds for binding radionuclides, and to methods of making radionuclide complexes. Also, the invention pertains to methods of extracting radionuclides. Additionally, the invention pertains to methods of delivering radionuclides to target locations. In one aspect, the invention includes a compound comprising: a) a calix[n]arene group, wherein n is an integer greater than 3, the calix[n]arene group comprising an upper rim and a lower rim; b) at least one ionizable group attached to the lower rim; and c) an ion selected from the group consisting of lanthanide and actinide elements bound to the ionizable group. In another aspect, the invention includes a method of extracting a radionuclide, comprising: a) providing a sample comprising a radionuclide; b) providing a calix[n]arene compound in contact with the sample, wherein n is an integer greater than 3; and c) extracting radionuclide from the sample into the calix[n]arene compound. In yet another aspect, the invention includes a method of delivering a radionuclide to a target location, comprising: a) providing a calix[n]arene compound, wherein n is an integer greater than 3, the calix[n]arene compound comprising at least one ionizable group; b) providing a radionuclide bound to the calix[n]arene compound; and c) providing an antibody attached to the calix[n]arene compound, the antibody being specific for a material found at the target location.

Improved thermodynamic model for interaction of EDTA with trivalent actinides and lanthanide to ionic strength of 6.60 m

NASA Astrophysics Data System (ADS)

Thakur, Punam; Xiong, Yongliang; Borkowski, Marian; Choppin, Gregory R.

2014-05-01

The dissociation constants of ethylenediaminetetraacetic acid (H4EDTA), and the stability constants of Am3+, Cm3+and Eu3+ with EDTA4- have been determined at 25 °C, over a range of concentration varying from 0.1 to 6.60 m NaClO4 using potentiometric titration and an extraction technique, respectively. The formation of only 1:1 complex, M(EDTA)-, where (M = Am3+, Cm3+ and Eu3+), was observed under the experimental conditions. The observed ionic strength dependencies of the dissociation constants and the stability constants have been described successfully over the entire ionic strength range using the Pitzer model. The thermodynamic stability constant: logβ1010=20.55±0.18 for Am3+, logβ1010=20.43±0.20 for Cm3+ and logβ1010=20.65±0.19 for Eu3+ were calculated by extrapolation of data to zero ionic strength in an NaClO4 medium. In addition, logβ1010 of 20.05 ± 0.40 for Am3+ was obtained by simultaneously modeling data both in NaCl and NaClO4 media. For all stability constants, the Pitzer model gives an excellent representation of the data using interaction parameters β(0), β(1), and Cϕ determined in this work. The improved model presented in this work would enable researchers to model accurately the potential mobility of actinides (III) and light rare earth elements to ionic strength of 6.60 m in low temperature environments in the presence of EDTA.

Predicting the optical observables for nucleon scattering on even-even actinides

NASA Astrophysics Data System (ADS)

Martyanov, D. S.; Soukhovitskiĩ, E. Sh.; Capote, R.; Quesada, J. M.; Chiba, S.

2017-09-01

The previously derived Lane consistent dispersive coupled-channel optical model for nucleon scattering on 232Th and 238U nuclei is extended to describe scattering on even-even actinides with Z = 90-98. A soft-rotator-model (SRM) description of the low-lying nuclear structure is used, where the SRM Hamiltonian parameters are adjusted to the observed collective levels of the target nucleus. SRM nuclear wave functions (mixed in K quantum number) have been used to calculate the coupling matrix elements of the generalized optical model. The “effective” deformations that define inter-band couplings are derived from the SRM Hamiltonian parameters. Conservation of nuclear volume is enforced by introducing a dynamic monopolar term to the deformed potential, leading to additional couplings between rotational bands. The fitted static deformation parameters are in very good agreement with those derived by Wang and collaborators using the Weizsäcker-Skyrme global mass model (WS4), allowing use of the latter to predict cross sections for nuclei without experimental data. A good description of the scarce “optical” experimental database is achieved. SRM couplings and volume conservation allow a precise calculation of the compound-nucleus formation cross sections, which is significantly different from that calculated with rigid-rotor potentials coupling the ground-state rotational band. The derived parameters can be used to describe both neutron- and proton-induced reactions. Supported by International Atomic Energy Agency, through the IAEA Research Contract 19263, by the Spanish Ministry of Economy and Competitivity under Contracts FPA2014-53290-C2-2-P and FPA2016-77689-C2-1-R.

Atlas of Atomic Spectral Lines of Neptunium Emitted by Inductively Coupled Plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeKalb, E.L. and Edelson, M. C.

1987-08-01

Optical emission spectra from high-purity Np-237 were generated with a glovebox-enclosed inductively coupled plasma (ICP) source. Spectra covering the 230-700 nm wavelength range are presented along with general commentary on the methodology used in collecting the data. The Ames Laboratory Nuclear Safeguards and Security Program has been charged with the task of developing optical spectroscopic methods to analyze the composition of spent nuclear fuels. Such materials are highly radioactive even after prolonged 'cooling' and are chemically complex. Neptunium (Np) is a highly toxic by-product of nuclear power generation and is found, in low abundance, in spent nuclear fuels. This atlasmore » of the optical emission spectrum of Np, as produced by an inductively coupled plasma (ICP) spectroscopic source, is part of a general survey of the ICP emission spectra of the actinide elements. The ICP emission spectrum of the actinides originates almost exclusively from the electronic relaxation of excited, singly ionized species. Spectral data on the Np ion emission spectrum (i.e., the Np II spectrum) have been reported by Tomkins and Fred [1] and Haaland [2]. Tomkins and Fred excited the Np II spectrum with a Cu spark discharge and identified 114 Np lines in the 265.5 - 436.3 nm spectral range. Haaland, who corrected some spectral line misidentifications in the work of Tomkins and Fred, utilized an enclosed Au spark discharge to excite the Np II spectrum and reported 203 Np lines within the 265.4 - 461.0 nm wavelength range.« less

Structure and thermodynamics of uranium-containing iron garnets

NASA Astrophysics Data System (ADS)

Guo, Xiaofeng; Navrotsky, Alexandra; Kukkadapu, Ravi K.; Engelhard, Mark H.; Lanzirotti, Antonio; Newville, Matthew; Ilton, Eugene S.; Sutton, Stephen R.; Xu, Hongwu

2016-09-01

Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca3UxZr2-xFe3O12 (x = 0.5-0.7), along with the endmember phase, Ca3(Zr2)SiFe3+2O12, for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in the phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe3+. U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Our structural and thermodynamic analysis further provides explanation for the formation of natural uranium garnet, elbrusite-(Zr), and supports the potential use of Ca3UxZr2-xFe3O12 as viable waste form phases for U and other actinides.

Comparison of the Chernobyl and Fukushima nuclear accidents: a review of the environmental impacts.

PubMed

Steinhauser, Georg; Brandl, Alexander; Johnson, Thomas E

2014-02-01

The environmental impacts of the nuclear accidents of Chernobyl and Fukushima are compared. In almost every respect, the consequences of the Chernobyl accident clearly exceeded those of the Fukushima accident. In both accidents, most of the radioactivity released was due to volatile radionuclides (noble gases, iodine, cesium, tellurium). However, the amount of refractory elements (including actinides) emitted in the course of the Chernobyl accident was approximately four orders of magnitude higher than during the Fukushima accident. For Chernobyl, a total release of 5,300 PBq (excluding noble gases) has been established as the most cited source term. For Fukushima, we estimated a total source term of 520 (340-800) PBq. In the course of the Fukushima accident, the majority of the radionuclides (more than 80%) was transported offshore and deposited in the Pacific Ocean. Monitoring campaigns after both accidents reveal that the environmental impact of the Chernobyl accident was much greater than of the Fukushima accident. Both the highly contaminated areas and the evacuated areas are smaller around Fukushima and the projected health effects in Japan are significantly lower than after the Chernobyl accident. This is mainly due to the fact that food safety campaigns and evacuations worked quickly and efficiently after the Fukushima accident. In contrast to Chernobyl, no fatalities due to acute radiation effects occurred in Fukushima. © 2013.

New Synthetic Methods and Structure-Property Relationships in Neptunium, Plutonium, and Americium Borates. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Albrecht-Schmitt, Thomas Edward

The past three years of support by the Heavy Elements Chemistry Program have been highly productive in terms of advanced degrees awarded, currently supported graduate students, peer-reviewed publications, and presentations made at universities, national laboratories, and at international conferences. Ph.D. degrees were granted to Shuao Wang and Juan Diwu, who both went on to post-doctoral appointments at the Glenn T. Seaborg Center at Lawrence Berkeley National Laboratory with Jeff Long and Ken Raymond, respectively. Pius Adelani completed his Ph.D. with me and is now a post-doc with Peter C. Burns. Andrea Alsobrook finished her Ph.D. and is now a post-docmore » at Savannah River with Dave Hobbs. Anna Nelson completed her Ph.D. and is now a post-doc with Rod Ewing at the University of Michigan. As can be gleaned from this list, students supported by the Heavy Elements Chemistry grant have remained interested in actinide science after leaving my program. This follows in line with previous graduates in this program such as Richard E. Sykora, who did his post-doctoral work at Oak Ridge National Laboratory with R. G. Haire, and Amanda C. Bean, who is a staff scientist at Los Alamos National Laboratory, and Philip M. Almond and Thomas C. Shehee, who are both staff scientists at Savannah River National Laboratory, Gengbang Jin who is a staff scientist at Argonne National Lab, and Travis Bray who has been a post-doc at both LBNL and ANL. Clearly this program is serving as a pipe-line for students to enter into careers in the national laboratories. About half of my students depart the DOE complex for academia or industry. My undergraduate researchers also remain active in actinide chemistry after leaving my group. Dan Wells was a productive undergraduate of mine, and went on to pursue a Ph.D. on uranium and neptunium chalcogenides with Jim Ibers at Northwestern. After earning his Ph.D., he went directly into the nuclear industry.« less

Interplay between Diffusion, Accretion and Nuclear Reactions in the Atmospheres of Sirius and Przybylski's Star

NASA Astrophysics Data System (ADS)

Yushchenko, A.; Gopka, V.; Goriely, S.; Lambert, D.; Shavrina, A.; Kang, Y. W.; Rostopchin, S.; Valyavin, G.; Lee, B.-C.; Kim, C.

2007-06-01

The abundance anomalies in chemically peculiar B-F stars are usually explained by diffusion of chemical elements in the stable atmospheres of these stars. But it is well known that peculiar stars with similar temperatures and gravities show very different chemical compositions. We show that the abundance patterns of several stars can be influenced by accretion and (or) nuclear reactions in stellar atmospheres. The first case is one of the hottest Am stars - Sirius. We determined the abundances of more than 50 chemical elements in the atmosphere of Sirius A and show that Sirius A was contaminated by s-process enriched matter from Sirius B (now a white dwarf). The second case is the well known Przybylski's star. The abundance pattern of this star is the second most studied one after the Sun with abundances determined for about 60 chemical elements. Spectral lines of radioactive elements with short decay times were found in the spectrum of this star. We report the results of our investigation on the stratification of chemical elements in the atmosphere of Przybylski's star and the new identification of lines corresponding to short-lived actinides in its spectrum. Possible explanations of the abundances pattern of Przybylski's star (as well as HR465 and HD965) can be the natural radioactive decays of thorium and uranium, the explosion of a companion as a supernova or the spallation reactions. These three hypotheses and (or) diffusion can possibly explain the abundance pattern of Przybylski's star and several similar objects such as HR465 and HD965.

Chemical resolution of Pu+ from U+ and Am+ using a band-pass reaction cell inductively coupled plasma mass spectrometer.

PubMed

Tanner, Scott D; Li, Chunsheng; Vais, Vladimir; Baranov, Vladimir I; Bandura, Dmitry R

2004-06-01

Determination of the concentration and distribution of the Pu and Am isotopes is hindered by the isobaric overlaps between the elements themselves and U, generally requiring time-consuming chemical separation of the elements. A method is described in which chemical resolution of the elemental ions is obtained through ion-molecule reactions in a reaction cell of an ICPMS instrument. The reactions of "natural" U(+), (242)Pu(+), and (243)Am(+) with ethylene, carbon dioxide, and nitric oxide are reported. Since the net sensitivities to the isotopes of an element are similar, chemical resolution is inferred when one isobaric element reacts rapidly with a given gas and the isobar (or in this instance surrogate isotope) is unreactive or slowly reactive. Chemical resolution of the m/z 238 isotopes of U and Pu can be obtained using ethylene as a reaction gas, but little improvement in the resolution of the m/z 239 isobars is obtained. However, high efficiency of reaction of U(+) and UH(+) with CO(2), and nonreaction of Pu(+), allows the sub-ppt determination of (239)Pu, (240)Pu, and (242)Pu (single ppt for (238)Pu) in the presence of 7 orders of magnitude excess U matrix without prior chemical separation. Similarly, oxidation of Pu(+) by NO, and nonreaction of Am(+), permit chemical resolution of the isobars of Pu and Am over 2-3 orders of magnitude relative concentration. The method provides the potential for analysis of the actinides with reduced sample matrix separation.

Real-time monitoring and control of the plasma hearth process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Power, M.A.; Carney, K.P.; Peters, G.G.

1996-05-01

A distributed monitoring and control system is proposed for a plasma hearth, which will be used to decompose hazardous organic materials, encapsulate actinide waste in an obsidian-like slag, and reduce storage volume of actinide waste. The plasma hearth will be installed at ANL-West with the assistance of SAIC. Real-time monitoring of the off-gas system is accomplished using a Sun Workstation and embedded PCs. LabWindows/CVI software serves as the graphical user interface.

Chronopotentiometry of refractory metals, actinides and oxyanions in molten salts: A review

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.

1992-01-01

The applications of chronopotentiometry to the study of electrochemical behavior of three technologically important areas of refractory metals, actinides, and oxyanions in molten salts are critically reviewed. Chronopotentiometry is a very versatile diagnostic tool to understand the reaction mechanism of the electrode processes for the electrochemical reduction/oxidation of these electroactive species in molten salt solutions. Well adherent, compact, and uniformly thick coatings of refractory metals may be electrodeposited from their solutions in molten salts.

Compact fission counter for DANCE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, C Y; Chyzh, A; Kwan, E

2010-11-06

The Detector for Advanced Neutron Capture Experiments (DANCE) consists of 160 BF{sub 2} crystals with equal solid-angle coverage. DANCE is a 4{pi} {gamma}-ray calorimeter and designed to study the neutron-capture reactions on small quantities of radioactive and rare stable nuclei. These reactions are important for the radiochemistry applications and modeling the element production in stars. The recognition of capture event is made by the summed {gamma}-ray energy which is equivalent of the reaction Q-value and unique for a given capture reaction. For a selective group of actinides, where the neutron-induced fission reaction competes favorably with the neutron capture reaction, additionalmore » signature is needed to distinguish between fission and capture {gamma} rays for the DANCE measurement. This can be accomplished by introducing a detector system to tag fission fragments and thus establish a unique signature for the fission event. Once this system is implemented, one has the opportunity to study not only the capture but also fission reactions. A parallel-plate avalanche counter (PPAC) has many advantages for the detection of heavy charged particles such as fission fragments. These include fast timing, resistance to radiation damage, and tolerance of high counting rate. A PPAC also can be tuned to be insensitive to {alpha} particles, which is important for experiments with {alpha}-emitting actinides. Therefore, a PPAC is an ideal detector for experiments requiring a fast and clean trigger for fission. A PPAC with an ingenious design was fabricated in 2006 by integrating amplifiers into the target assembly. However, this counter was proved to be unsuitable for this application because of issues related to the stability of amplifiers and the ability to separate fission fragments from {alpha}'s. Therefore, a new design is needed. A LLNL proposal to develop a new PPAC for DANCE was funded by NA22 in FY09. The design goal is to minimize the mass for the proposed counter and still be able to maintain a stable operation under extreme radioactivity and the ability to separate fission fragments from {alpha}'s. In the following sections, the description is given for the design and performance of this new compact PPAC, for studying the neutron-induced reactions on actinides using DANCE at LANL.« less

Mechanical environmental transport of actinides and ¹³⁷Cs from an arid radioactive waste disposal site.

PubMed

Snow, Mathew S; Clark, Sue B; Morrison, Samuel S; Watrous, Matthew G; Olson, John E; Snyder, Darin C

2015-10-01

Aeolian and pluvial processes represent important mechanisms for the movement of actinides and fission products at the Earth's surface. Soil samples taken in the early 1970's near a Department of Energy radioactive waste disposal site (the Subsurface Disposal Area, SDA, located in southeastern Idaho) provide a case study for studying the mechanisms and characteristics of environmental actinide and (137)Cs transport in an arid environment. Multi-component mixing models suggest actinide contamination within 2.5 km of the SDA can be described by mixing between 2 distinct SDA end members and regional nuclear weapons fallout. The absence of chemical fractionation between (241)Am and (239+240)Pu with depth for samples beyond the northeastern corner and lack of (241)Am in-growth over time (due to (241)Pu decay) suggest mechanical transport and mixing of discrete contaminated particles under arid conditions. Occasional samples northeast of the SDA (the direction of the prevailing winds) contain anomalously high concentrations of Pu with (240)Pu/(239)Pu isotopic ratios statistically identical to those in the northeastern corner. Taken together, these data suggest flooding resulted in mechanical transport of contaminated particles into the area between the SDA and a flood containment dike in the northeastern corner, following which subsequent contamination spreading in the northeastern direction resulted from wind transport of discrete particles. Copyright © 2015 Elsevier Ltd. All rights reserved.

Actinides in deer tissues at the rocky flats environmental technology site.

PubMed

Todd, Andrew S; Sattelberg, R Mark

2005-11-01

Limited hunting of deer at the future Rocky Flats National Wildlife Refuge has been proposed in U.S. Fish and Wildlife planning documents as a compatible wildlife-dependent public use. Historically, Rocky Flats site activities resulted in the contamination of surface environmental media with actinides, including isotopes of americium, plutonium, and uranium. In this study, measurements of actinides [Americium-241 (241Am); Plutonium-238 (238Pu); Plutonium-239,240 (239,240Pu); uranium-233,244 (233,234U); uranium-235,236 (235,236U); and uranium-238 (238U)] were completed on select liver, muscle, lung, bone, and kidney tissue samples harvested from resident Rocky Flats deer (N = 26) and control deer (N = 1). In total, only 17 of the more than 450 individual isotopic analyses conducted on Rocky Flats deer tissue samples measured actinide concentrations above method detection limits. Of these 17 detects, only 2 analyses, with analytical uncertainty values added, exceeded threshold values calculated around a 1 x 10(-6) risk level (isotopic americium, 0.01 pCi/g; isotopic plutonium, 0.02 pCi/g; isotopic uranium, 0.2 pCi/g). Subsequent, conservative risk calculations suggest minimal human risk associated with ingestion of these edible deer tissues. The maximum calculated risk level in this study (4.73 x 10(-6)) is at the low end of the U.S. Environmental Protection Agency's acceptable risk range.

Development of Metallic Fuels for Actinide Transmutation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayes, Steven Lowe; Fielding, Randall Sidney; Benson, Michael Timothy

Research and development activities on metallic fuels are focused on their potential use for actinide transmutation in future sodium fast reactors. As part of this application, there is also a need for a near zero-loss fabrication process and a desire to demonstrate a multifold increase in burnup potential. The incorporation of Am and Np into the traditional U-20Pu-10Zr metallic fuel alloy was demonstrated in the US during the Integral Fast Reactor Program of the 1980’s and early 1990’s. However, the conventional counter gravity injection casting method performed under vacuum, previously used to fabricate these metallic fuel alloys, was not optimizedmore » for mitigating loss of the volatile Am constituent in the casting charge; as a result, approximately 40% of the Am casting charge failed to be incorporated into the as-cast fuel alloys. Fabrication development efforts of the past few years have pursued an optimized bottom-pour casting method to increase utilization of the melted charge to near 100%, and a differential pressure casting approach, performed under an argon overpressure, has been demonstrated to result in essentially no loss of Am due to volatilization during fabrication. In short, a path toward zero-loss fabrication of metallic fuels including minor actinides has been shown to be feasible. Irradiation testing of advanced metallic fuel alloys in the Advanced Test Reactor (ATR) has been underway since 2003. Testing in the ATR is performed inside of cadmium-shrouded positions to remove >99% of the thermal flux incident on the test fuels, resulting in an epi-thermal driven fuel test that is free from gross flux depression and producing an essentially prototypic radial temperature profile inside the fuel rodlets. To date, three irradiation test series (AFC-1,2,3) have been completed. Over 20 different metallic fuel alloys have been tested to burnups as high as 30% with constituent compositions of Pu up to 30%, Am up to 12%, Np up to 10%, and Zr between 10 and 60%. In general, the performance of all of these substantially disparate metallic fuel alloys has been observed to be excellent, and their irradiation behaviors are generally consistent with historic norms for metallic fuels without minor actinide additions and having lower Pu or Zr contents. Future work is being undertaken with a view toward increasing the burnup potential of metallic fuels even more. Design innovations under investigation include: 1) lowering the fuel smear density in order to accommodate more swelling, 2) annular fuel geometry to eliminate the need for a sodium bond, 3) minor alloy additions to stabilize lanthanide fission products inside the fuel and prevent their transport to the cladding where they can participate in fuel-cladding chemical interaction (FCCI), and 4) coatings/liners on the cladding inner surface to mitigate FCCI and enable higher temperature operation. This paper will present the current state of development of metallic fuels for actinide transmutation in the US. Highlights will include recent results from metallic fuel casting experiments, experiments to identify alloy additions to immobilize lanthanide fission products, and postirradiation examinations of annular metallic fuels at low burnup.« less

The combined hybrid system: A symbiotic thermal reactor/fast reactor system for power generation and radioactive waste toxicity reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hollaway, W.R.

1991-08-01

If there is to be a next generation of nuclear power in the United States, then the four fundamental obstacles confronting nuclear power technology must be overcome: safety, cost, waste management, and proliferation resistance. The Combined Hybrid System (CHS) is proposed as a possible solution to the problems preventing a vigorous resurgence of nuclear power. The CHS combines Thermal Reactors (for operability, safety, and cost) and Integral Fast Reactors (for waste treatment and actinide burning) in a symbiotic large scale system. The CHS addresses the safety and cost issues through the use of advanced reactor designs, the waste management issuemore » through the use of actinide burning, and the proliferation resistance issue through the use of an integral fuel cycle with co-located components. There are nine major components in the Combined Hybrid System linked by nineteen nuclear material mass flow streams. A computer code, CHASM, is used to analyze the mass flow rates CHS, and the reactor support ratio (the ratio of thermal/fast reactors), IFR of the system. The primary advantages of the CHS are its essentially actinide-free high-level radioactive waste, plus improved reactor safety, uranium utilization, and widening of the option base. The primary disadvantages of the CHS are the large capacity of IFRs required (approximately one MW{sub e} IFR capacity for every three MW{sub e} Thermal Reactor) and the novel radioactive waste streams produced by the CHS. The capability of the IFR to burn pure transuranic fuel, a primary assumption of this study, has yet to be proven. The Combined Hybrid System represents an attractive option for future nuclear power development; that disposal of the essentially actinide-free radioactive waste produced by the CHS provides an excellent alternative to the disposal of intact actinide-bearing Light Water Reactor spent fuel (reducing the toxicity based lifetime of the waste from roughly 360,000 years to about 510 years).« less

Isolation and purification of protactinium-231.

PubMed

Jerome, S M; Collins, S M; Happel, S; Ivanov, P; Russell, B C

2018-04-01

Protactinium-231 is one of the lesser known actinides, yet the measurement of this radionuclide is central to dating studies in both paleoclimate and nuclear forensics measurements; furthermore, it is important as the immediate parent nuclide of the 227 Ac decay chain. In this paper, we present the preparatory work for an upcoming CCRI(II) supplementary comparison of this radionuclide. The material used in this work was of poorly known provenance, and it was necessary to carry out a chemical purification of this material prior to use. A new extraction chromatography resin, TK 400, which has been developed for the separation of 231 Pa, was tested at NPL. The aims of the work were achieved; the recovery of 231 Pa was ~85%, the decay products were recovered in good yield (~95%) and stable element impurities were removed. Copyright © 2017. Published by Elsevier Ltd.