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

Synthesis and characterisation of PuPO4 - a potential analytical standard for EPMA actinide quantification

NASA Astrophysics Data System (ADS)

Wright, K. E.; Popa, K.; Pöml, P.

2018-01-01

Transmutation nuclear fuels contain weight percentage quantities of actinide elements, including Pu, Am and Np. Because of the complex spectra presented by actinide elements using electron probe microanalysis (EPMA), it is necessary to have relatively pure actinide element standards to facilitate overlap correction and accurate quantitation. Synthesis of actinide oxide standards is complicated by their multiple oxidation states, which can result in inhomogeneous standards or standards that are not stable at atmospheric conditions. Synthesis of PuP4 results in a specimen that exhibits stable oxidation-reduction chemistry and is sufficiently homogenous to serve as an EPMA standard. This approach shows promise as a method for producing viable actinide standards for microanalysis.

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.

On the suitability of lanthanides as actinide analogs

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

Raymond, Kenneth; Szigethy, Geza

2008-07-01

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

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.

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

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

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)

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

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

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.

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.

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.

Nonaqueous method for dissolving lanthanide and actinide metals

DOEpatents

Crisler, L.R.

1975-11-11

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

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.

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.

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

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.

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.

Thermodynamic Properties of Actinides and Actinide Compounds

NASA Astrophysics Data System (ADS)

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

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

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.

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.

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.

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

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

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.

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.

Actinide targets for the synthesis of super-heavy elements

DOE PAGES

Roberto, J.; Alexander, Charles W.; Boll, Rose Ann; ...

2015-06-18

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

Mixed monofunctional extractants for trivalent actinide/lanthanide separations: TALSPEAK-MME

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

Johnson, Aaron T.; Nash, Kenneth L.

The basic features of an f-element extraction process based on a solvent composed of equimolar mixtures of Cyanex-923 (a mixed trialkyl phosphine oxide) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) extractants in n-dodecane are investigated in this report. This system, which combines features of the TRPO and TALSPEAK processes, is based on co-extraction of trivalent lanthanides and actinides from 0.1 to 1.0 M HNO 3 followed by application of a buffered aminopolycarboxylate solution strip to accomplish a Reverse TALSPEAK selective removal of actinides. This mixed-extractant medium could enable a simplified approach to selective trivalent f-element extraction and actinide partitioning in amore » single process. As compared with other combined process applications in development for more compact actinide partitioning processes (DIAMEX-SANEX, GANEX, TRUSPEAK, ALSEP), this combination features only monofunctional extractants with high solubility limits and comparatively low molar mass. Selective actinide stripping from the loaded extractant phase is done using a glycine-buffered solution containing N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) or triethylenetetramine-N,N,N',N'',N''',N'''-hexaacetic acid (TTHA). Lastly, the results reported provide evidence for simplified interactions between the two extractants and demonstrate a pathway toward using mixed monofunctional extractants to separate trivalent actinides (An) from fission product lanthanides (Ln).« less

Mixed monofunctional extractants for trivalent actinide/lanthanide separations: TALSPEAK-MME

DOE PAGES

Johnson, Aaron T.; Nash, Kenneth L.

2015-08-20

The basic features of an f-element extraction process based on a solvent composed of equimolar mixtures of Cyanex-923 (a mixed trialkyl phosphine oxide) and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) extractants in n-dodecane are investigated in this report. This system, which combines features of the TRPO and TALSPEAK processes, is based on co-extraction of trivalent lanthanides and actinides from 0.1 to 1.0 M HNO 3 followed by application of a buffered aminopolycarboxylate solution strip to accomplish a Reverse TALSPEAK selective removal of actinides. This mixed-extractant medium could enable a simplified approach to selective trivalent f-element extraction and actinide partitioning in amore » single process. As compared with other combined process applications in development for more compact actinide partitioning processes (DIAMEX-SANEX, GANEX, TRUSPEAK, ALSEP), this combination features only monofunctional extractants with high solubility limits and comparatively low molar mass. Selective actinide stripping from the loaded extractant phase is done using a glycine-buffered solution containing N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA) or triethylenetetramine-N,N,N',N'',N''',N'''-hexaacetic acid (TTHA). Lastly, the results reported provide evidence for simplified interactions between the two extractants and demonstrate a pathway toward using mixed monofunctional extractants to separate trivalent actinides (An) from fission product lanthanides (Ln).« less

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

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

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

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

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.

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

Selle, J E

Attempts were made to apply the Kaufman method of calculating binary phase diagrams to the calculation of binary phase diagrams between the rare earths, actinides, and the refractory transition metals. Difficulties were encountered in applying the method to the rare earths and actinides, and modifications were necessary to provide accurate representation of known diagrams. To calculate the interaction parameters for rare earth-rare earth diagrams, it was necessary to use the atomic volumes for each of the phases: liquid, body-centered cubic, hexagonal close-packed, and face-centered cubic. Determination of the atomic volumes of each of these phases for each element is discussedmore » in detail. In some cases, empirical means were necessary. Results are presented on the calculation of rare earth-rare earth, rare earth-actinide, and actinide-actinide diagrams. For rare earth-refractory transition metal diagrams and actinide-refractory transition metal diagrams, empirical means were required to develop values for the enthalpy of vaporization for rare earth elements and values for the constant (C) required when intermediate phases are present. Results of using the values determined for each element are presented.« less

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

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.

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

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.

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.

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

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

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

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.

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.

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

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

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

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

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.

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

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

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.

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.

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

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

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

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

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

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

Final Project Report for ER15351 “A Study of New Actinide Zintl Ion Materials”

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

Peter K. Dorhout

2007-11-12

The structural chemistry of actinide main-group metal materials provides the fundamental basis for the understanding of structural coordination chemistry and the formation of materials with desired or predicted structural features. The main-group metal building blocks, comprising sulfur-group, phosphorous-group, or silicon-group elements, have shown versatility in oxidation state, coordination, and bonding preferences. These building blocks have allowed us to elucidate a series of structures that are unique to the actinide elements, although we can find structural relationships to transition metal and 4f-element materials. In the past year, we investigated controlled metathesis and self-propagating reactions between actinide metal halides and alkali metalmore » salts of main-group metal chalcogenides such as K-P-S salts. Ternary plutonium thiophosphates have resulted from these reactions at low temperature in sealed ampules. we have also focused efforts to examine reactions of Th, U, and Pu halide salts with other alkali metal salts such as Na-Ge-S and Na-Si-Se and copper chloride to identify if self-propagating reactions may be used as a viable reaction to prepare new actinide materials and we prepared a series of U and Th copper chalcogenide materials. Magnetic measurements continued to be a focus of actinide materials prepared in our laboratory. We also contributed to the XANES work at Los Alamos by preparing materials for study and for comparison with environmental samples.« 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.

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

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.

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.

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.

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.

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

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

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

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

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

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.

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

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.

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

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.

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.

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.

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.

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

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.

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

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.

Accelerator-driven transmutation of spent fuel elements

DOEpatents

Venneri, Francesco; Williamson, Mark A.; Li, Ning

2002-01-01

An apparatus and method is described for transmuting higher actinides, plutonium and selected fission products in a liquid-fuel subcritical assembly. Uranium may also be enriched, thereby providing new fuel for use in conventional nuclear power plants. An accelerator provides the additional neutrons required to perform the processes. The size of the accelerator needed to complete fuel cycle closure depends on the neutron efficiency of the supported reactors and on the neutron spectrum of the actinide transmutation apparatus. Treatment of spent fuel from light water reactors (LWRs) using uranium-based fuel will require the largest accelerator power, whereas neutron-efficient high temperature gas reactors (HTGRs) or CANDU reactors will require the smallest accelerator power, especially if thorium is introduced into the newly generated fuel according to the teachings of the present invention. Fast spectrum actinide transmutation apparatus (based on liquid-metal fuel) will take full advantage of the accelerator-produced source neutrons and provide maximum utilization of the actinide-generated fission neutrons. However, near-thermal transmutation apparatus will require lower standing

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).

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.

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.

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

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.

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.

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)

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.

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.

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.

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

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

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.

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.

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.

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.

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.

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.

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

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.

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.

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

Using Principal Component Analysis to Improve Fallout Characterization

DTIC Science & Technology

2017-03-23

between actinide location and elemental composition in fallout from historic atmospheric nuclear weapons testing. Fifty spherical fallout samples were...mathematical approach to solving the complex system of elemental variables while establishing correlations to actinide incorporation within the fallout...1. The double hump curve for uranium-235 showing the effective fission yield by mass number for thermal neutrons. Reproduced with permission from

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)

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.

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.

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.

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

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)

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.

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

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

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

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.

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

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

Electronic Structure of Actinides under Pressure

NASA Astrophysics Data System (ADS)

Johansson, Borje

2006-03-01

The series of heavy radioactive elements known as the actinides all have similar elemental properties. However, when the volume per atom in the condensed phase is illustrated as a function of atomic number, perhaps the most dramatic anomaly in the periodic table becomes apparent. The atomic volume of americium is almost 50% larger than it is for the preceding element plutonium. For the element after americium, curium, the atomic volume is very close to that of americium. The same holds also for the next elements berkelium and californium. Accordingly from americium and onwards the actinides behave very similar to the corresponding rare-earth elements - a second lanthanide series of metallic elements can be identified. This view is strongly supported by the fact that all these elements adopt the dhcp structure, a structure typical for the lanthanides. The reason for this behavior is found in the behavior of the 5f electrons. For the earlier actinides, up to and including plutonium, the 5f electrons form metallic states and contribute most significantly to the bonding. In Np and Pu they even dominate the bonding, while all of a sudden they become localized in Am, very much like the 4f electrons in the lanthanide series, and contribute no longer to the cohesion. This withdrawal of 5f bonding gives rise to the large volume expansion between plutonium and americium. This difference between the light and heavy actinide suggests that it would be most worthwhile to strongly compress the transplutonium elements, thereby forcing the individual 5f electron wave functions into strong contact with each other (overlap). Recently high pressure experiments have been performed for americium and curium and dramatic crystal structure changes have been observed. These results and other high pressure data will be discussed in relation to the basic electronic structure of these elements.

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.

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

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

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.

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.

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.

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.

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.

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

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

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.

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

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

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.

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.

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

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.

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.

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

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

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.

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.

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.

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

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.

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

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.

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

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

Uranium and thorium complexes of the phosphaethynolate ion

DOE PAGES

Camp, Clément; Settineri, Nicholas; Lefèvre, Julia; ...

2015-06-20

New tris-amidinate actinide (Th, U) complexes containing a rare O-bound terminal phosphaethynolate (OCP⁻) ligand were synthesized and fully characterized. The cyanate (OCN⁻) and thiocyanate (SCN⁻) analogs were prepared for comparison and feature a preferential N-coordination to the actinide metals. The Th(amid) 3(OCP) complex reacts with Ni(COD) 2 to yield the heterobimetallic adduct (amid) 3Th(μ-η 1(O):η 2(C,P)-OCP)Ni(COD) featuring an unprecedented reduced (OCP⁻) bent fragment bridging the two metals.

An Investigation of Chitosan for Sorption of Radionuclides

DTIC Science & Technology

2012-06-05

heavy metals, uranium and other actinides , and the rare earths. Alkali and alkaline earth metals have received little attention due to their low...15]. The importance and role of metal hydrolysis on biomass sorption has also been addressed by Gadd and White, for the case of 14 actinides , which are...added to plastic screw-top vials (2 mL, 4 mL or 15 mL) containing a given mass of sorbent at room temperature (20◦C ± 2◦C) or at elevated temperature (37

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.

Apparatus and 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 non-volatile fission products, are reprocessed and separated in a molten metal solvent housed in the reaction region of a separation vessel which includes a reflux region positioned above the molten tin solvent. The reflux region minimizes loss of evaporated solvent during the separation of the actinide fuels from the volatile fission products. Additionally, inclusion of the reflux region permits the separation of the more volatile fission products (noncondensable) from the less volatile ones (condensable).

Colloid formation during waste form reaction: Implications for nuclear waste disposal

USGS Publications Warehouse

Bates, J. K.; Bradley, J.; Teetsov, A.; Bradley, C. R.; Buchholtz ten Brink, Marilyn R.

1992-01-01

Insoluble plutonium- and americium-bearing colloidal particles formed during simulated weathering of a high-level nuclear waste glass. Nearly 100 percent of the total plutonium and americium in test ground water was concentrated in these submicrometer particles. These results indicate that models of actinide mobility and repository integrity, which assume complete solubility of actinides in ground water, underestimate the potential for radionuclide release into the environment. A colloid-trapping mechanism may be necessary for a waste repository to meet long-term performance specifications.

Functionalized expanded porphyrins

DOEpatents

Sessler, Jonathan L; Pantos, Patricia J

2013-11-12

Disclosed are functionalized expanded porphyrins that can be used as spectrometric sensors for high-valent actinide cations. The disclosed functionalized expanded porphyrins have the advantage over unfunctionalized systems in that they can be immobilized via covalent attachment to a solid support comprising an inorganic or organic polymer or other common substrates. Substrates comprising the disclosed functionalized expanded porphyrins are also disclosed. Further, disclosed are methods of making the disclosed compounds (immobilized and free), methods of using them as sensors to detect high valent actinides, devices that comprise the disclosed compounds, and kits.

Separation of actinides from irradiated An-Zr based fuel by electrorefining on solid aluminium cathodes in molten LiCl-KCl

NASA Astrophysics Data System (ADS)

Souček, P.; Murakami, T.; Claux, B.; Meier, R.; Malmbeck, R.; Tsukada, T.; Glatz, J.-P.

2015-04-01

An electrorefining process for metallic spent nuclear fuel treatment is being investigated in ITU. Solid aluminium cathodes are used for homogeneous recovery of all actinides within the process carried out in molten LiCl-KCl eutectic salt at a temperature of 500 °C. As the selectivity, efficiency and performance of solid Al has been already shown using un-irradiated An-Zr alloy based test fuels, the present work was focused on laboratory-scale demonstration of the process using irradiated METAPHIX-1 fuel composed of U67-Pu19-Zr10-MA2-RE2 (wt.%, MA = Np, Am, Cm, RE = Nd, Ce, Gd, Y). Different electrorefining techniques, conditions and cathode geometries were used during the experiment yielding evaluation of separation factors, kinetic parameters of actinide-aluminium alloy formation, process efficiency and macro-structure characterisation of the deposits. The results confirmed an excellent separation and very high efficiency of the electrorefining process using solid Al cathodes.

One-group fission cross sections for plutonium and minor actinides inserted in calculated neutron spectra of fast reactor cooled with lead-208 or lead-bismuth eutectic

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

Khorasanov, G. L.; Blokhin, A. I.

The paper is dedicated to one-group fission cross sections of Pu and MA in LFRs spectra with the aim to increase these values by choosing a coolant which hardens neutron spectra. It is shown that replacement of coolant from Pb-Bi with Pb-208 in the fast reactor RBEC-M, designed in Russia, leads to increasing the core mean neutron energy. As concerns fuel Pu isotopes, their one-group fission cross sections become slightly changed, while more dramatically Am-241 one-group fission cross section is changed. Another situation occurs in the lateral blanket containing small quantities of minor actinides. It is shown that as amore » result of lateral blanket mean neutron energy hardening the one-group fission cross sections of Np-237, Am-241 and Am-243 increases up to 8-11%. This result allows reducing the time of minor actinides burning in FRs. (authors)« less

NEW COLUMN SEPARATION METHOD FOR EMERGENCY URINE SAMPLES

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

Maxwell, S; Brian Culligan, B

2007-08-28

The Savannah River Site Environmental Bioassay Lab participated in the 2007 NRIP Emergency Response program administered by the National Institute for Standards and Technology (NIST) in May, 2007. A new rapid column separation method was applied directly to the NRIP 2007 emergency urine samples, with only minimal sample preparation to reduce preparation time. Calcium phosphate precipitation, previously used to pre-concentrate actinides and Sr-90 in NRIP 2006 urine and water samples, was not used for the NRIP 2007 urine samples. Instead, the raw urine was acidified and passed directly through the stacked resin columns (TEVA+TRU+SR Resins) to separate the actinides andmore » strontium from the NRIP urine samples more quickly. This improvement reduced sample preparation time for the NRIP 2007 emergency urine analyses significantly. This approach works well for small volume urine samples expected during an emergency response event. Based on initial feedback from NIST, the SRS Environmental Bioassay Lab had the most rapid analysis times for actinides and strontium-90 analyses for NRIP 2007 urine samples.« less

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

Supercritical fluid extraction and separation of uranium from other actinides.

PubMed

Quach, Donna L; Mincher, Bruce J; Wai, Chien M

2014-06-15

The feasibility of separating U from nitric acid solutions of mixed actinides using tri-n-butylphosphate (TBP)-modified supercritical fluid carbon dioxide (sc-CO2) was investigated. The actinides U, Np, Pu, and Am were extracted into sc-CO2 modified with TBP from a range of nitric acid concentrations, in the absence of, or in the presence of, a number of traditional reducing and/or complexing agents to demonstrate the separation of these metals from U under sc-CO2 conditions. The separation of U from Pu using sc-CO2 was successful at nitric acid concentrations of less than 3M in the presence of acetohydroxamic acid (AHA) or oxalic acid (OA) to mitigate Pu extraction, and the separation of U from Np was successful at nitric acid concentrations of less than 1M in the presence of AHA, OA, or sodium nitrite to mitigate Np extraction. Americium was not well extracted under any condition studied. Copyright © 2014 Elsevier B.V. All rights reserved.

High-resolution X-ray absorption spectroscopy as a probe of crystal-field and covalency effects in actinide compounds

DOE PAGES

Butorin, Sergei M.; Kvashnina, Kristina O.; Vegelius, Johan R.; ...

2016-07-01

Applying the high-energy resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS), we were able to probe, for the first time to our knowledge, the crystalline electric field (CEF) splittings of the 5f shell directly in the HERFD-XAS spectra of actinides. Using ThO 2 as an example, data measured at the Th 3d edge were interpreted within the framework of the Anderson impurity model. Because the charge-transfer satellites were also resolved in the HERFD-XAS spectra, the analysis of these satellites revealed that ThO 2 is not an ionic compound as previously believed. The Th 6d occupancy in the ground statemore » was estimated to be twice that of the Th 5f states. Here, we demonstrate that HERFD-XAS allows for characterization of the CEF interaction and degree of covalency in the ground state of actinide compounds as it is extensively done for 3d transition metal systems.« less

Preliminary Analysis of High-Flux RSG-GAS to Transmute Am-241 of PWR’s Spent Fuel in Asian Region

NASA Astrophysics Data System (ADS)

Budi Setiawan, M.; Kuntjoro, S.

2018-02-01

A preliminary study of minor actinides (MA) transmutation in the high flux profile RSG-GAS research reactor was performed, aiming at an optimal transmutation loading for present nuclear energy development. The MA selected in the analysis includes Am-241 discharged from pressurized water reactors (PWRs) in Asian region. Until recently, studies have been undertaken in various methods to reduce radiotoxicity from actinides in high-level waste. From the cell calculation using computer code SRAC2006, it is obtained that the target Am-241 which has a cross section of the thermal energy absorption in the region (group 8) is relatively large; it will be easily burned in the RSG-GAS reactor. Minor actinides of Am-241 which can be inserted in the fuel (B/T fuel) is 2.5 kg which is equivalent to Am-241 resulted from the partition of spent fuel from 2 units power reactors PWR with power 1000MW(th) operated for one year.

High Precision Isotopic Analysis of Actinide Bearing Materials: Performance of a New Generation of Purpose Built Actinide Multi-Collector ICPMS Instruments

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

Eiden, Gregory C.; Duffin, Andrew M.; Liezers, Martin

2014-11-14

Recently, a new class of multi-collector inductively coupled plasma mass spectrometers (MC-ICPMS) has been introduced commercially that includes detector arrays purpose built for actinide measurements. These detector arrays significantly enhance the data quality possible for applications encountered in nuclear forensics. Two such instruments are described in this paper, the NeptunePlusTM, developed by Thermo-Fisher (Bremen, Germany), and the NuPlasma2, developed by Nu Instruments (Wrexham, UK). Research results are presented that have been obtained by the authors using the first commercial NeptunePlusTM. This paper also presents performance characteristics and results for traditional liquid introduction, including a means for ultra-trace detection via electrochemicalmore » separation prior to solution nebulization, as well as solid sample introduction with femtosecond-laser ablation. We also discuss the advantages and limitations of the current systems for detection of the transient signals associated with these two methods for introducing sample into the plasma.« less

Energy Frontier Research Center Materials Science of Actinides (A "Life at the Frontiers of Energy Research" contest entry from the 2011 Energy Frontier Research Centers (EFRCs) Summit and Forum)

ScienceCinema

Burns, Peter (Director, Materials Science of Actinides); MSA Staff

2017-12-09

'Energy Frontier Research Center Materials Science of Actinides' was submitted by the EFRC for Materials Science of Actinides (MSA) to the 'Life at the Frontiers of Energy Research' video contest at the 2011 Science for Our Nation's Energy Future: Energy Frontier Research Centers (EFRCs) Summit and Forum. Twenty-six EFRCs created short videos to highlight their mission and their work. MSA is directed by Peter Burns at the University of Notre Dame, and is a partnership of scientists from ten institutions.The Office of Basic Energy Sciences in the U.S. Department of Energy's Office of Science established the 46 Energy Frontier Research Centers (EFRCs) in 2009. These collaboratively-organized centers conduct fundamental research focused on 'grand challenges' and use-inspired 'basic research needs' recently identified in major strategic planning efforts by the scientific community. The overall purpose is to accelerate scientific progress toward meeting the nation's critical energy challenges.

Actinide electronic structure and atomic forces

NASA Astrophysics Data System (ADS)

Albers, R. C.; Rudin, Sven P.; Trinkle, Dallas R.; Jones, M. D.

2000-07-01

We have developed a new method[1] of fitting tight-binding parameterizations based on functional forms developed at the Naval Research Laboratory.[2] We have applied these methods to actinide metals and report our success using them (see below). The fitting procedure uses first-principles local-density-approximation (LDA) linear augmented plane-wave (LAPW) band structure techniques[3] to first calculate an electronic-structure band structure and total energy for fcc, bcc, and simple cubic crystal structures for the actinide of interest. The tight-binding parameterization is then chosen to fit the detailed energy eigenvalues of the bands along symmetry directions, and the symmetry of the parameterization is constrained to agree with the correct symmetry of the LDA band structure at each eigenvalue and k-vector that is fit to. By fitting to a range of different volumes and the three different crystal structures, we find that the resulting parameterization is robust and appears to accurately calculate other crystal structures and properties of interest.

Evaluation of actinide biosorption by microorganisms

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

Happel, A.M.

1996-06-01

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

Electronic, structural, and thermodynamic properties of mixed actinide dioxides (U, Pu, Am) O2 from hybrid density functional theory

NASA Astrophysics Data System (ADS)

Ma, Li; Ray, Asok K.

2010-03-01

As a continuation of our studies of pure actinide metals using hybrid density functional theory,footnotetextR. Atta-Fynn and A. K. Ray, Europhysics Letters, 85, 27008-p1- p6 (2009); Chemical Physics Letters, 482, 223-227 (2009). we present here a systematic study of the electronic and geometric structure properties of mixed actinide dioxides, U0.5Pu0.5O2, U0.5Am0.5O2, Pu0.5Am0.5 O2 and U0.8Pu0.2O2. The fraction of exact Hartree-Fock exchange used was 40%. To investigate the effect of spin-orbit coupling on the ground state electronic and geometric structure properties, computations have been carried out at two theoretical levels, one at the scalar-relativistic level with no spin-orbit coupling and one at the fully relativistic level with spin-orbit coupling. Thermodynamic properties have been calculated by a coupling of first-principles calculation and lattice dynamics.

Extraction of Trivalent Actinides and Lanthanides from Californium Campaign Rework Solution Using TODGA-based Solvent Extraction System

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

Benker, Dennis; Delmau, Laetitia Helene; Dryman, Joshua Cory

This report presents the studies carried out to demonstrate the possibility of quantitatively extracting trivalent actinides and lanthanides from highly acidic solutions using a neutral ligand-based solvent extraction system. These studies stemmed from the perceived advantage of such systems over cationexchange- based solvent extraction systems that require an extensive feed adjustment to make a low-acid feed. The targeted feed solutions are highly acidic aqueous phases obtained after the dissolution of curium targets during a californium (Cf) campaign. Results obtained with actual Cf campaign solutions, but highly diluted to be manageable in a glove box, are presented, followed by results ofmore » tests run in the hot cells with Cf campaign rework solutions. It was demonstrated that a solvent extraction system based on the tetraoctyl diglycolamide molecule is capable of quantitatively extracting trivalent actinides from highly acidic solutions. This system was validated using actual feeds from a Cf campaign.« less

Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal-Organic Frameworks.

PubMed

Dolgopolova, Ekaterina A; Ejegbavwo, Otega A; Martin, Corey R; Smith, Mark D; Setyawan, Wahyu; Karakalos, Stavros G; Henager, Charles H; Zur Loye, Hans-Conrad; Shustova, Natalia B

2017-11-22

Growing necessity for efficient nuclear waste management is a driving force for development of alternative architectures toward fundamental understanding of mechanisms involved in actinide (An) 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 was built stepwise, which was only feasible due to preparation of the first examples of actinide-based frameworks with "unsaturated" metal nodes. The first successful 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 biactinide frameworks with minimal structural density. Overall, the 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.

Status of plutonium ceramic immobilization processes and immobilization forms

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

Ebbinghaus, B.B.; Van Konynenburg, R.A.; Vance, E.R.

1996-05-01

Immobilization in a ceramic followed by permanent emplacement in a repository or borehole is one of the alternatives currently being considered by the Fissile Materials Disposition Program for the ultimate disposal of excess weapons-grade plutonium. To make Pu recovery more difficult, radioactive cesium may also be incorporated into the immobilization form. Valuable data are already available for ceramics form R&D efforts to immobilize high-level and mixed wastes. Ceramics have a high capacity for actinides, cesium, and some neutron absorbers. A unique characteristic of ceramics is the existence of mineral analogues found in nature that have demonstrated actinide immobilization over geologicmore » time periods. The ceramic form currently being considered for plutonium disposition is a synthetic rock (SYNROC) material composed primarily of zirconolite (CaZrTi{sub 2}O{sub 7}), the desired actinide host phase, with lesser amounts of hollandite (BaAl{sub 2}Ti{sub 6}O{sub 16}) and rutile (TiO{sub 2}). Alternative actinide host phases are also being considered. These include pyrochlore (Gd{sub 2}Ti{sub 2}O{sub 7}), zircon (ZrSiO{sub 4}), and monazite (CePO{sub 4}), to name a few of the most promising. R&D activities to address important technical issues are discussed. Primarily these include moderate scale hot press fabrications with plutonium, direct loading of PuO{sub 2} powder, cold press and sinter fabrication methods, and immobilization form formulation issues.« less

Overview of reductants utilized in nuclear fuel reprocessing/recycling

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

Patricia Paviet-Hartmann; Catherine Riddle; Keri Campbell

2013-10-01

Most of the aqueous processes developed, or under consideration worldwide for the recycling of used nuclear fuel (UNF) utilize the oxido-reduction properties of actinides to separate them from other radionuclides. Generally, after acid dissolution of the UNF, (essentially in nitric acid solution), actinides are separated from the raffinate by liquid-liquid extraction using specific solvents, associated along the process, with a particular reductant that will allow the separation to occur. For example, the industrial PUREX process utilizes hydroxylamine as a plutonium reductant. Hydroxylamine has numerous advantages: not only does it have the proper attributes to reduce Pu(IV) to Pu(III), but itmore » is also a non-metallic chemical that is readily decomposed to innocuous products by heating. However, it has been observed that the presence of high nitric acid concentrations or impurities (such as metal ions) in hydroxylamine solutions increase the likelihood of the initiation of an autocatalytic reaction. Recently there has been some interest in the application of simple hydrophilic hydroxamic ligands such as acetohydroxamic acid (AHA) for the stripping of tetravalent actinides in the UREX process flowsheet. This approach is based on the high coordinating ability of hydroxamic acids with tetravalent actinides (Np and Pu) compared with hexavalent uranium. Thus, the use of AHA offers a route for controlling neptunium and plutonium in the UREX process by complexant based stripping of Np(IV) and Pu(IV) from the TBP solvent phase, while U(VI) ions are not affected by AHA and remain solvated in the TBP phase. In the European GANEX process, AHA is also used to form hydrophilic complexes with actinides and strip them from the organic phase into nitric acid. However, AHA does not decompose completely when treated with nitric acid and hampers nitric acid recycling. In lieu of using AHA in the UREX + process, formohydroxamic acid (FHA), although not commercially available, hold promises as a replacement for AHA. FHA undergoes hydrolysis to formic acid which is volatile, thus allowing the recycling of nitric acid. Unfortunately, FHA powder was not stable in the experiments we ran in our laboratory. In addition, AHA and FHA also decompose to hydroxylamine which may undergo an autocatalytic reaction. Other reductants are available and could be extremely useful for actinides separation. The review presents the current plutonium reductants used in used nuclear fuel reprocessing and will introduce innovative and novel reductants that could become reducers for future research on UNF separation.« less

Nuclear energy waste-space transportation and removal

NASA Technical Reports Server (NTRS)

Burns, R. E.

1975-01-01

A method for utilizing the decay heat of actinide wastes to power an electric thrust vehicle is proposed. The vehicle, launched by shuttle to earth orbit and to earth escape by a tug, obtains electrical power from the actinide waste heat by thermionic converters. The heavy gamma ray and neutron shielding which is necessary as a safety feature is removed in orbit and returned to earth for reuse. The problems associated with safety are dealt with in depth. A method for eliminating fission wastes via chemical propulsion is briefly discussed.

The CAT-ACT Beamline at ANKA: A new high energy X-ray spectroscopy facility for CATalysis and ACTinide research

NASA Astrophysics Data System (ADS)

Zimina, A.; Dardenne, K.; Denecke, M. A.; Grunwaldt, J. D.; Huttel, E.; Lichtenberg, H.; Mangold, S.; Pruessmann, T.; Rothe, J.; Steininger, R.; Vitova, T.

2016-05-01

A new hard X-ray beamline for CATalysis and ACTinide research has been built at the synchrotron radiation facility ANKA. The beamline design is dedicated to X-ray spectroscopy, including ‘flux hungry’ photon-in/photon-out and correlative techniques with a special infrastructure for radionuclide and catalysis research. The CAT-ACT beamline will help serve the growing need for high flux/hard X-ray spectroscopy in these communities. The design, the first spectra and the current status of this project are reported.

Actinide management with commercial fast reactors

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

Ohki, Shigeo

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

Properties of metallic glasses containing actinide metals. I. Thermal properties of U--M glasses (M = V, Cr, Mn, Fe, Co, and Ni)

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

Giessen, B.C.; Elliott, R.O.

1978-01-01

The results of a preparative and calorimetric study forming part of a continuing investigation of the new actinide glasses are reported. Specifically, lower bounds for the composition limits of glass formation (G.F.) at moderate cooling rates have been obtained for the U-M (M = Mn, Fe, Co, Ni) systems and the thermal stabilities of glasses in these four systems as well as for a U-V glass and a U-Cr glass have been surveyed.

Potentialities of mass spectrometry (ICP-MS) for actinides determination in urine.

PubMed

Bouvier-Capely, C; Ritt, J; Baglan, N; Cossonnet, C

2004-05-01

The applicability of inductively coupled plasma-mass spectrometry (ICP-MS) for determining actinides in urine was investigated. Performances of ICP-MS including detection limit and analysis time were studied and compared with alpha spectrometry performances. In the field of individual monitoring of workers, the comparison chart obtained in this study can be used as a guide for medical laboratories to select the most adequate procedure to be carried out depending on the case in question (the radioisotope to be measured, the required sensitivity, and the desired response time).

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.

Phase Behavior and Equations of State of the Actinide Oxides

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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.

Managing Zirconium Chemistry and Phase Compatibility in Combined Process Separations for Minor Actinide Partitioning

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

Wall, Nathalie; Nash, Ken; Martin, Leigh

In response to the NEUP Program Supporting Fuel Cycle R&D Separations and Waste Forms call DEFOA- 0000799, this report describes the results of an R&D project focusing on streamlining separation processes for advanced fuel cycles. An example of such a process relevant to the U.S. DOE FCR&D program would be one combining the functions of the TRUEX process for partitioning of lanthanides and minor actinides from PUREX(UREX) raffinates with that of the TALSPEAK process for separating transplutonium actinides from fission product lanthanides. A fully-developed PUREX(UREX)/TRUEX/TALSPEAK suite would generate actinides as product(s) for reuse (or transmutation) and fission products as waste.more » As standalone, consecutive unit-operations, TRUEX and TALSPEAK employ different extractant solutions (solvating (CMPO, octyl(phenyl)-N,Ndiisobutylcarbamoylmethylphosphine oxide) vs. cation exchanging (HDEHP, di-2(ethyl)hexylphosphoric acid) extractants), and distinct aqueous phases (2-4 M HNO 3 vs. concentrated pH 3.5 carboxylic acid buffers containing actinide selective chelating agents). The separate processes may also operate with different phase transfer kinetic constraints. Experience teaches (and it has been demonstrated at the lab scale) that, with proper control, multiple process separation systems can operate successfully. However, it is also recognized that considerable economies of scale could be achieved if multiple operations could be merged into a single process based on a combined extractant solvent. The task of accountability of nuclear materials through the process(es) also becomes more robust with fewer steps, providing that the processes can be accurately modeled. Work is underway in the U.S. and Europe on developing several new options for combined processes (TRUSPEAK, ALSEP, SANEX, GANEX, ExAm are examples). There are unique challenges associated with the operation of such processes, some relating to organic phase chemistry, others arising from the variable composition of the aqueous medium. This project targets in particular two problematic issues in designing combined process systems: managing the chemistry of challenging aqueous species (like Zr 4+) and optimizing the composition and properties of combined extractant organic phases.« less

Increased retention of americium in kidneys as compared with plutonium in an actinide wound contamination model in the rat.

PubMed

Griffiths, Nina M; Coudert, Sylvie; Molina, Thibaut; Wilk, Jean-Claude; Renault, Daniel; Berard, Philippe; Van der Meeren, Anne

2014-11-01

Americium-241 ((241)Am) presents a potential risk for nuclear industry workers associated with reactor decommissioning and aging combustible materials. The purpose of this study was to investigate Am renal retention after actinide contamination by wounding in the rat. Anesthetized rats were contaminated with Mixed Oxide (MOX) (7.1% Plutonium [Pu] by mass and containing 27% Am as % total alpha activity), Pu or Am nitrate following an incision wound of the hind leg. Times of euthanasia ranged from 2 hours to 5 months after contamination. Pu and Am levels were quantified following radiochemistry and alpha-spectrophotometry. Initial data show that over the experimental period the proportion of Am in kidneys as a fraction of total kidney alpha activity was elevated as compared to MOX powder indicating a specific retention in this organ. The percentage of Pu was similar to the powder. After MOX contamination, kidney to liver ratios appeared to increase more markedly for Am (from 0.2 at 7 days to 0.6 at 90 days) as compared with Pu (0.1 at 7 days to 0.2 at 90 days). In accordance with tissue actinide retention the dose from Am to the kidney increases with time. For comparison, the ratio of estimated equivalent doses due to Am to kidney is 1.5-fold greater than for Pu (around 90 versus 60 mSv). After actinide contamination of wounds, Am is concentrated in the kidneys as compared to Pu leading to potential exposure of renal tissue to both alpha particles and gamma radiation.

Estimated inventory of radionuclides in former Soviet Union naval reactors dumped in the Kara Sea

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

Mount, M.E.; Sheaffer, M.K.; Abbott, D.T.

1993-07-01

Radionuclide inventories have been estimated for the reactor cores, reactor components, and primary system corrosion products in the former Soviet Union naval reactors dumped at the Abrosimov Inlet, Tsivolka Inlet, Stepovoy Inlet, Techeniye Inlet, and Novaya Zemlya Depression sites in the Kara Sea between 1965 and 1988. For the time of disposal, the inventories are estimated at 69 to 111 kCi of actinides plus daughters and 3,053 to 7,472 kCi of fission products in the reactor cores, 917 to 1,127 kCi of activation products in the reactor components, and 1.4 to 1.6 kCi of activation products in the primary systemmore » corrosion products. At the present time, the inventories are estimated to have decreased to 23 to 38 kCi of actinides plus daughters and 674 to 708 kCi of fission products in the reactor cores, 124 to 126 kCi of activation products in the reactor components, and 0.16 to 0.17 kCi of activation products in the primary system corrosion products. Twenty years from now, the inventories are projected to be 11 to 18 kCi of actinides plus daughters and 415 to 437 kCi of fission products in the reactor cores, 63.5 to 64 kCi of activation products in the reactor components, and 0.014 to 0.015 kCi of activation products in the primary system corrosion products. All actinide activities are estimated to be within a factor of two.« 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

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

NASA Astrophysics Data System (ADS)

Gregson, Matthew; Lu, Erli; Mills, David P.; Tuna, Floriana; McInnes, Eric J. L.; Hennig, Christoph; Scheinost, Andreas C.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Kerridge, Andrew; Liddle, Stephen T.

2017-02-01

Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal-ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

Fluid extraction

DOEpatents

Wai, Chien M.; Laintz, Kenneth E.

1999-01-01

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated .beta.-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated .beta.-diketone and a trialkyl phosphate, or a fluorinated .beta.-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated .beta.-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

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

Laser-Induced Ionization Efficiency Enhancement On A Filament For Thermal Ionization Mass Spectrometry

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

Siegfried, M.

2015-10-14

The evaluation of trace Uranium and Plutonium isotope ratios for nanogram to femtogram material quantities is a vital tool for nuclear counter-proliferation and safeguard activities. Thermal Ionization Mass Spectrometry (TIMS) is generally accepted as the state of the art technology for highly accurate and ultra-trace measurements of these actinide ratios. However, the very low TIMS ionization yield (typically less than 1%) leaves much room for improvement. Enhanced ionization of Nd and Sm from a TIMS filament was demonstrated using wavelength resonance with a nanosecond (pulse width) laser operating at 10 Hz when light was directed toward the filament.1 For thismore » study, femtosecond and picosecond laser capabilities were to be employed to study the dissociation and ionization mechanisms of actinides/lanthanides and measure the enhanced ionization of the metal of interest. Since the underlying chemistry of the actinide/lanthanide carbides produced and dissociated on a TIMS filament is not well understood, the experimental parameters affecting the photodissociation and photoionization with one and two laser beams were to be investigated.« less

Developing an in-situ Detector of Neutron-Induced Fission for Actinide Sputtering Characterization

NASA Astrophysics Data System (ADS)

Fellers, Deion

2016-09-01

The physical mechanism describing the transfer of large amounts of energy due to fission in a material is not well understood and represents one of the modern challenges facing nuclear scientists, with applications including nuclear energy and national defense. Fission fragments cause damage to the material from sputtering of matter as they pass through or near the material's surface. We have developed a new technique at the Los Alamos Neutron Science Center for characterizing the ejecta by using ultracold neutrons (neutrons with kinetic energy less than 300 neV) to induce fission at finely controlled depths in an actinide. This program will ultimately provide a detailed description of the properties of the sputtered particles as a function of the depth of the fission in the material. A key component of this project is accurately quantifying the number of neutron induced fissions in the sample. This poster depicts the development of an in-situ detector of neutron-induced fission for the AShES (Actinide Sputtering from ultracold neutron Exposure at the Surface) experiment.

Energy Frontier Research Center Materials Science of Actinides (A "Life at the Frontiers of Energy Research" contest entry from the 2011 Energy Frontier Research Centers (EFRCs) Summit and Forum)

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

Burns, Peter; Lenzen, Meehan

"Energy Frontier Research Center Materials Science of Actinides" was submitted by the EFRC for Materials Science of Actinides (MSA) to the "Life at the Frontiers of Energy Research" video contest at the 2011 Science for Our Nation's Energy Future: Energy Frontier Research Centers (EFRCs) Summit and Forum. Twenty-six EFRCs created short videos to highlight their mission and their work. MSA is directed by Peter Burns at the University of Notre Dame, and is a partnership of scientists from ten institutions.The Office of Basic Energy Sciences in the U.S. Department of Energy's Office of Science established the 46 Energy Frontier Researchmore » Centers (EFRCs) in 2009. These collaboratively-organized centers conduct fundamental research focused on 'grand challenges' and use-inspired 'basic research needs' recently identified in major strategic planning efforts by the scientific community. The overall purpose is to accelerate scientific progress toward meeting the nation's critical energy challenges.« less

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.

Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?

DOE PAGES

Knight, Andrew W.; Chiarizia, Renato; Soderholm, L.

2017-05-10

In this paper, the extraction behavior of a quaternary alkylammonium salt extractant was investigated for its selectivity for trivalent actinides over trivalent lanthanides in nitrate and thiocyanate media. The selectivity was evaluated by solvent extraction experiments through radiochemical analysis of 241Am and 152/154Eu. Solvent extraction distribution and slope-analysis experiments were performed with americium(III) and europium(III) with respect to the ligand (nitrate and thiocyanate), extractant, and metal (europium only) concentrations. Further evaluation of the equilibrium expression that governs the extraction process indicated the appropriate use of the saturation method for estimation of the aggregation state of quaternary ammonium extractants in themore » organic phase. From the saturation method, we observed an average aggregation number of 5.4 ± 0.8 and 8.5 ± 0.9 monomers/aggregate for nitrate and thiocyanate, respectively. Through a side-by-side comparison of the nitrate and thiocyanate forms, we discuss the potential role of the aggregation in the increased selectivity for trivalent actinides over trivalent lanthanides in thiocyanate media.« less

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes.

PubMed

Gregson, Matthew; Lu, Erli; Mills, David P; Tuna, Floriana; McInnes, Eric J L; Hennig, Christoph; Scheinost, Andreas C; McMaster, Jonathan; Lewis, William; Blake, Alexander J; Kerridge, Andrew; Liddle, Stephen T

2017-02-03

Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal-ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

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.

Bonding nature and electron delocalization of An(COT)2, An = Th, Pa, U.

PubMed

Páez-Hernández, Dayán; Murillo-López, Juliana A; Arratia-Pérez, Ramiro

2011-08-18

A systematic study of a series of An(COT)(2) compounds, where An = Th, Pa, U, and COT represents cyclooctatetraene, has been performed using relativistic density functional theory. The ZORA Hamiltonian was applied for the inclusion of relativistic effects, taking into account all of the electrons for the optimization and explicitly including spin-orbit coupling effects. Time-dependent density functional theory (TDDFT) was used to calculate the excitation energies with the GGA SAOP functional, and the electronic transitions were analyzed using double group irreducible representations. The calculated excitation energies are in perfect correlation with the increment of the ring delocalization as it increases along the actinide series. These results are sufficient to ensure that, for these complexes, the increment in delocalization, as indicated by ELF bifurcation and NICS analysis, leads to a shift in the maximum wavelength of absorption in the visible region. Also, delocalization in the COT ring increases along the actinide series, so the systems become more aromatic because of a modulation induced by the actinides. © 2011 American Chemical Society

Extraction Selectivity of a Quaternary Alkylammonium Salt for Trivalent Actinides over Trivalent Lanthanides: Does Extractant Aggregation Play a Role?

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

Knight, Andrew W.; Chiarizia, Renato; Soderholm, L.

In this paper, the extraction behavior of a quaternary alkylammonium salt extractant was investigated for its selectivity for trivalent actinides over trivalent lanthanides in nitrate and thiocyanate media. The selectivity was evaluated by solvent extraction experiments through radiochemical analysis of 241Am and 152/154Eu. Solvent extraction distribution and slope-analysis experiments were performed with americium(III) and europium(III) with respect to the ligand (nitrate and thiocyanate), extractant, and metal (europium only) concentrations. Further evaluation of the equilibrium expression that governs the extraction process indicated the appropriate use of the saturation method for estimation of the aggregation state of quaternary ammonium extractants in themore » organic phase. From the saturation method, we observed an average aggregation number of 5.4 ± 0.8 and 8.5 ± 0.9 monomers/aggregate for nitrate and thiocyanate, respectively. Through a side-by-side comparison of the nitrate and thiocyanate forms, we discuss the potential role of the aggregation in the increased selectivity for trivalent actinides over trivalent lanthanides in thiocyanate media.« less

Experimental findings on actinide recovery utilizing oxidation by peroxydisulfate followed by ion exchange: Fuel cycle research & development

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

Hobbs, D. T.; Shehee, T. C.

2015-08-31

Our research seeks to determine if inorganic ion-exchange materials can be exploited to provide effective minor actinide (Am, Cm) separation from lanthanides. Previous work has established that a number of inorganic and UMOF ion-exchange materials exhibit varying affinities for actinides and lanthanides, which may be exploited for effective separations. During FY15, experimental work focused on investigating methods to oxidize americium in dilute nitric and perchloric acid with subsequent ion-exchange performance measurements of ion exchangers with the oxidized americium in dilute nitric acid. Ion-exchange materials tested included a variety of alkali titanates. Americium oxidation testing sought to determine the influence thatmore » other redox active components may have on the oxidation of Am III. Experimental findings indicated that Ce III, Np V, and Ru II are oxidized by peroxydisulfate, but there are no indications that the presence of Ce III, Np V, and Ru II affected the rate or extent of americium oxidation at the concentrations of peroxydisulfate being used.« less

Actinide Solubility and Speciation in the WIPP [PowerPoint

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

Reed, Donald T.

2015-11-02

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

a Chirped Pulse Fourier Transform Microwave Cp-Ftmw Spectrometer with Laser Ablation Source to Search for Actinide-Containing Molecules and Noble Metal Clusters

NASA Astrophysics Data System (ADS)

Marshall, Frank E.; Gillcrist, David Joseph; Persinger, Thomas D.; Moon, Nicole; Grubbs, G. S., II

2016-06-01

Microwave spectroscopic techniques have traditionally been part of the foundation of molecular structure and this conference. Instrumental developments by Brooks Pate and sourcing developments by Steve Cooke on these instruments have allowed for the dawning of a new era in modern microwave spectroscopic techniques. With these advances and the growth of powerful computational approaches, microwave spectroscopists can now search for molecules and/or cluster systems of actinide and noble metal-containing species with increasing certainty in molecular assignment even with the difficulties presented with spin-orbit coupling and relativistic effects. Spectrometer and ablation design will be presented along with any preliminary results on actinide-containing molecules or noble metal clusters or interactions. G. G. Brown, B. C. Dian, K. O. Douglass, S. M. Geyer, S. T. Shipman, B. H. Pate, Rev. Sci. Instrum. 79 (2008) 053103-1 - 053103-13 G. S. Grubbs II, C. T. Dewberry, K. C. Etchison, K. E. Kerr, S. A. Cooke, Rev. Sci. Instrum. 78 (2007) 096106-1 - 096106-3

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

PubMed Central

Gregson, Matthew; Lu, Erli; Mills, David P.; Tuna, Floriana; McInnes, Eric J. L.; Hennig, Christoph; Scheinost, Andreas C.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Kerridge, Andrew; Liddle, Stephen T.

2017-01-01

Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal–ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle. PMID:28155857

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

Chemical Properties of Elements 99 and 100 [Einsteinium and Fermium

DOE R&D Accomplishments Database

Seaborg, G. T.; Thompson, S. G.; Harvey, B. G.; Choppin, G. R.

1954-07-23

A description of some of the chemical properties and of the methods used in the separations of elements 99 [Einsteinium] and 100 [Fermium] are given. The new elements exhibit the properties expected for the tenth and eleventh actinide elements. Attempts to produce an oxidation state greater than III of element 99 have been unsuccessful. In normal aqueous media only the III state of element 100 appears to exist. The relative spacings of the elution peaks of the new elements in some separations with ion exchange resin columns are the same as the relative spacings of the homologous lanthanide elements. The results of experiments involving cation exchange resins with very concentrated hydrochloric acid eluant show that the new elements, like the earlier actinides, are more strongly complexed than the lanthanides. The new elements also exist partially as anions in concentrated hydrochloric acid, as do earlier actinide elements, and they may be partially separated from each other by means of ion exchange resins. With some eluants interesting reversals of elution positions are observed in the region Bk-Cf-99-100, indicating complex ion formation involving unusual factors.

Description of the Hexadecapole Deformation Parameter in the sdg Interacting Boson Model

NASA Astrophysics Data System (ADS)

Liu, Yu-xin; Sun, Di; Wang, Jia-jun; Han, Qi-zhi

1998-04-01

The hexadecapole deformation parameter β4 of the rare-earth and actinide nuclei is investigated in the framework of the sdg interacing boson model. An explicit relation between the geometric hexadecapole deformation parameter β4 and the intrinsic deformation parameters epsilon4, epsilon2 are obtained. The deformation parameters β4 of the rare-earths and actinides are determined without any free parameter. The calculated results agree with experimental data well. It also shows that the SU(5) limit of the sdg interacting boson model can describe the β4 systematics as well as the SU(3) limit.

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.

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).

The behavior and importance of lactic acid complexation in Talspeak extraction systems

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

Grimes, Travis S.; Nilsson, Mikael; Nash, Kenneth L.

2008-07-01

Advanced partitioning of spent nuclear fuel in the UREX +la process relies on the TALSPEAK process for separation of fission-product lanthanides from trivalent actinides. The classic TALSPEAK utilizes an aqueous medium of both lactic acid and diethylenetriaminepentaacetic acid and the extraction reagent di(2-ethylhexyl)phosphoric acid in an aromatic diluent. In this study, the specific role of lactic acid and the complexes involved in the extraction of the trivalent actinides and lanthanides have been investigated using {sup 14}C-labeled lactic acid. Our results show that lactic acid partitions between the phases in a complex fashion. (authors)

Magnetocrystalline anisotropy in UMn 2 Ge 2 and related Mn-based actinide ferromagnets

DOE PAGES

Parker, David S.; Ghimire, Nirmal; Singleton, John; ...

2015-05-04

We presenmore » t magnetization isotherms in pulsed magnetic fields up to 62 Tesla, supported by first principles calculations, demonstrating a huge uniaxial magnetocrystalline anisotropy energy - approximately 20 MJ/m 3 - in UMn 2 Ge 2 . This large anisotropy results from the extremely strong spin-orbit coupling affecting the uranium 5 f electrons, which in the calculations exhibit a substantial orbital moment exceeding 2 μ B. Finally, we also find from theoretical calculations that a number of isostructural Mn-actinide compounds are expected to have similarly large anisotropy.« less

Spectroscopy of neutron rich nuclei using cold neutron induced fission of actinide targets at the ILL: The EXILL campaign

NASA Astrophysics Data System (ADS)

Blanc, A.; de France, G.; Drouet, F.; Jentschel, M.; Köster, U.; Mancuso, C.; Mutti, P.; Régis, J. M.; Simpson, G.; Soldner, T.; Ur, C. A.; Urban, W.; Vancraeyenest, A.

2013-12-01

One way to explore exotic nuclei is to study their structure by performing γ-ray spectroscopy. At the ILL, we exploit a high neutron flux reactor to induce the cold fission of actinide targets. In this process, fission products that cannot be accessed using standard spontaneous fission sources are produced with a yield allowing their detailed study using high resolution γ-ray spectroscopy. This is what was pursued at the ILL with the EXILL (for EXOGAM at the ILL) campaign. In the present work, the EXILL setup and performance will be presented.

Process to remove rare earth from IFR electrolyte

DOEpatents

Ackerman, John P.; Johnson, Terry R.

1994-01-01

The invention is a process for the removal of rare earths from molten chloride electrolyte salts used in the reprocessing of integrated fast reactor fuel (IFR). The process can be used either continuously during normal operation of the electrorefiner or as a batch process. The process consists of first separating the actinide values from the salt before purification by removal of the rare earths. After replacement of the actinides removed in the first step, the now-purified salt electrolyte has the same uranium and plutonium concentration and ratio as when the salt was removed from the electrorefiner.

Solvent for the simultaneous recovery of radionuclides from liquid radioactive wastes

DOEpatents

Romanovskiy, Valeriy Nicholiavich; Smirnov, Igor V.; Babain, Vasiliy A.; Todd, Terry A.; Brewer, Ken N.

2002-01-01

The present invention relates to solvents, and methods, for selectively extracting and recovering radionuclides, especially cesium and strontium, rare earths and actinides from liquid radioactive wastes. More specifically, the invention relates to extracting agent solvent compositions comprising complex organoboron compounds, substituted polyethylene glycols, and neutral organophosphorus compounds in a diluent. The preferred solvent comprises a chlorinated cobalt dicarbollide, diphenyl-dibutylmethylenecarbamoylphosphine oxide, PEG-400, and a diluent of phenylpolyfluoroalkyl sulfone. The invention also provides a method of using the invention extracting agents to recover cesium, strontium, rare earths and actinides from liquid radioactive waste.

Method for the simultaneous recovery of radionuclides from liquid radioactive wastes using a solvent

DOEpatents

Romanovskiy, Valeriy Nicholiavich; Smirnov, Igor V.; Babain, Vasiliy A.; Todd, Terry A.; Brewer, Ken N.

2001-01-01

The present invention relates to solvents, and methods, for selectively extracting and recovering radionuclides, especially cesium and strontium, rare earths and actinides from liquid radioactive wastes. More specifically, the invention relates to extracting agent solvent compositions comprising complex organoboron compounds, substituted polyethylene glycols, and neutral organophosphorus compounds in a diluent. The preferred solvent comprises a chlorinated cobalt dicarbollide, diphenyl-dibutylmethylenecarbamoylphosphine oxide, PEG-400, and a diluent of phenylpolyfluoroalkyl sulfone. The invention also provides a method of using the invention extracting agents to recover cesium, strontium, rare earths and actinides from liquid radioactive waste.

Electrodeposition of biaxially textured layers on a substrate

DOEpatents

Bhattacharya, Raghu N; Phok, Sovannary; Spagnol, Priscila; Chaudhuri, Tapas

2013-11-19

Methods of producing one or more biaxially textured layer on a substrate, and articles produced by the methods, are disclosed. An exemplary method may comprise electrodepositing on the substrate a precursor material selected from the group consisting of rare earths, transition metals, actinide, lanthanides, and oxides thereof. An exemplary article (150) may comprise a biaxially textured base material (130), and at least one biaxially textured layer (110) selected from the group consisting of rare earths, transition metals, actinides, lanthanides, and oxides thereof. The at least one biaxially textured layer (110) is formed by electrodeposition on the biaxially textured base material (130).

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.

Process to remove rare earth from IFR electrolyte

DOEpatents

Ackerman, J.P.; Johnson, T.R.

1992-01-01

The invention is a process for the removal of rare earths from molten chloride electrolyte salts used in the reprocessing of integrated fast reactor fuel (IFR). The process can be used either continuously during normal operation of the electrorefiner or as a batch process. The process consists of first separating the actinide values from the salt before purification by removal of the rare earths. After replacement of the actinides removed in the first step, the now-purified salt electrolyte has the same uranium and plutonium concentration and ratio as when the salt was removed from the electrorefiner.

Process to remove rare earth from IFR electrolyte

DOEpatents

Ackerman, J.P.; Johnson, T.R.

1994-08-09

The invention is a process for the removal of rare earths from molten chloride electrolyte salts used in the reprocessing of integrated fast reactor fuel (IFR). The process can be used either continuously during normal operation of the electrorefiner or as a batch process. The process consists of first separating the actinide values from the salt before purification by removal of the rare earths. After replacement of the actinides removed in the first step, the now-purified salt electrolyte has the same uranium and plutonium concentration and ratio as when the salt was removed from the electrorefiner. 1 fig.

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.

The reduced transition probabilities for excited states of rare-earths and actinide even-even nuclei

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

Ghumman, S. S.

The theoretical B(E2) ratios have been calculated on DF, DR and Krutov models. A simple method based on the work of Arima and Iachello is used to calculate the reduced transition probabilities within SU(3) limit of IBA-I framework. The reduced E2 transition probabilities from second excited states of rare-earths and actinide even–even nuclei calculated from experimental energies and intensities from recent data, have been found to compare better with those calculated on the Krutov model and the SU(3) limit of IBA than the DR and DF models.

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.

Local structure in solid solutions of stabilised zirconia with actinide dioxides (UO{sub 2}, NpO{sub 2})

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

Walter, Marcus, E-mail: marcus.walter@vkta.d; Somers, Joseph; Bouexiere, Daniel

2011-04-15

The local structure of (Zr,Lu,U)O{sub 2-x} and (Zr,Y,Np)O{sub 2-x} solid solutions has been investigated by extended X-ray absorption fine structure (EXAFS). Samples were prepared by mixing reactive (Zr,Lu)O{sub 2-x} and (Zr,Y)O{sub 2-x} precursor materials with the actinide oxide powders, respectively. Sintering at 1600 {sup o}C in Ar/H{sub 2} yields a fluorite structure with U(IV) and Np(IV). As typical for stabilised zirconia the metal-oxygen and metal-metal distances are characteristic for the different metal ions. The bond lengths increase with actinide concentration, whereas highest adaptation to the bulk stabilised zirconia structure was observed for U---O and Np---O bonds. The Zr---O bond showsmore » only a slight increase from 2.14 A at 6 mol% actinide to 2.18 A at infinite dilution in UO{sub 2} and NpO{sub 2}. The short interatomic distance between Zr and the surrounding oxygen and metal atoms indicate a low relaxation of Zr with respect to the bulk structure, i.e. a strong Pauling behaviour. -- Graphical abstract: Metal-oxygen bond distances in (Zr,Lu,U)O{sub 2-x} solid solutions with different oxygen vacancy concentrations (Lu/Zr=1 and Lu/Zr=0.5). Display Omitted Research Highlights: {yields} EXAFS indicates high U and Np adaption to the bulk structure of stabilised zirconia. {yields} Zr---O bond length is 2.18 A at infinite Zr dilution in UO{sub 2} and NpO{sub 2}. {yields} Low relaxation (strong Pauling behaviour) of Zr explains its low solubility in UO{sub 2}.« less

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.

PROCESSING ALTERNATIVES FOR DESTRUCTION OF TETRAPHENYLBORATE

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

Lambert, D; Thomas Peters, T; Samuel Fink, S

Two processes were chosen in the 1980's at the Savannah River Site (SRS) to decontaminate the soluble High Level Waste (HLW). The In Tank Precipitation (ITP) process (1,2) was developed at SRS for the removal of radioactive cesium and actinides from the soluble HLW. Sodium tetraphenylborate was added to the waste to precipitate cesium and monosodium titanate (MST) was added to adsorb actinides, primarily uranium and plutonium. Two products of this process were a low activity waste stream and a concentrated organic stream containing cesium tetraphenylborate and actinides adsorbed on monosodium titanate (MST). A copper catalyzed acid hydrolysis process wasmore » built to process (3, 4) the Tank 48H cesium tetraphenylborate waste in the SRS's Defense Waste Processing Facility (DWPF). Operation of the DWPF would have resulted in the production of benzene for incineration in SRS's Consolidated Incineration Facility. This process was abandoned together with the ITP process in 1998 due to high benzene in ITP caused by decomposition of excess sodium tetraphenylborate. Processing in ITP resulted in the production of approximately 1.0 million liters of HLW. SRS has chosen a solvent extraction process combined with adsorption of the actinides to decontaminate the soluble HLW stream (5). However, the waste in Tank 48H is incompatible with existing waste processing facilities. As a result, a processing facility is needed to disposition the HLW in Tank 48H. This paper will describe the process for searching for processing options by SRS task teams for the disposition of the waste in Tank 48H. In addition, attempts to develop a caustic hydrolysis process for in tank destruction of tetraphenylborate will be presented. Lastly, the development of both a caustic and acidic copper catalyzed peroxide oxidation process will be discussed.« less

High-pressure synthesis and characterization of new actinide borates, AnB4O8 (An=Th, U).

PubMed

Hinteregger, Ernst; Hofer, Thomas S; Heymann, Gunter; Perfler, Lukas; Kraus, Florian; Huppertz, Hubert

2013-11-18

New actinide borates ThB4O8 and UB4O8 were synthesized under high-pressure, high-temperature conditions (5.5 GPa/1100 °C for thorium borate, 10.5 GPa/1100 °C for the isotypic uranium borate) in a Walker-type multianvil apparatus from their corresponding actinide oxide and boron oxide. The crystal structure was determined on basis of single-crystal X-ray diffraction data that were collected at room temperature. Both compounds crystallized in the monoclinic space group C2/c (Z=4). Lattice parameters for ThB4O8: a=1611.3(3), b=419.86(8), c=730.6(2) pm; β=114.70(3)°; V=449.0(2) Å(3); R1=0.0255, wR2=0.0653 (all data). Lattice parameters for UB4O8: a=1589.7(3), b=422.14(8), c=723.4(2) pm; β=114.13(3)°; V=443.1(2) Å(3); R1=0.0227, wR2=0.0372 (all data). The new AnB4O8 (An=Th, U) structure type is constructed from corner-sharing BO4 tetrahedra, which form layers in the bc plane. One of the four independent oxygen atoms is threefold-coordinated. The actinide cations are located between the boron-oxygen layers. In addition to Raman spectroscopic investigations, DFT calculations were performed to support the assignment of the vibrational bands. © 2013 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This isan open access article under the terms of the Creative Commons AttributionLicense, which permits use, distribution and reproduction in any medium,provided the original work is properly cited.

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.

Actinide-contaminated Skin: Comparing Decontamination Efficacy of Water, Cleansing Gels, and DTPA Gels.

PubMed

Tazrart, A; Bolzinger, M A; Lamart, S; Coudert, S; Angulo, J F; Jandard, V; Briançon, S; Griffiths, N M

2018-07-01

Skin contamination by alpha-emitting actinides is a risk to workers during nuclear fuel production and reactor decommissioning. Also, the list of items for potential use in radiological dispersal devices includes plutonium and americium. The actinide chemical form is important and solvents such as tributyl phosphate, used to extract plutonium, can influence plutonium behavior. This study investigated skin fixation and efficacy of decontamination products for these actinide forms using viable pig skin in the Franz cell diffusion system. Commonly used or recommended decontamination products such as water, cleansing gel, diethylenetriamine pentaacetic acid, or octadentate hydroxypyridinone compound 3,4,3-LI(1,2-HOPO), as well as diethylenetriamine pentaacetic acid hydrogel formulations, were tested after a 2-h contact time with the contaminant. Analysis of skin samples demonstrated that more plutonium nitrate is bound to skin as compared to plutonium-tributyl phosphate, and fixation of americium to skin was also significant. The data show that for plutonium-tributyl phosphate all the products are effective ranging from 80 to 90% removal of this contaminant. This may be associated with damage to the skin by this complex and suggests a mechanical/wash-out action rather than chelation. For removal of americium and plutonium, both Trait Rouge cleansing gel and diethylenetriamine pentaacetic acid are better than water, and diethylenetriamine pentaacetic acid hydrogel is better than Osmogel. The different treatments, however, did not significantly affect the activity in deeper skin layers, which suggests a need for further improvement of decontamination procedures. The new diethylenetriamine pentaacetic acid hydrogel preparation was effective in removing americium, plutonium, and plutonium-tributyl phosphate from skin; such a formulation offers advantages and thus merits further assessment.

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).

Communication—Quantitative Voltammetric Analysis of High Concentration Actinides in Molten Salts

DOE PAGES

Hoyt, Nathaniel C.; Willit, James L.; Williamson, Mark A.

2017-01-18

Previous electroanalytical studies have shown that cyclic voltammetry can provide accurate quantitative measurements of actinide concentrations at low weight loadings in molten salts. However, above 2 wt%, the techniques were found to underpredict the concentrations of the reactant species. Here this work will demonstrate that much of the discrepancy is caused by uncompensated resistance and cylindrical diffusion. An improved electroanalytical approach has therefore been developed using the results of digital simulations to take these effects into account. This approach allows for accurate electroanalytical predictions across the full range of weight loadings expected to be encountered in operational nuclear fuel processingmore » equipment.« less

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.

Ultra low-level measurements of actinides by sector field ICP-MS.

PubMed

Pointurier, F; Baglan, N; Hémet, P

2004-01-01

In the present work, a double-focusing sector field inductively coupled plasma-mass spectrometer was optimised for ultra trace and isotopic analyses of actinide long-lived isotopes in low concentration solutions of the fgml(-1) to the ngml(-1) range. Sensitivities of about 3GHz/(microgml(-1)), with as low a background as 0.1cps, were obtained for U using a conventional concentric pneumatic nebuliser. Detection limits are below the fg range for 239Pu and 240Pu. With natural U, a precision lower than 0.5% RSD is currently obtained for 235U/238U isotopic ratio at the 200pgml(-1) level.

Communication—Quantitative Voltammetric Analysis of High Concentration Actinides in Molten Salts

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

Hoyt, Nathaniel C.; Willit, James L.; Williamson, Mark A.

Previous electroanalytical studies have shown that cyclic voltammetry can provide accurate quantitative measurements of actinide concentrations at low weight loadings in molten salts. However, above 2 wt%, the techniques were found to underpredict the concentrations of the reactant species. Here this work will demonstrate that much of the discrepancy is caused by uncompensated resistance and cylindrical diffusion. An improved electroanalytical approach has therefore been developed using the results of digital simulations to take these effects into account. This approach allows for accurate electroanalytical predictions across the full range of weight loadings expected to be encountered in operational nuclear fuel processingmore » equipment.« less

Low-temperature synthesis of actinide tetraborides by solid-state metathesis reactions

DOEpatents

Lupinetti, Anthony J [Los Alamos, NM; Garcia, Eduardo [Los Alamos, NM; Abney, Kent D [Los Alamos, NM

2004-12-14

The synthesis of actinide tetraborides including uranium tetraboride (UB.sub.4), plutonium tetraboride (PuB.sub.4) and thorium tetraboride (ThB.sub.4) by a solid-state metathesis reaction are demonstrated. The present method significantly lowers the temperature required to .ltoreq.850.degree. C. As an example, when UCl.sub.4 is reacted with an excess of MgB.sub.2, at 850.degree. C., crystalline UB.sub.4 is formed. Powder X-ray diffraction and ICP-AES data support the reduction of UCl.sub.3 as the initial step in the reaction. The UB.sub.4 product is purified by washing water and drying.

Voltammetry Method Evaluation

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

Hoyt, N.; Pereira, C.; Willit, J.

2016-07-29

The purpose of the ANL MPACT Voltammetry project is to evaluate the suitability of previously developed cyclic voltammetry techniques to provide electroanalytical measurements of actinide concentrations in realistic used fuel processing scenarios. The molten salts in these scenarios are very challenging as they include high concentrations of multiple electrochemically active species, thereby creating a variety of complications. Some of the problems that arise therein include issues related to uncompensated resistance, cylindrical diffusion, and alloying of the electrodeposited metals. Improvements to the existing voltammetry technique to account for these issues have been implemented, resulting in good measurements of actinide concentrations acrossmore » a wide range of adverse conditions.« less

Extraction of metals using supercritical fluid and chelate forming legand

DOEpatents

Wai, Chien M.; Laintz, Kenneth E.

1998-01-01

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated .beta.-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated .beta.-diketone and a trialkyl phosphate, or a fluorinated .beta.-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated .beta.-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

Extraction of metals using supercritical fluid and chelate forming ligand

DOEpatents

Wai, C.M.; Laintz, K.E.

1998-03-24

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated {beta}-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated {beta}-diketone and a trialkyl phosphate, or a fluorinated {beta}-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated {beta}-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process. 7 figs.

SRNL Development of Recovery Processes for Mark-18A Heavy Actinide Targets

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

Allender, Jeffrey S.; Bridges, Nicholas J.; Loftin, Bradley M.

2015-07-14

Savannah River National Laboratory (SRNL) and Oak Ridge National Laboratory (ORNL) are developing plans for the recovery of rare and unique isotopes contained within heavy-actinide target assemblies, specifically the Mark-18A. Mark-18A assemblies were irradiated in Savannah River Site (SRS) reactors in the 1970s under extremely high neutron-flux conditions and produced, virtually, the world's supply of plutonium-244, an isotope of key importance to high-precision actinide measurement and other scientific and nonproliferation uses; and curium highly enriched in heavy isotopes (e.g., curium-246 and curium-248). In 2015 and 2016, SRNL is pursuing tasks that would reduce program risk and budget requirements, including furthermore » characterization of unprocessed targets; engineering studies for the use of the SRNL Shielded Cells Facility (SCF) for recovery; and development of onsite and offsite shipping methods including a replacement for the heavy (70 ton) cask previously used for onsite transfer of irradiated items at SRS. A status update is provided for the characterization, including modeling using the Monte Carlo N-Particle Transport Code (MCNP); direct non-destructive assay measurements; and cask design.« less

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.

Requirements for Predictive Density Functional Theory Methods for Heavy Materials Equation of State

NASA Astrophysics Data System (ADS)

Mattsson, Ann E.; Wills, John M.

2012-02-01

The difficulties in experimentally determining the Equation of State of actinide and lanthanide materials has driven the development of many computational approaches with varying degree of empiricism and predictive power. While Density Functional Theory (DFT) based on the Schr"odinger Equation (possibly with relativistic corrections including the scalar relativistic approach) combined with local and semi-local functionals has proven to be a successful and predictive approach for many materials, it is not giving enough accuracy, or even is a complete failure, for the actinides. To remedy this failure both an improved fundamental description based on the Dirac Equation (DE) and improved functionals are needed. Based on results obtained using the appropriate fundamental approach of DFT based on the DE we discuss the performance of available semi-local functionals, the requirements for improved functionals for actinide/lanthanide materials, and the similarities in how functionals behave in transition metal oxides. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Estimated inventory of radionuclides in Former Soviet Union Naval Reactors dumped in the Kara Sea and their associated health risk

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

Mount, M.E.; Layton, D.W.; Schwertz, N.L.

1993-05-01

Radionuclide inventories have bin estimated for the reactor cores, reactor components, and primary system corrosion products in the former Soviet Union naval reactors dumped at the Abrosimov Inlet, Tsivolka Inlet, Stepovoy Inlet, Techeniye Inlet, and Novaya Zemlya Depression sites in the Kara Sea between 1965 and 1988. For the time of disposal, the inventories are estimated at 17 to 66 kCi of actinides plus daughters and 1695 to 4782 kCi of fission products in the reactor cores, 917 to 1127 kCi of activation products in the reactor components, and 1.4 to 1.6 kCi of activation products in the primary systemmore » corrosion products. At the present time, the inventories are estimated to have decreased to 6 to 24 kCi of actinides plus daughters and 492 to 540 kCi of fission products in the reactor cores, 124 to 126 kCi of activation products in the reactor components, and 0.16 to 0.17 kCi of activation products in the primary system corrosion products. All actinide activities are estimated to be within a factor of two.« less

Laboratory actinide partitioning - Whitlockite/liquid and influence of actinide concentration levels

NASA Technical Reports Server (NTRS)

Benjamin, T. M.; Jones, J. H.; Heuser, W. R.; Burnett, D. S.

1983-01-01

The partition coefficients between synthetic whitlockite (beta Ca-phosphate) and coexisting silicate melts are determined for the actinide elements Th, U and Pu. Experiments were performed at 1 bar pressure and 1250 C at oxygen fugacities from 10 to the -8.5 to 10 to the -0.7 bars, and partitioning was determined from trace element radiography combined with conventional electron microprobe analysis. Results show Pu to be more readily incorporated into crystalline phases than U or Th under reducing conditions, which is attributed to the observation that Pu exists primarily in the trivalent state, while U and Th are tetravalent. Corrected partition coefficients for whitlockite of 3.6, less than or equal to 0.6, 1.2, 0.5 and less than or equal to 0.002 are estimated for Pu(+3), Pu(+4), Th(+4), U(+4) and U(+6), respectively. Experiments performed at trace levels and percent levels of UO2 indicate that Si is involved in U substitution in whitlockite, and show a reduced partition coefficient at higher concentrations of U that can be explained by effects on melt structure or the fraction of tetravalent U.

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.

Determining the dissolution rates of actinide glasses: A time and temperature Product Consistency Test study

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

Daniel, W.E.; Best, D.R.

1995-12-01

Vitrification has been identified as one potential option for the e materials such as Americium (Am), Curium (Cm), Neptunium (Np), and Plutonium (Pu). A process is being developed at the Savannah River Site to safely vitrify all of the highly radioactive Am/Cm material and a portion of the fissile (Pu) actinide materials stored on site. Vitrification of the Am/Cm will allow the material to be transported and easily stored at the Oak Ridge National Laboratory. The Am/Cm glass has been specifically designed to be (1) highly durable in aqueous environments and (2) selectively attacked by nitric acid to allow recoverymore » of the valuable Am and Cm isotopes. A similar glass composition will allow for safe storage of surplus plutonium. This paper will address the composition, relative durability, and dissolution rate characteristics of the actinide glass, Loeffler Target, that will be used in the Americium/Curium Vitrification Project at Westinghouse Savannah River Company near Aiken, South Carolina. The first part discusses the tests performed on the Loeffler Target Glass concerning instantaneous dissolution rates. The second part presents information concerning pseudo-activation energy for the one week glass dissolution process.« less

XAS and TRLIF spectroscopy of uranium and neptunium in seawater.

PubMed

Maloubier, Melody; Solari, Pier Lorenzo; Moisy, Philippe; Monfort, Marguerite; Den Auwer, Christophe; Moulin, Christophe

2015-03-28

Seawater contains radionuclides at environmental levels; some are naturally present and others come from anthropogenic nuclear activity. In this report, the molecular speciation in seawater of uranium(VI) and neptunium(V) at a concentration of 5 × 10(-5) M has been investigated for the first time using a combination of two spectroscopic techniques: Time-resolved laser-induced fluorescence (TRLIF) for U and extended X-ray absorption fine structure (EXAFS) for U and Np at the LIII edge. In parallel, the theoretical speciation of uranium and neptunium in seawater at the same concentration is also discussed and compared to spectroscopic data. The uranium complex was identified as the neutral carbonato calcic complex UO2(CO3)3Ca2, which has been previously described in other natural systems. In the case of neptunium, the complex identified is mainly a carbonato complex whose exact stoichiometry is more difficult to assess. The knowledge of the actinide molecular speciation and reactivity in seawater is of fundamental interest in the particular case of uranium recovery and more generally regarding the actinide life cycle within the biosphere in the case of accidental release. This is the first report of actinide direct speciation in seawater medium that can complement inventory data.

Determination of Uncertainties for +III and +IV Actinide Solubilities in the WIPP Geochemistry Model for the 2009 Compliance Recertification Application

NASA Astrophysics Data System (ADS)

Ismail, A. E.; Xiong, Y.; Nowak, E. J.; Brush, L. H.

2009-12-01

The Waste Isolation Pilot Plant (WIPP) is a U.S. Department of Energy (DOE) repository in southeast New Mexico for defense-related transuranic (TRU) waste. Every five years, the DOE is required to submit an application to the Environmental Protection Agency (EPA) demonstrating the WIPP’s continuing compliance with the applicable EPA regulations governing the repository. Part of this recertification effort involves a performance assessment—a probabilistic evaluation of the repository performance with respect to regulatory limits on the amount of releases from the repository to the accessible environment. One of the models used as part of the performance assessment process is a geochemistry model, which predicts solubilities of the radionuclides in the brines that may enter the repository in the different scenarios considered by the performance assessment. The dissolved actinide source term comprises actinide solubilities, which are input parameters for modeling the transport of radionuclides as a result of brine flow through and from the repository. During a performance assessment, the solubilities are modeled as the product of a “base” solubility determined from calculations based on the chemical conditions expected in the repository, and an uncertainty factor that describes the potential deviations of the model from expected behavior. We will focus here on a discussion of the uncertainties. To compute a cumulative distribution function (CDF) for the uncertainties, we compare published, experimentally measured solubility data to predictions made using the established WIPP geochemistry model. The differences between the solubilities observed for a given experiment and the calculated solubilities from the model are used to form the overall CDF, which is then sampled as part of the performance assessment. We will discuss the methodology used to update the CDF’s for the +III actinides, obtained from data for Nd, Am, and Cm, and the +IV actinides, obtained from data for Th, and present results for the calculations of the updated CDF’s. We compare the CDF’s to the distributions computed for the previous recertification, and discuss the potential impact of the changes on the geochemistry model. This research is funded by WIPP programs administered by the U.S. Department of Energy. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.

Site preferences of actinide cations in [NZP] compounds

NASA Astrophysics Data System (ADS)

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

2000-07-01

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

Low temperature route to uranium nitride

DOEpatents

Burrell, Anthony K.; Sattelberger, Alfred P.; Yeamans, Charles; Hartmann, Thomas; Silva, G. W. Chinthaka; Cerefice, Gary; Czerwinski, Kenneth R.

2009-09-01

A method of preparing an actinide nitride fuel for nuclear reactors is provided. The method comprises the steps of a) providing at least one actinide oxide and optionally zirconium oxide; b) mixing the oxide with a source of hydrogen fluoride for a period of time and at a temperature sufficient to convert the oxide to a fluoride salt; c) heating the fluoride salt to remove water; d) heating the fluoride salt in a nitrogen atmosphere for a period of time and at a temperature sufficient to convert the fluorides to nitrides; and e) heating the nitrides under vacuum and/or inert atmosphere for a period of time sufficient to convert the nitrides to mononitrides.

Rapid methods for the isolation of actinides Sr, Tc and Po from raw urine.

PubMed

McAlister, Daniel R; Horwitz, E Philip; Harvey, James T

2011-08-01

Rapid methods for the isolation and analysis of individual actinides (Th, U, Pu, Am/Cm) and Sr, Tc and Po from small volumes of raw urine have been developed. The methods involve acidification of the sample and the addition of aluminum nitrate or aluminum chloride salting-out agent prior to isolation of the desired analyte using a tandem combination of prefilter material and extraction chromatographic resin. The method has been applied to the separation of individual analytes from spiked urine samples. Analytes were recovered in high yield and radionuclide purity with separation times as low as 30 min. The chemistry employed is compatible with automation on the ARSIIe instrument.

SEPARATION OF METAL SALTS BY ADSORPTION

DOEpatents

Gruen, D.M.

1959-01-20

It has been found that certain metal salts, particularly the halides of iron, cobalt, nickel, and the actinide metals, arc readily absorbed on aluminum oxide, while certain other salts, particularly rare earth metal halides, are not so absorbed. Use is made of this discovery to separate uranium from the rare earths. The metal salts are first dissolved in a molten mixture of alkali metal nitrates, e.g., the eutectic mixture of lithium nitrate and potassium nitrate, and then the molten salt solution is contacted with alumina, either by slurrying or by passing the salt solution through an absorption tower. The process is particularly valuable for the separation of actinides from lanthanum-group rare earths.

Simulation of Fast Neutronics in an Accelerator-Driven Sub-Critical Core

NASA Astrophysics Data System (ADS)

Gwyn Rosaire, C.; Sattarov, Akhdiyor; McIntyre, Peter; Tsvetkov, Pavel

2011-10-01

Accelerator-driven subcritical fission in a molten salt core (ADSMS) is being developed as a technology for green nuclear power. ADSMS burns its fertile fuel to completion, it cannot melt down, and it destroys long-lived minor actinides. The ADSMS core consists of a vessel filled with a molten salt eutectic of UCl3 and NaCl. The fast neutronics of ADSMS makes possible two unique benefits: isobreeding, a steady-state equilibrium in which ^238U is bred to ^239Pu and the ^239Pu fissions, and destruction of minor actinides, in which fission of the intermediary nuclides dominates of breeding. Results of simulations of the fast neutronics in the ADSMS core will be presented.

Dual roles of f electrons in mixing Al 3 p character into d -orbital conduction bands for lanthanide and actinide dialuminides

DOE PAGES

Altman, Alison B.; Pemmaraju, C. D.; Alayoglu, Selim; ...

2018-01-15

Correlated electron phenomena in lanthanide and actinide materials are driven by a complex interplay between the f and d orbitals. Here in this study, aluminum K-edge x-ray absorption spectroscopy and density functional theory calculations are used to evaluate the electronic structure of the dialuminides, MAl 2 (M = Ce, Sm, Eu, Yb, Lu, U, and Pu). The results show how the energy and occupancy of the 4f or 5f orbitals impacts mixing of Al 3p character into the 5d or 6d conduction bands, which has implications for understanding the magnetic and structural properties of correlated electron systems.

Radiation and Thermal Ageing of Nuclear Waste Glass

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

Weber, William J

2014-01-01

The radioactive decay of fission products and actinides incorporated into nuclear waste glass leads to self-heating and self-radiation effects that may affect the stability, structure and performance of the glass in a closed system. Short-lived fission products cause significant self-heating for the first 600 years. Alpha decay of the actinides leads to self-radiation damage that can be significant after a few hundred years, and over the long time periods of geologic disposal, the accumulation of helium and radiation damage from alpha decay may lead to swelling, microstructural evolution and changes in mechanical properties. Four decades of research on the behaviormore » of nuclear waste glass are reviewed.« less

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.

Ageing of a phosphate ceramic used to immobilize chloride contaminated actinide waste

NASA Astrophysics Data System (ADS)

Metcalfe, B. L.; Donald, I. W.; Fong, S. K.; Gerrard, L. A.; Strachan, D. M.; Scheele, R. D.

2009-03-01

A process for the immobilization of intermediate level waste containing a significant quantity of chloride using Ca3(PO4)2 as the host material has been developed. Waste ions are incorporated into two phosphate-based phases, chlorapatite [Ca5(PO4)3Cl] and spodiosite [Ca2(PO4)Cl]. Non-active trials performed using Sm as the actinide surrogate demonstrated the durability of these phases in aqueous solution. Trials of the process, in which actinide-doped materials were used, were performed at PNNL which confirmed the wasteform resistant to aqueous leaching. Initial leach trials conducted on 239Pu/241Am loaded ceramic at 313 K/28 days gave normalized mass losses of 1.2 × 10-5 g m-2 and 2.7 × 10-3 g m-2 for Pu and Cl, respectively. In order to assess the response of the phases to radiation-induced damage, accelerated ageing trials were performed on samples in which the 239Pu was replaced with 238Pu. No changes to the crystalline structure of the waste were detected in the XRD spectra after the samples had experienced an α radiation fluence of 4 × 1018 g-1. Leach trials showed that there was an increase in the P and Ca release rates but no change in the Pu release rate.

Optimisation of composite metallic fuel for minor actinide transmutation in an accelerator-driven system

NASA Astrophysics Data System (ADS)

Uyttenhove, W.; Sobolev, V.; Maschek, W.

2011-09-01

A potential option for neutralization of minor actinides (MA) accumulated in spent nuclear fuel of light water reactors (LWRs) is their transmutation in dedicated accelerator-driven systems (ADS). A promising fuel candidate dedicated to MA transmutation is a CERMET composite with Mo metal matrix and (Pu, Np, Am, Cm)O 2-x fuel particles. Results of optimisation studies of the CERMET fuel targeting to increasing the MA transmutation efficiency of the EFIT (European Facility for Industrial Transmutation) core are presented. In the adopted strategy of MA burning the plutonium (Pu) balance of the core is minimized, allowing a reduction in the reactivity swing and the peak power form-factor deviation and an extension of the cycle duration. The MA/Pu ratio is used as a variable for the fuel optimisation studies. The efficiency of MA transmutation is close to the foreseen theoretical value of 42 kg TW -1 h -1 when level of Pu in the actinide mixture is about 40 wt.%. The obtained results are compared with the reference case of the EFIT core loaded with the composite CERCER fuel, where fuel particles are incorporated in a ceramic magnesia matrix. The results of this study offer additional information for the EFIT fuel selection.

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

SiC Schottky Diode Detectors for Measurement of Actinide Concentrations from Alpha Activities in Molten Salt Electrolyte

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

Windl, Wolfgang; Blue, Thomas

In this project, we have designed a 4H-SiC Schottky diode detector device in order to monitor actinide concentrations in extreme environments, such as present in pyroprocessing of spent fuel. For the first time, we have demonstrated high temperature operation of such a device up to 500 °C in successfully detecting alpha particles. We have used Am-241 as an alpha source for our laboratory experiments. Along with the experiments, we have developed a multiscale model to study the phenomena controlling the device behavior and to be able to predict the device performance. Our multiscale model consists of ab initio modeling tomore » understand defect energetics and their effect on electronic structure and carrier mobility in the material. Further, we have developed the basis for a damage evolution model incorporating the outputs from ab initio model in order to predict respective defect concentrations in the device material. Finally, a fully equipped TCAD-based device model has been developed to study the phenomena controlling the device behavior. Using this model, we have proven our concept that the detector is capable of performing alpha detection in a salt bath with the mixtures of actinides present in a pyroprocessing environment.« less

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.

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

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.

Mixed Metal Phosphonate- Phosphate Resins for Separation of Lanthanides from Actinides

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

Clearfield, Abraham

As indicated in the previous annual report the goals of this project are to develop procedures for efficient separation of lanthanides from actinides and curium from americium. These processes are required for the nuclear fuel cycle to minimize the waste and recover the valuable actinides. The basis for our study is that we have prepared a group of compounds that are porous and favor the uptake of ions with charges 3+ and 4+ over ions of lesser charge. The general formula for these materials is M(O 3PC 6H 4PO 3) 1-x/2(APO 4)x·nH 2O: where M=Zr 4+, Sn 4+, A=H, Na,more » or K and X=O, 0.5, 0.8, 1.0, 1.33 and 1.61-3. One of our tasks is to determine which members of this group of compounds are effective in carrying out the required separations. A difficulty in obtaining this required information is that the compounds are amorphous. That is they are not crystalline, therefore we need to resort to synchrotron data to obtain structural data which will be presented in detail. This information will be provided as a separate section.« less

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.

Demonstration of the TRUEX process for partitioning of actinides from actual ICPP tank waste using centrifugal contactors in a shielded cell facility

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

Law, J.D.; Brewer, K.N.; Herbst, R.S.

1996-09-01

TRUEX is being evaluated at Idaho Chemical Processing Plant (ICPP) for separating actinides from acidic radioactive waste stored at ICPP; efforts have culminated in a recent demonstration with actual tank waste. A continuous countercurrent flowsheet test was successfully completed at ICPP using waste from tank WM-183. This demonstration was performed using 24 states of 2-cm dia centrifugal contactors in the shielded hot cell at the ICPP Remote Analytical Laboratory. The flowsheet had 8 extraction stages, 5 scrub stages, 6 strip stages, 3 solvent wash stages, and 2 acid rinse stages. A centrifugal contactor stage in the scrub section was notmore » working during testing, and the scrub feed (aqueous) solution followed the solvent into the strip section, eliminating the scrub section in the flowsheet. An overall removal efficiency of 99.97% was obtained for the actinides, reducing the activity from 457 nCi/g in the feed to 0.12 nCi/g in the aqueous raffinate, well below the NRC Class A LLW requirement of 10 nCi/g for non-TRU waste.The 0.04 M HEDPA strip section back-extracted 99.9998% of the actinide from the TRUEX solvent. Removal efficiencies of >99. 90, 99.96, 99.98, >98.89, 93.3, and 89% were obtained for {sup 241}Am, {sup 238}Pu, {sup 239}Pu, {sup 235}U, {sup 238}U, and {sup 99}Tc. Fe was partially extracted by the TRUEX solvent, resulting in 23% of the Fe exiting in the strip product. Hg was also extracted by the TRUEX solvent (73%) and stripped from the solvent in the 0.25 M Na2CO3 wash section. Only 1.4% of the Hg exited with the high activity waste strip product.« less

Analysis methodology and development of a statistical tool for biodistribution data from internal contamination with actinides.

PubMed

Lamart, Stephanie; Griffiths, Nina M; Tchitchek, Nicolas; Angulo, Jaime F; Van der Meeren, Anne

2017-03-01

The aim of this work was to develop a computational tool that integrates several statistical analysis features for biodistribution data from internal contamination experiments. These data represent actinide levels in biological compartments as a function of time and are derived from activity measurements in tissues and excreta. These experiments aim at assessing the influence of different contamination conditions (e.g. intake route or radioelement) on the biological behavior of the contaminant. The ever increasing number of datasets and diversity of experimental conditions make the handling and analysis of biodistribution data difficult. This work sought to facilitate the statistical analysis of a large number of datasets and the comparison of results from diverse experimental conditions. Functional modules were developed using the open-source programming language R to facilitate specific operations: descriptive statistics, visual comparison, curve fitting, and implementation of biokinetic models. In addition, the structure of the datasets was harmonized using the same table format. Analysis outputs can be written in text files and updated data can be written in the consistent table format. Hence, a data repository is built progressively, which is essential for the optimal use of animal data. Graphical representations can be automatically generated and saved as image files. The resulting computational tool was applied using data derived from wound contamination experiments conducted under different conditions. In facilitating biodistribution data handling and statistical analyses, this computational tool ensures faster analyses and a better reproducibility compared with the use of multiple office software applications. Furthermore, re-analysis of archival data and comparison of data from different sources is made much easier. Hence this tool will help to understand better the influence of contamination characteristics on actinide biokinetics. Our approach can aid the optimization of treatment protocols and therefore contribute to the improvement of the medical response after internal contamination with actinides.

Bias estimates used in lieu of validation of fission products and minor actinides in MCNP K eff calculations for PWR burnup credit casks

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

Mueller, Don E.; Marshall, William J.; Wagner, John C.

The U.S. Nuclear Regulatory Commission (NRC) Division of Spent Fuel Storage and Transportation recently issued Interim Staff Guidance (ISG) 8, Revision 3. This ISG provides guidance for burnup credit (BUC) analyses supporting transport and storage of PWR pressurized water reactor (PWR) fuel in casks. Revision 3 includes guidance for addressing validation of criticality (k eff) calculations crediting the presence of a limited set of fission products and minor actinides (FP&MA). Based on previous work documented in NUREG/CR-7109, recommendation 4 of ISG-8, Rev. 3, includes a recommendation to use 1.5 or 3% of the FP&MA worth to conservatively cover the biasmore » due to the specified FP&MAs. This bias is supplementary to the bias and bias uncertainty resulting from validation of k eff calculations for the major actinides in SNF and does not address extension to actinides and fission products beyond those identified herein. The work described in this report involves comparison of FP&MA worths calculated using SCALE and MCNP with ENDF/B-V, -VI, and -VII based nuclear data and supports use of the 1.5% FP&MA worth bias when either SCALE or MCNP codes are used for criticality calculations, provided the other conditions of the recommendation 4 are met. The method used in this report may also be applied to demonstrate the applicability of the 1.5% FP&MA worth bias to other codes using ENDF/B V, VI or VII based nuclear data. The method involves use of the applicant s computational method to generate FP&MA worths for a reference SNF cask model using specified spent fuel compositions. The applicant s FP&MA worths are then compared to reference values provided in this report. The applicants FP&MA worths should not exceed the reference results by more than 1.5% of the reference FP&MA worths.« 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

Rational Ligand Design for U(VI) and Pu(IV)

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

Szigethy, Geza

2009-08-12

Nuclear power is an attractive alternative to hydrocarbon-based energy production at a time when moving away from carbon-producing processes is widely accepted as a significant developmental need. Hence, the radioactive actinide power sources for this industry are necessarily becoming more widespread, which is accompanied by the increased risk of exposure to both biological and environmental systems. This, in turn, requires the development of technology designed to remove such radioactive threats efficiently and selectively from contaminated material, whether that be contained nuclear waste streams or the human body. Raymond and coworkers (University of California, Berkeley) have for decades investigated the interactionmore » of biologically-inspired, hard Lewis-base ligands with high-valent, early-actinide cations. It has been established that such ligands bind strongly to the hard Lewis-acidic early actinides, and many poly-bidentate ligands have been developed and shown to be effective chelators of actinide contaminants in vivo. Work reported herein explores the effect of ligand geometry on the linear U(IV) dioxo dication (uranyl, UO 2 2+). The goal is to utilize rational ligand design to develop ligands that exhibit shape selectivity towards linear dioxo cations and provides thermodynamically favorable binding interactions. The uranyl complexes with a series of tetradentate 3-hydroxy-pyridin-2-one (3,2-HOPO) ligands were studied in both the crystalline state as well as in solution. Despite significant geometric differences, the uranyl affinities of these ligands vary only slightly but are better than DTPA, the only FDA-approved chelation therapy for actinide contamination. The terepthalamide (TAM) moiety was combined into tris-beidentate ligands with 1,2- and 3,2-HOPO moieties were combined into hexadentate ligands whose structural preferences and solution thermodynamics were measured with the uranyl cation. In addition to achieving coordinative saturation, these ligands exhibited increased uranyl affinity compared to bis-Me-3,2-HOPO ligands. This result is due in part to their increased denticity, but is primarily the result of the presence of the TAM moiety. In an effort to explore the relatively unexplored coordination chemistry of Pu(IV) with bidentate moieties, a series of Pu(IV) complexes were also crystallized using bidentate hydroxypyridinone and hydroxypyrone ligands. The geometries of these complexes are compared to that of the analogous Ce(IV) complexes. While in some cases these showed the expected structural similarities, some ligand systems led to significant coordination changes. A series of crystal structure analyses with Ce(IV) indicated that these differences are most likely the result of crystallization condition differences and solvent inclusion effects.« 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.

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

Exploratory study of fission product yields of neutron-induced fission of U 235 ,   U 238 , and Pu 239 at 8.9 MeV

DOE PAGES

Bhatia, C.; Fallin, B. F.; Gooden, M. E.; ...

2015-06-05

Using dual-fission chambers each loaded with a thick (200–400–mg/cm 2) actinide target of 235,238U or 239Pu and two thin (~10–100–μg/cm 2) reference foils of the same actinide, the cumulative yields of fission products ranging from 92Sr to 147Nd have been measured at E n = 8.9MeV. The 2H(d,n) 3He reaction provided the quasimonoenergetic neutron beam. Here, the experimental setup and methods used to determine the fission product yield (FPY) are described, and results for typically eight high-yield fission products are presented.

Electrochemistry of actinides and fission products in molten salts-Data review

NASA Astrophysics Data System (ADS)

Zhang, Jinsuo

2014-04-01

The thermodynamic and electrochemical properties of actinides and fission products in the molten salt determine the pyroprocessing separation performance. Extensive measurements have been carried out to provide fundamental data for evaluating the separation efficiency and technology feasibility of pyroprocessing although the technology has been very well developed in laboratory. The state of the art of fundamental data for substance or materials involved in pyropocessing will be reviewed in the present article. The available data will be summarized and reanalyzed. New correlations, which extend the available data to a broad range of applications, will be developed based on available data from different measurements. Further research topics on providing fundamental data that is needed for scaling the current laboratory technology to industrial applications are identified.

Feasibility of space disposal of radioactive nuclear waste. 2: Technical summary

NASA Technical Reports Server (NTRS)

1974-01-01

The feasibility of transporting radioactive waste produced in the process of generating electricity in nuclear powerplants into space for ultimate disposal was investigated at the request of the AEC as a NASA in-house effort. The investigation is part of a broad AEC study of methods for long-term storage or disposal of radioactive waste. The results of the study indicate that transporting specific radioactive wastes, particularly the actinides with very long half-lives, into space using the space shuttle/tug as the launch system, appears feasible from the engineering and safety viewpoints. The space transportation costs for ejecting the actinides out of the solar system would represent less than a 5-percent increase in the average consumer's electric bill.

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

NASA Astrophysics Data System (ADS)

Garza, Alejandro J.; Sousa Alencar, Ana G.; Scuseria, Gustavo E.

2015-12-01

Singlet-paired coupled cluster doubles (CCD0) is a simplification of CCD that relinquishes a fraction of dynamic correlation in order to be able to describe static correlation. Combinations of CCD0 with density functionals that recover specifically the dynamic correlation missing in the former have also been developed recently. Here, we assess the accuracy of CCD0 and CCD0+DFT (and variants of these using Brueckner orbitals) as compared to well-established quantum chemical methods for describing ground-state properties of singlet actinide molecules. The f0 actinyl series (UO22+, NpO23+, PuO24+), the isoelectronic NUN, and thorium (ThO, ThO2+) and nobelium (NoO, NoO2) oxides are studied.

Separation and preconcentration of actinides from concentrated nitric acid by extraction chromatography in microsystems.

PubMed

Losno, Marion; Pellé, Julien; Marie, Mylène; Ferrante, Ivan; Brennetot, René; Descroix, Stéphanie; Mariet, Clarisse

2018-08-01

An original method of monolith impregnation in microsystem for the analysis of radionuclides in nitric acid is reported. Three microcolumns made of monolith poly(AMA-co-EDMA) were impregnated in COC microsystems. The robustness of the microsystems in nitric acid media until 8 M was demonstrated. High exchange capacity and affinity for tetravalent and hexavalent actinides in concentrated nitric media were obtained. The retention characteristics of the microcolumns impregnated by TBP, TBP-CMPO and DAAP were compared with those of the equivalent commercial particulate resins TBP™, TRU™ and UTEVA™ respectively. The separation of U, Th and Eu was validated in a classical microsystem and a procedure is proposed in a centrifugal microsystem. Copyright © 2018. Published by Elsevier B.V.

GTA Welding Research and Development for Plutonium Containment

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

Sessions, C.E.

2002-02-21

This paper discusses the development of two welding systems that are used to contain actinide metals and oxides for long term storage. The systems are termed the bagless transfer system (BTS) and the outer container welder (OCW) system. The BTS is so named because it permits the containment of actinides without a polymeric package (i.e., bag). The development of these two systems was directed by Department of Energy Standard 3013, hereafter referred to as DOE 3013. This document defines the product and container requirements. In addition, it references national codes and standards for leak rates, ANSI N14.5, and design, Americanmore » Society of Mechanical Engineers (ASME) Boiler and Pressure Vessel Code Section VIII (BandPVC).« less

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

Fluorination process using catalyst

DOEpatents

Hochel, Robert C.; Saturday, Kathy A.

1985-01-01

A process for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3, AgF.sub.2 and NiF.sub.2, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF.sub.3 and AgF.sub.2, whereby the fluorination is significantly enhanced.

Fluorination process using catalysts

DOEpatents

Hochel, R.C.; Saturday, K.A.

1983-08-25

A process is given for converting an actinide compound selected from the group consisting of uranium oxides, plutonium oxides, uranium tetrafluorides, plutonium tetrafluorides and mixtures of said oxides and tetrafluorides, to the corresponding volatile actinide hexafluoride by fluorination with a stoichiometric excess of fluorine gas. The improvement involves conducting the fluorination of the plutonium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/, AgF/sub 2/ and NiF/sub 2/, whereby the fluorination is significantly enhanced. The improvement also involves conducting the fluorination of one of the uranium compounds in the presence of a fluoride catalyst selected from the group consisting of CoF/sub 3/ and AgF/sub 2/, whereby the fluorination is significantly enhanced.

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.

Plutonium-239 + 240 and Americium-241 in soils east of Rocky Flats, Colorado

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

Litaor, M.I.; Barth, G.R.; Molzer, P.C.

1994-11-01

Soils east of the Rocky Flats (RF) near Golden, CO, were contaminated with Pu-239 + 240 and Am-241 as a result of past waste-storage practices. The physiocochemical parameters that govern the actinides distribution in the soil are poorly understood. Twenty-six soil pits at various distances and directions from a contaminated site at RF were excavated, sampled, and analyzed for actinide activities as well as selected physical, chemical, and mineralogical attributes. Plutonium-239+240 and Am-241 activities in the soils ranged form 164 280 Bq/kg to 0.0037 Bq/kg, decreasing with distance from the source. More than 90% of the Pu-239 + 240 andmore » Am-241 activities were confined to the upper 12 cm of the soil, regardless of the soil characteristics, or distance and direction from the source. Evidence of preferential transport in macropores formed along decayed root channels was observed in four soil pits and had translocated Pu-239 + 240 to a depth of 90 cm. This transport mechanism increased by a factor of 30 the level of Pu-239 + 240 activity at this depth. Earthworm activity is probably important in the redistribution of actinides in the upper 40 cm of many of the soils investigated. Planning of future remedial activities at RF should consider the findings of this contaminant-transport study. 34 refs., 5 figs., 2 tabs.« 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.

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.

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.

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.

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.

Simultaneous separation and detection of actinides in acidic solutions using an extractive scintillating resin.

PubMed

Roane, J E; DeVol, T A

2002-11-01

An extractive scintillating resin was evaluated for the simultaneous separation and detection of actinides in acidic solutions. The transuranic extractive scintillating (TRU-ES) resin is composed of an inert macroporous polystyrene core impregnated with organic fluors (diphenyloxazole and 1,4-bis-(4-methyl-5-phenyl-2-oxazolyl)benzene) and an extractant (octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide in tributyl phosphate). The TRU-ES resin was packed into FEP Teflon tubing to produce a flow cell (0.2-mL free column volume), which is placed into a scintillation detection system to obtain pulse height spectra and time series data during loading and elution of actinides onto/from the resin. The alpha-particle absolute detection efficiencies ranged from 77% to 96.5%, depending on the alpha energy and quench. In addition to the on-line analyses, off-line analyses of the effluent can be conducted using conventional detection methods. The TRU-ES resin was applied to the quantification of a mixed radionuclide solution and two actual waste samples. The on-line characterization of the mixed radionuclide solution was within 10% of the reported activities whereas the agreement with the waste samples was not as good due to sorption onto the sample container walls and the oxidation state of plutonium. Agreement between the on-line and off-line analyses was within 35% of one another for both waste samples.

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

PubMed

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

2017-12-06

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

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

Ellis, D.E.; Gubanov, V.A.; Rosen, A.

The electronic structure of actinide monoxides AcO and dioxides AcO/sub 2/, where Ac = Th, U, Np, Pu, Am, Cm and Bk has been studied by molecular cluster methods based on the first-principles one-electron local density theory. Molecular orbitals for nearest neighbor clusters AcO/sup 10 -//sub 6/ and AcO/sup 12 -//sub 8/ representative of monoxide and dioxide lattices were obtained using non-relativistic spin-restricted and spin-polarized Hartree-Fock-Slater models for the entire series. Fully relativistic Dirac-Slater calculations were performed for ThO, UO and NpO in order to explore magnitude of spin-orbit splittings and level shifts in valence structure. Self-consistent iterations were carriedmore » out for NpO, in which the NpO/sub 6/ cluster was embedded in the molecular field of the solid. Finally, a ''moment polarized'' model which combines both spin-polarization and relativistic effects in a consistent fashion was applied to the NpO system. Covalent mixing of oxygen 2p and Ac 5f orbitals was found to increase rapidly across the actinide series; metal s,p,d covalency was found to be nearly constant. Mulliken atomic population analysis of cluster eigenvectors shows that free-ion crystal field models are unreliable, except for the light actinides. X-ray photoelectron line shapes have been calculated and are found to compare rather well with experimental data on the dioxides.« less

Ageing of a phosphate ceramic used to immobilize chloride-contaminated actinide waste

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

Metcalfe, Brian; Donald, Ian W.; Fong, Shirley K.

2009-03-31

At AWE, we have developed a process for the immobilization of ILW waste containing a significant quantity of chloride with Ca 3(PO 4) 2 as the host material. Waste ions are incorporated into two phosphate-based phases, chlorapatite [Ca 5(PO 4) 3Cl] and spodiosite [Ca 2(PO 4)Cl]. Non-active trials performed at AWE with Sm as the actinide surrogate demonstrated the durability of these phases in aqueous solution. Trials of the process, in which actinide-doped materials were used, wer performed at PNNL where the waste form was found to be resistant to aqueous leaching. Initial leach trials conducted on 239Pu / 241Ammore » loaded ceramic at 40°C/28 days gave normalized mass losses of 1.2 x 10 -5 g.m -2 and 2.7 x 10 -3 g.m -2 for Pu and Cl respectively. In order to assess the response of the phases to radiation-induced damage, accelerated ageing trials were performed on samples in which the 239Pu was replaced with 238Pu. No changes to the crystalline structure of the waste were detected in the XRD patterns after the samples had experienced an α radiation dose of 4 x 10 18 g -1. Leach trials showed that there was an increase in the P and Ca release rates but no change in the Pu release rate.« less

Ageing of a phosphate ceramic used to immobilize chloride contaminated actinide waste

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

Metcalfe, Brian L.; Donald, Ian W.; Fong, Shirley K.

2009-03-31

AWE has developed a process for the immobilization of ILW waste containing a significant quantity of chloride using Ca3(PO4)2 as the host material. Waste ions are incorporated into two phosphate based phases, chlorapatite, Ca5(PO4)3Cl, and spodiosite, Ca2(PO4)Cl. Non-active trials performed at AWE using samarium as the actinide surrogate demonstrated the durability of these phases in aqueous solution. Trials of the process using actinide-doped material were performed at PNNL which confirmed the immobilized wasteform resistant to aqueous leaching. Initial leach trials conducted on 239Pu /241Am loaded ceramic at 40°C/28 days gave normalized mass losses of 1.2 x 10-5 g.m-2 and 2.7more » x 10-3 g.m-2 for Pu and Cl respectively. In order to assess the response of the phases to radiation-induced damage, accelerated ageing trials were performed on samples in which the 239Pu was replaced by 238Pu. No changes to the crystalline structure of the waste were detected using XRD after the samples had experienced a radiation dose of 4 x 1018 α.g-1. Leach trials showed that there had been an increase in the P and Ca release rates but no change in the Pu release rate.« less

Complete recovery of actinides from UREX-like raffinates using a combination of hard and soft donor ligands. II. soft donor structure variation

DOE PAGES

Zalupski, Peter R.; Klaehn, John R.; Peterman, Dean R.

2015-07-30

The feasibility of simultaneous separation of uranium, neptunium, plutonium, americium, and curium from a simulated dissolved used fuel simulant adjusted to 1.0 M nitric acid is investigated using a mixture of the soft donor bis(bis-3,5-trifluoromethyl)phenyl) dithiophosphinic acid (“0”) and the hard donor synergist trioctylphosphine oxide (TOPO) dissolved in toluene. The results reported in this work are compared to our recent demonstration of a complete actinide recovery from a simulated dissolved fuel solution using a synergistic combination of bis(o-trifluoromethylphenyl)dithiophosphinic acid (“1”) and TOPO dissolved in either toluene or trifluoromethylphenyl sulfone. While the extraction efficiency of americium was enhanced for the liquid-liquidmore » system containing “0”, enabling to accomplish a trivalent An/Ln separation at 1.0 M HNO3, the extraction of neptunium was drastically diminished, relative to “1”. The partitioning behavior of curium was also negatively impacted, introducing an effective opportunity for americium/curium separation. Radiometric and spectrophotometric studies demonstrate that the complete actinide recovery using the solvent based upon “0” and TOPO is not feasible. Additionally, the importance of radiolytic degradation processes is discussed through the comparisons of extraction properties of liquid-liquid systems based on both soft donor reagents.« less

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

Diaconescu, Paula L.; Garcia, Evan

The objective of our research project was to study the reactivity of uranium complexes supported by ferrocene-based ligands. In addition, this research provides training of graduate students as the next generation of actinide scientists.

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

REMOVAL OF RADIOACTIVE IONS FROM WATERS

DOEpatents

Silker, W.B.

1962-04-10

A process for removing neutron-reaction products, such as phosphorus, arsenic, manganese, copper, zinc, lanthanides, and actinides, from aqueous solutions by sorption on particles of aluminum metal is described. (AEC)

Nuclear fuel alloys or mixtures and method of making thereof

DOEpatents

Mariani, Robert Dominick; Porter, Douglas Lloyd

2016-04-05

Nuclear fuel alloys or mixtures and methods of making nuclear fuel mixtures are provided. Pseudo-binary actinide-M fuel mixtures form alloys and exhibit: body-centered cubic solid phases at low temperatures; high solidus temperatures; and/or minimal or no reaction or inter-diffusion with steel and other cladding materials. Methods described herein through metallurgical and thermodynamics advancements guide the selection of amounts of fuel mixture components by use of phase diagrams. Weight percentages for components of a metallic additive to an actinide fuel are selected in a solid phase region of an isothermal phase diagram taken at a temperature below an upper temperature limit for the resulting fuel mixture in reactor use. Fuel mixtures include uranium-molybdenum-tungsten, uranium-molybdenum-tantalum, molybdenum-titanium-zirconium, and uranium-molybdenum-titanium systems.

CACAO: A project for a laboratory for the production and characterization of thin radioactive layers

NASA Astrophysics Data System (ADS)

Bacri, C. O.; Petitbon, V.; Pierre, S.; Cacao Group

2010-02-01

CACAO, Chimie des Actinides et Cibles radioActives à Orsay (actinide chemistry and radioactive targets at Orsay), is a project under construction that consists of the installation of a hot laboratory dedicated to the production and characterization of thin radioactive layers. The project aims to be a joint CNRS-CEA national laboratory to overcome difficulties related mainly to safety issues and to the lack of knowledge and potential manpower. The first goal is to fulfill, at least, the needs of the whole French community, and to be able to coordinate the different activities related to radioactive targets. For this purpose, itis important to be complementary to already existing international installations. Inside this framework, it will of course be possible to produce and/or characterize targets for other users.

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

Bernard, D.; Fabbris, O.

Two different experiments performed in the 8 MWth MELUSINE experimental power pool reactor aimed at analyzing 1 GWd/t spent fuel pellets doped with several actinides. The goal was to measure the averaged neutron induced capture cross section in two very different neutron spectra (a PWR-like and an under-moderated one). This paper summarizes the combined deterministic APOLLO2-stochastic TRIPOLI4 analysis using the JEFF-3.1.1 European nuclear data library. A very good agreement is observed for most of neutron induced capture cross section of actinides and a clear underestimation for the {sup 241}Am(n,{gamma}) as an accurate validation of its associated isomeric ratio are emphasized.more » Finally, a possible huge resonant fluctuation (factor of 2.7 regarding to the 1=0 resonance total orbital momenta) is suggested for isomeric ratio. (authors)« less

Dynamical approach to heavy-ion induced fusion using actinide target

NASA Astrophysics Data System (ADS)

Aritomo, Y.; Hagino, K.; Chiba, S.; Nishio, K.

2012-10-01

To treat heavy-ion reactions using actinide target nucleus, we propose a model which takes into account the coupling to the collective states of interacting nuclei in the penetration of the Coulomb barrier and the dynamical evolution of nuclear shape from the contact configuration. A fluctuation-dissipation model (Langevin equation) was applied in the dynamical calculation, where effect of nuclear orientation at the initial impact on the prolately deformed target nucleus was considered. Using this model, we analyzed the experimental data for the mass distribution of fission fragments (MDFF) in the reaction of 36S+238U at several incident energies. Fusion-fission, quasifission and deep-quasi-fission are separated as different trajectories on the potential energy surface. We estimated the fusion cross section of the reaction.

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.;

Crystal field effect in light actinide dioxides and oxychalcogenides-a unified phenomenological description

NASA Astrophysics Data System (ADS)

Gajek, Z.

2004-05-01

The electronic properties of the actinide ions in the series of semi-conducting, antiferromagnetic compounds: dioxides, AnO2 and oxychalcogenides, AnOY, where An=U, Np and Y=S, Se, are re-examined from the point of view of the consistency of the crystal field (CF) model. The discussion is based on the supposition that the effective metal-ligand interaction solely determines the net CF effect in non-metallic compounds. The main question we address here is, whether a reliable, consistent description of the CF effect in terms of the intrinsic parameters can be achieved for this particular family of compounds. Encouraging calculations reported previously for the AnO2 and UOY series serve as a reference data in the present estimation of electronic structure parameters for neptunium oxychalcogenides.

Predictions of Actinide Solubilities under Near-Field Conditions Expected in the WIPP

NASA Astrophysics Data System (ADS)

Brush, L. H.; Xiong, Y.

2009-12-01

The Waste Isolation Pilot Plant (WIPP) is a U.S. Department of Energy (DOE) repository in southeast New Mexico for defense-related transuranic (TRU) waste. The repository, which opened in March 1999, is located at a subsurface depth of 655 m (2150 ft) in the Salado Fm., a Permian bedded-salt formation. The repository will eventually contain the equivalent of 844,000 208 L (55 gal) drums of TRU waste. After filling the rooms and access drifts and installing panel closures, creep closure of the salt will crush the steel waste containers in most cases and encapsulate the waste. The WIPP actinide source term model used for long-term performance assessment (PA) of the repository comprises dissolved and suspended submodels (solubilities and colloids). This presentation will describe the solubilities. From the standpoint of long-term PA, the order of importance of the radioelements in the TRU waste to be emplaced in the WIPP is Pu ~ Am >> U > Th >> Np ~ Cm and fission products. The DOE has included all of these actinides, but not fission products, in the WIPP Actinide Source Term Program (ASTP). Anoxic corrosion of Fe- and Al-base metals and microbial consumption of cellulosic, plastic, and rubber materials will produce gas and create strongly reducing conditions in the WIPP after closure. The use of MgO as an engineered barrier to consume microbially produced CO2 will result in low fCO2 and basic pH. Under these conditions, Th, U, Np, Pu, and Am will speciate essentially entirely as Th(IV), U(IV), Np(IV), Pu(III), and Am(III); or Th(IV), U(VI), Np(V), Pu(IV), and Am(III). The DOE has developed thermodynamic speciation-and-solubility models for +III, +IV, and +V actinides in brines. Experimental data for Nd, Am, and Cm species were used to parameterize the +III Pitzer activity-coefficient model; data for Th species were used for the +IV model; and data for Np(V) species were used for the +V model. These models include the effects of the organic ligands acetate, citrate, EDTA, and oxalate in TRU waste. The oxidation-state analogy was then used to extend the +III model to Pu(III), and the +IV model to Pu(IV), U(IV), and Np(IV). The solubility of U(VI) was estimated. For the recent WIPP Compliance Recertification Application PA Baseline Calculations, we calculated actinide solubilities with fCO2 buffered at 3.14 × 10-6 atm by the brucite-hydromagnesite carbonation reaction, with pH maintained at ~9 by the brucite dissolution-precipitation reaction, and with estimated concentrations of the organic ligands in brines from the Salado and the Castile Fm., which underlies the Salado. The calculated +III, +IV, and +V solubilities are 1.56 × 10-6, 5.64 × 10-8, and 4.07 × 10-7 M, respectively, in Salado brine; and 1.51 × 10-6, 6.98 × 10-8, and 8.75 × 10-7 M in Castile brine. The U(VI) solubility estimated for both brines is 1 × 10-3 M. This research is funded by WIPP programs administered by the U.S. Department of Energy. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.

Investigation of the feasibility of a small scale transmutation device

NASA Astrophysics Data System (ADS)

Sit, Roger Carson

This dissertation presents the design and feasibility of a small-scale, fusion-based transmutation device incorporating a commercially available neutron generator. It also presents the design features necessary to optimize the device and render it practical for the transmutation of selected long-lived fission products and actinides. Four conceptual designs of a transmutation device were used to study the transformation of seven radionuclides: long-lived fission products (Tc-99 and I-129), short-lived fission products (Cs-137 and Sr-90), and selective actinides (Am-241, Pu-238, and Pu-239). These radionuclides were chosen because they are major components of spent nuclear fuel and also because they exist as legacy sources that are being stored pending a decision regarding their ultimate disposition. The four designs include the use of two different devices; a Deuterium-Deuterium (D-D) neutron generator (for one design) and a Deuterium-Tritium (D-T) neutron generator (for three designs) in configurations which provide different neutron energy spectra for targeting the radionuclide for transmutation. Key parameters analyzed include total fluence and flux requirements; transmutation effectiveness measured as irradiation effective half-life; and activation products generated along with their characteristics: activity, dose rate, decay, and ingestion and inhalation radiotoxicity. From this investigation, conclusions were drawn about the feasibility of the device, the design and technology enhancements that would be required to make transmutation practical, the most beneficial design for each radionuclide, the consequence of the transmutation, and radiation protection issues that are important for the conceptual design of the transmutation device. Key conclusions from this investigation include: (1) the transmutation of long-lived fission products and select actinides can be practical using a small-scale, fusion driven transmutation device; (2) the transmutation of long-lived fission products could result in an irradiation effective half-life of a few years with a three order magnitude increase in the on-target neutron flux accomplishable through a combination of technological enhancements to the source and system design optimization; (3) the transmutation of long-lived fission products requires a thermal-slow energy spectrum to prevent the generation of activation products with half-lives even longer than the original radionuclide; (4) there is no benefit in trying to transmute short-lived fission products due to the ineffectiveness of the transmutation process and the generation of a multiplicity of counterproductive activation products; (5) for actinides, irradiation effective half-lives of < 1 year can be achieved with a four orders magnitude increase in the on-target flux; (6) the ideal neutron energy spectra for transmuting actinides is highly dependent on the particular radionuclide and its fission-to-capture ratio as they determine the generationrate of other actinides; and (7) the methodology developed in this dissertation provides a mechanism that can be used for studying the feasibility of transmuting other radionuclides, and its application can be extended to studying the production of radionuclides of interest in a transmutation process. Although large-scale transmutation technology is presently being researched world-wide for spent fuel management applications, such technology will not be viable for a couple of decades. This dissertation investigated the concept of a small-scale transmutation device using present technology. The results of this research show that with reasonable enhancements, transmutation of specific radionuclides can be practical in the near term.

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

R. Wigeland; T. Taiwo; M. Todosow

The recently completed comprehensive evaluation and screening of nuclear fuel cycle options identified a number of potentially promising fuel cycles for R&D that offer what could be considered by decision-makers as having the potential for significant improvement compared to the current U.S. fuel cycle. The fuel cycles that consistently performed the best were recycle fuel cycles that used self-sustaining fast reactors operating with either U/Pu or U/TRU recycle fuel and also included options where the fast reactors provided fissile materials to support operation of thermal reactors. However, based on the evaluation criteria and metrics used in the study, there wasmore » no difference in benefit between recycle of U/Pu and U/TRU (where TRU is plutonium and the minor actinides) while there were differences in the challenges for developing and deploying such fuel cycles, with U/TRU recycle being more challenging. This observation prompted the question as to the desirability of pursuing R&D on U/TRU recycle given that there may not be an increase in benefit. As a result, activities have been pursued to further investigate the performance differences between U/Pu and U/TRU recycle based on considering issues beyond those used in the evaluation and screening study to identify, if possible, areas where there are significant benefits of U/TRU recycle compared to U/Pu recycle. These new considerations focused on several areas, but especially on the impact on disposal of the HLW, which in the case of U/Pu recycle contains all of the minor actinides along with fission products, while in the case of U/TRU recycle only contains the losses of minor actinides from the reprocessing and recycle fuel fabrication operations. This difference in content has several implications. One impact is on the time dependent decay heat which can affect handling and the use of space in a geologic repository. Another impact concerns the HLW form and volume, since presence of minor actinides may adversely affect the ability to reduce HLW volume. The short-term radioactivity and long-term radiotoxicity of the HLW is also affected, which may be of more or less importance depending on the specific geologic disposal environment. To study these potential effects, a range of waste forms and disposal environments were used in the analysis, documenting to what extent the recycle of minor actinides in addition to plutonium may offer further benefit. Another area of investigation concerned the recycle fuel, for the fast reactor and for the thermal reactors they may support. Information to date indicates that U/Pu fuel may be simpler to fabricate and has a much more extensive database than U/TRU fuel, one of the reasons for the increased challenge for developing and deploying a U/TRU fuel cycle, and also indicates that heterogeneous recycle of the minor actinides may be even more difficult as compared to homogeneous recycle. This information was reviewed and updated to reflect the most recent studies for the purpose of informing on all aspects of the differences between U/Pu and U/TRU recycle. The results of all of these investigations will be presented to provide information on the findings concerning the value of U/TRU recycle.« less

Electron-Transfer-Enhanced Cation-Cation Interactions in Homo- and Heterobimetallic Actinide Complexes: A Relativistic Density Functional Theory Study.

PubMed

Zheng, Ming; Chen, Fang-Yuan; Tian, Jia-Nan; Pan, Qing-Jiang

2018-04-02

To provide deep insight into cation-cation interactions (CCIs) involving hexavalent actinyl species that are major components in spent nuclear fuel and pose important implications for the effective removal of radiotoxic pollutants in the environment, a series of homo- and heterobimetallic actinide complexes supported by cyclopentadienyl (Cp) and polypyrrolic macrocycle (H 4 L) ligands were systematically investigated using relativistic density functional theory. The metal sort in both parts of (THF)(H 2 L)(OAn VI O) and (An') III Cp 3 from U to Np to Pu, as well as the substituent bonding to Cp from electron-donating Me to H to electron-withdrawing Cl, SiH 3 , and SiMe 3 , was changed. Over 0.70 electrons are unraveled to transfer from the electron-rich U III to the electron-deficient An VI of the actinyl moiety, leading to a more stable An V -U IV isomer; in contrast, uranylneptunium and uranylplutonium complexes behave as electron-resonance structures between VI-III and V-IV. These were further corroborated by geometrical and electronic structures. The energies of CCIs (i.e., O exo -An' bonds) were calculated to be -19.6 to -41.2 kcal/mol, affording those of OUO-Np (-23.9 kcal/mol) and OUO-Pu (-19.6 kcal/mol) with less electron transfer (ET) right at the low limit. Topological analyses of the electron density at the O exo -An' bond critical points demonstrate that the CCIs are ET or dative bonds in nature. A positive correlation has been built between the CCIs' strength and corresponding ET amount. It is concluded that the CCIs of O exo -An' are driven by the electrostatic attraction between the actinyl oxo atom (negative) and the actinide ion (positive) and enhanced by their ET. Finally, experimental syntheses of (THF)(H 2 L)(OU VI O)(An') III Cp 3 (An' = U and Np) were well reproduced by thermodynamic calculations that yielded negative free energies in a tetrahydrofuran solution but a positive one for their uranylplutonium analogue, which was synthetically inaccessible. So, our thermodynamics would provide implications for the synthetic possibility of other theoretically designed bimetallic actinide complexes.

Multidimensionally constrained relativistic mean-field study of triple-humped barriers in actinides

NASA Astrophysics Data System (ADS)

Zhao, Jie; Lu, Bing-Nan; Vretenar, Dario; Zhao, En-Guang; Zhou, Shan-Gui

2015-01-01

Background: Potential energy surfaces (PES's) of actinide nuclei are characterized by a two-humped barrier structure. At large deformations beyond the second barrier, the occurrence of a third barrier was predicted by macroscopic-microscopic model calculations in the 1970s, but contradictory results were later reported by a number of studies that used different methods. Purpose: Triple-humped barriers in actinide nuclei are investigated in the framework of covariant density functional theory (CDFT). Methods: Calculations are performed using the multidimensionally constrained relativistic mean field (MDC-RMF) model, with the nonlinear point-coupling functional PC-PK1 and the density-dependent meson exchange functional DD-ME2 in the particle-hole channel. Pairing correlations are treated in the BCS approximation with a separable pairing force of finite range. Results: Two-dimensional PES's of 226,228,230,232Th and 232,235,236,238U are mapped and the third minima on these surfaces are located. Then one-dimensional potential energy curves along the fission path are analyzed in detail and the energies of the second barrier, the third minimum, and the third barrier are determined. The functional DD-ME2 predicts the occurrence of a third barrier in all Th nuclei and 238U . The third minima in 230 ,232Th are very shallow, whereas those in 226 ,228Th and 238U are quite prominent. With the functional PC-PK1 a third barrier is found only in 226 ,228 ,230Th . Single-nucleon levels around the Fermi surface are analyzed in 226Th, and it is found that the formation of the third minimum is mainly due to the Z =90 proton energy gap at β20≈1.5 and β30≈0.7 . Conclusions: The possible occurrence of a third barrier on the PES's of actinide nuclei depends on the effective interaction used in multidimensional CDFT calculations. More pronounced minima are predicted by the DD-ME2 functional, as compared to the functional PC-PK1. The depth of the third well in Th isotopes decreases with increasing neutron number. The origin of the third minimum is due to the proton Z =90 shell gap at relevant deformations.

Humic Acid Complexation of Th, Hf and Zr in Ligand Competition Experiments: Metal Loading and Ph Effects

NASA Technical Reports Server (NTRS)

Stern, Jennifer C.; Foustoukos, Dionysis I.; Sonke, Jeroen E.; Salters, Vincent J. M.

2014-01-01

The mobility of metals in soils and subsurface aquifers is strongly affected by sorption and complexation with dissolved organic matter, oxyhydroxides, clay minerals, and inorganic ligands. Humic substances (HS) are organic macromolecules with functional groups that have a strong affinity for binding metals, such as actinides. Thorium, often studied as an analog for tetravalent actinides, has also been shown to strongly associate with dissolved and colloidal HS in natural waters. The effects of HS on the mobilization dynamics of actinides are of particular interest in risk assessment of nuclear waste repositories. Here, we present conditional equilibrium binding constants (Kc, MHA) of thorium, hafnium, and zirconium-humic acid complexes from ligand competition experiments using capillary electrophoresis coupled with ICP-MS (CE- ICP-MS). Equilibrium dialysis ligand exchange (EDLE) experiments using size exclusion via a 1000 Damembrane were also performed to validate the CE-ICP-MS analysis. Experiments were performed at pH 3.5-7 with solutions containing one tetravalent metal (Th, Hf, or Zr), Elliot soil humic acid (EHA) or Pahokee peat humic acid (PHA), and EDTA. CE-ICP-MS and EDLE experiments yielded nearly identical binding constants for the metal- humic acid complexes, indicating that both methods are appropriate for examining metal speciation at conditions lower than neutral pH. We find that tetravalent metals form strong complexes with humic acids, with Kc, MHA several orders of magnitude above REE-humic complexes. Experiments were conducted at a range of dissolved HA concentrations to examine the effect of [HA]/[Th] molar ratio on Kc, MHA. At low metal loading conditions (i.e. elevated [HA]/[Th] ratios) the ThHA binding constant reached values that were not affected by the relative abundance of humic acid and thorium. The importance of [HA]/[Th] molar ratios on constraining the equilibrium of MHA complexation is apparent when our estimated Kc, MHA values attained at very low metal loading conditions are compared to existing literature data. Overall, experimental data suggest that the tetravalent transition metal/-actinide-humic acid complexation is important over a wide range of pH values, including mildly acidic conditions, and thus, these complexes should be included in speciation models.

The Most Useful Actinide Isotope: Americium-241.

ERIC Educational Resources Information Center

Navratil, James D.; And Others

1990-01-01

Reviewed is the discovery, nuclear and chemical properties, and uses of an isotope of Americium (Am-241). Production and separation techniques used in industry are emphasized. Processes are illustrated in flow sheets. (CW)

Fundamental Studies of Irradiation-Induced Defect Formation and Fission Product Dynamics in Oxide Fuels

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

Stubbins, James

2012-12-19

The objective of this research program is to address major nuclear fuels performance issues for the design and use of oxide-type fuels in the current and advanced nuclear reactor applications. Fuel performance is a major issue for extending fuel burn-up which has the added advantage of reducing the used fuel waste stream. It will also be a significant issue with respect to developing advanced fuel cycle processes where it may be possible to incorporate minor actinides in various fuel forms so that they can be 'burned' rather than join the used fuel waste stream. The potential to fission or transmutemore » minor actinides and certain long-lived fission product isotopes would transform the high level waste storage strategy by removing the need to consider fuel storage on the millennium time scale.« less

The disposal of nuclear waste in space

NASA Technical Reports Server (NTRS)

Burns, R. E.

1978-01-01

The important problem of disposal of nuclear waste in space is addressed. A prior study proposed carrying only actinide wastes to space, but the present study assumes that all actinides and all fission products are to be carried to space. It is shown that nuclear waste in the calcine (oxide) form can be packaged in a container designed to provide thermal control, radiation shielding, mechanical containment, and an abort reentry thermal protection system. This package can be transported to orbit via the Space Shuttle. A second Space Shuttle delivers an oxygen-hydrogen orbit transfer vehicle to a rendezvous compatible orbit and the mated OTV and waste package are sent to the preferred destination. Preferred locations are either a lunar crater or a solar orbit. Shuttle traffic densities (which vary in time) are given and the safety of space disposal of wastes discussed.

Method for digesting spent ion exchange resins and recovering actinides therefrom using microwave radiation

DOEpatents

Maxwell, III, Sherrod L.; Nichols, Sheldon T.

1999-01-01

The present invention relates to methods for digesting diphosphonic acid substituted cation exchange resins that have become loaded with actinides, rare earth metals, or heavy metals, in a way that allows for downstream chromatographic analysis of the adsorbed species without damage to or inadequate elution from the downstream chromatographic resins. The methods of the present invention involve contacting the loaded diphosphonic acid resin with concentrated oxidizing acid in a closed vessel, and irradiating this mixture with microwave radiation. This efficiently increases the temperature of the mixture to a level suitable for digestion of the resin without the use of dehydrating acids that can damage downstream analytical resins. In order to ensure more complete digestion, the irradiated mixture can be mixed with hydrogen peroxide or other oxidant, and reirradiated with microwave radiation.

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

Electric dipole moments of actinide atoms and RaO molecule

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

Flambaum, V. V.

We have calculated the atomic electric dipole moments (EDMs) induced in {sup 229}Pa and {sup 225}Ac by their respective nuclear Schiff moments S. The results are d({sup 229}Pa)=-9.5x10{sup -17} [S/(e fm)]e cm=-1.1x10{sup -20}{eta} e cm and d({sup 225}Ac)=-8.6x10{sup -17} [S/(e fm)]e cm=-0.8x10{sup -21}{eta} e cm. EDM of {sup 229}Pa is 3x10{sup 4} times larger than {sup 199}Hg EDM and 40 times larger than {sup 225}Ra EDM. Possible use of actinides in solid state experiments is also discussed. The (T,P)-odd spin-axis interaction in RaO molecule is 500 times larger than in TlF.

Uranium beam characterization at CIRCE for background and contamination determinations.

PubMed

De Cesare, M; De Cesare, N; D'Onofrio, A; Fifield, L K; Gialanella, L; Terrasi, F

2015-09-01

The Accelerator Mass Spectrometry (AMS) is the most sensitive technique, compared either to the Inductively Coupled Plasma (ICP-MS) or Thermal Ionization (TI-MS) mass spectrometer, for the actinide (e.g. (236)U, (x)Pu isotopes) measurements. They are present in environmental samples at the ultra trace level since atmospheric tests of Nuclear Weapons (NWs) performed in the past, deliberate dumping of nuclear waste, nuclear fuel reprocessing, on a large scale, and operation of Nuclear Power Plants (NPPs), on a small scale, have led to the release of a wide range of radioactive nuclides in the environment. At the Center for Isotopic Research on Cultural and Environmental heritage (CIRCE) in Caserta, Italy, an upgraded actinide AMS system, based on a 3-MV pelletron tandem accelerator, has been developed and routinely operated. At CIRCE a charge state distribution as a function of terminal voltage, the beam emittance, measured in the 20° actinides dedicated beam line, as well as the energy and position validation of the U ions were performed in order to determine the best measurement conditions. A (236)U/(238)U isotopic ratio background level of about 5×10(-12) or 3×10(-13), depending on the Time of Flight-Energy (TOF-E) configurations, as well as the spatial distribution of the (235)U, (238)U interferences ions and a (236)U contamination mass of about 0.5 fg have been determined. Copyright © 2015 Elsevier Ltd. All rights reserved.

Extended tests of an SU(3) partial dynamical symmetry

DOE PAGES

Couture, Aaron Joseph; Casten, Richard F.; Cakirli, R. B.

2015-01-16

Background: A recent survey of well-deformed rare earth nuclei showed that B(E2) values from the γ band to the ground band could be explained rather well by a parameter-free description in terms of a partial dynamical symmetry (PDS). Purpose: Our purpose in this paper is to extend this study to deformed and transitional nuclei in the actinide and A ~ 100 regions to determine if the success of the PDS description is general in medium- and heavy-mass nuclei and to investigate further where it breaks down. Method: As with the previous study we study the empirical relative B(E2 : γmore » to ground) values in comparison to a pure rotor (Alaga) model and to the SU(3) PDS. Results: The data for the actinides, albeit sparser than in the rare-earth region, are reasonably well accounted for by the PDS but with systematic discrepancies. For the Mo isotopes, the PDS improves on the Alaga rules but largely fails to account for the data. Conclusions: As in the rare earths, the parameter-free PDS gives improved predictions compared to the Alaga rules for the actinides. The differences between the PDS predictions and the data are shown to point directly to specific mixing effects. Finally, in the Mo isotopes, their transitional character is directly seen in the large deviations of the B(E2) values from the PDS in the direction of the selection rules of the vibrator.« less

Hardening neutron spectrum for advanced actinide transmutation experiments in the ATR.

PubMed

Chang, G S; Ambrosek, R G

2005-01-01

The most effective method for transmuting long-lived isotopes contained in spent nuclear fuel into shorter-lived fission products is in a fast neutron spectrum reactor. In the absence of a fast test reactor in the United States, initial irradiation testing of candidate fuels can be performed in a thermal test reactor that has been modified to produce a test region with a hardened neutron spectrum. Such a test facility, with a spectrum similar but somewhat softer than that of the liquid-metal fast breeder reactor (LMFBR), has been constructed in the INEEL's Advanced Test Reactor (ATR). The radial fission power distribution of the actinide fuel pin, which is an important parameter in fission gas release modelling, needs to be accurately predicted and the hardened neutron spectrum in the ATR and the LMFBR fast neutron spectrum is compared. The comparison analyses in this study are performed using MCWO, a well-developed tool that couples the Monte Carlo transport code MCNP with the isotope depletion and build-up code ORIGEN-2. MCWO analysis yields time-dependent and neutron-spectrum-dependent minor actinide and Pu concentrations and detailed radial fission power profile calculations for a typical fast reactor (LMFBR) neutron spectrum and the hardened neutron spectrum test region in the ATR. The MCWO-calculated results indicate that the cadmium basket used in the advanced fuel test assembly in the ATR can effectively depress the linear heat generation rate in the experimental fuels and harden the neutron spectrum in the test region.

On the influence of the americium isotopic vector on the cooling time of minor actinides bearing blankets in fast reactors

NASA Astrophysics Data System (ADS)

Kooyman, Timothée; Buiron, Laurent; Rimpault, Gerald

2018-05-01

In the heterogeneous minor actinides transmutation approach, the nuclei to be transmuted are loaded in dedicated targets often located at the core periphery, so that long-lived heavy nuclides are turned into shorter-lived fission products by fission. To compensate for low flux level at the core periphery, the minor actinides content in the targets is set relatively high (around 20 at.%), which has a negative impact on the reprocessing of the targets due to their important decay heat level. After a complete analysis of the main contributors to the heat load of the irradiated targets, it is shown here that the choice of the reprocessing order of the various feeds of americium from the fuel cycle depends on the actual limit for fuel reprocessing. If reprocessing of hot targets is possible, it is more interesting to reprocess first the americium feed with a high 243Am content in order to limit the total cooling time of the targets, while if reprocessing of targets is limited by their decay heat, it is more interesting to wait for an increase in the 241Am content before loading the americium in the core. An optimization of the reprocessing order appears to lead to a decrease of the total cooling time by 15 years compared to a situation where all the americium feeds are mixed together when two feeds from SFR are considered with a high reprocessing limit.

Experimental evidence for ternary colloid-facilitated transport of Th(IV) with hematite (α-Fe2O3) colloids and Suwannee River fulvic acid.

PubMed

Emerson, Hilary P; Hickok, Katherine A; Powell, Brian A

2016-12-01

Previous field experiments have suggested colloid-facilitated transport via inorganic and organic colloids as the primary mechanism of enhanced actinide transport in the subsurface at former nuclear weapons facilities. In this work, research was guided by the hypothesis that humic substances can enhance tetravalent actinide (An(IV)) migration by coating and mobilizing natural colloids in environmental systems and increasing An(IV) sorption to colloids. This mechanism is expected to occur under relatively acidic conditions where organic matter can sorb and coat colloid surfaces and facilitate formation of ternary colloid-ligand-actinide complexes. The objective of this work was to examine Th transport through packed columns in the presence of hematite colloids and/or Suwannee River fulvic acid (SRFA). In the presence of SRFA, with or without hematite colloids, significant transport (>60% recovery within the effluent) of thorium occurred through quartz columns. It is notable that the SRFA contributed to increased transport of both Th and hematite colloids, while insignificant transport occurred in the absence of fulvic acid. Further, in the presence of a natural sandy sediment (as opposed to pure quartz), transport is negligible in the presence of SRFA due to interactions with natural, clay-sized sediment coatings. Moreover, this data shows that the transport of Th through quartz columns is enhanced in ternary Th-colloid-SRFA and binary Th-SRFA systems as compared to a system containing only Th. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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.

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

Status of the French Research on Partitioning and Transmutation

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

Warin, Dominique

2007-07-01

The global energy context pleads in favor of a sustainable development of nuclear energy since the demand for energy will likely increase, whereas resources will tend to get scarcer and the prospect of global warming will drive down the consumption of fossil fuel sources. How we deal with radioactive waste is crucial in this context. The production of nuclear energy in France has been associated, since its inception, with the optimization of radioactive waste management, including the partitioning and the recycling of recoverable energetic materials. The public's concern regarding the long-term waste management made the French Government prepare and passmore » the December 1991 Law, requesting in particular, the study for fifteen years of solutions for still minimizing the quantity and the hazardousness of final waste, via partitioning and transmutation. At the end of these fifteen years of research, it is considered that partitioning techniques, which have been validated on real solutions, are at disposal. Indeed, aqueous process for separation of minor actinides from the PUREX raffinate has been brought to a point where there is reasonable assurance that industrial deployment can be successful. A key experiment has been the successful kilogram scale trials in the CEA-Marcoule Atalante facility in 2005 and this result, together with the results obtained in the frame of the successive European projects, constitutes a considerable step forward. For transmutation, CEA has conducted programs proving the feasibility of the elimination of minor actinides and fission products: fabrication of specific targets and fuels for transmutation tests in the HFR and Phenix reactors, neutronics and technology studies for critical reactors and ADS developments. Scenario studies have also allowed assessing the feasibility, at the level of cycle and fuel facilities, and the efficiency of transmutation in terms of the quantitative reduction of the final waste inventory depending of the reactor fleet (PWR-FR-ADS). Important results are now available concerning the possibility of significantly reducing the quantity and the radiotoxicity of long-lived waste in association with a sustainable development of nuclear energy. As France has confirmed its long-term approach to nuclear energy, the most effective implementation of P and T of minor actinides relies on the fast neutron GEN IV systems, which are designed to recycle and manage their own actinides. The perspective to deploy a first series of such systems around 2040 supports the idea that progress is being made: the long-term waste would only be made up of fission products, with very low amounts of minor actinides. In this sense, the new waste management law passed by the French Parliament on June 28, 2006, demands that P and T research continues in strong connection to GEN IV systems and ADS development and allowing the assessment of the industrial perspectives of such systems in 2012 and to put into operation a transmutation demo facility in 2020. (author)« less

METHOD OF MAKING SPHERICAL ACTINIDE CARBIDE

DOEpatents

White, G.D.; O'Rourke, D.C.

1962-12-25

This patent describes a method of making uniform, spherical, nonpyrophoric UC. UO/sub 2/ and carbon are mixed in stoichiometric proportions and passed through a plasma flame of inert gas at 10,000 to 13,000 deg C. (AEC)

Study of 236U/238U ratio at CIRCE using a 16-strip silicon detector with a TOF system

NASA Astrophysics Data System (ADS)

De Cesare, M.; De Cesare, N.; D'Onofrio, A.; Gialanella, L.; Terrasi, F.

2015-04-01

Accelerator Mass Spectrometry (AMS) is presently the most sensitive technique for the measurement of long-lived actinides, e.g. 236U and xPu isotopes. A new actinide AMS system, based on a 3-MV pelletron tandem accelerator, is operated at the Center for Isotopic Research on Cultural and Environmental Heritage (CIRCE) in Caserta, Italy. In this paper we report on the procedure adopted to increase the 236U abundance sensitivity as low as possible. The energy and position determinations of the 236U ions, using a 16-strip silicon detector have been obtained. A 236U/238U isotopic ratio background level of about 2.9×10-11 was obtained, summing over all the strips, using a Time of Flight-Energy (TOF-E) system with a 16-strip silicon detector (4.9×10-12 just with one strip).

Isotopic signatures: An important tool in today`s world

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

Rokop, D.J.; Efurd, D.W.; Benjamin, T.M.

1995-12-01

High-sensitivity/high-accuracy actinide measurement techniques developed to support weapons diagnostic capabilities at the Los Alamos National Laboratory are now being used for environmental monitoring. The measurement techniques used are Thermal Ionization Mass Spectrometry (TIMS), Alpha Spectrometry(AS), and High Resolution Gamma Spectrometry(HRGS). These techniques are used to address a wide variety of actinide inventory issues: Environmental surveillance, site characterizations, food chain member determination, sedimentary records of activities, and treaty compliance concerns. As little as 10 femtograms of plutonium can be detected in samples and isotopic signatures determined on samples containing sub-100 femtogram amounts. Uranium, present in all environmental samples, can generally yieldmore » isotopic signatures of anthropogenic origin when present at the 40 picogam/gram level. Solid samples (soils, sediments, fauna, and tissue) can range from a few particles to several kilograms in size. Water samples can range from a few milliliters to as much as 200 liters.« less

Actinide removal from spent salts

DOEpatents

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

2002-01-01

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

Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

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

Kagan, Benjamin D.; Lichtscheidl, Alejandro G.; Erickson, Karla A.

Trimethyltin fluoride (Me₃SnF) is a mild and selective reagent for the installation of actinide fluoride bonds as demonstrated by the room temperature synthesis of a variety of organometallic and inorganic thorium(IV), uranium(IV), and uranium(V) fluoride complexes ((1,2,4-tBu₃C₅H₂)₂ThF₂, (C₅Me₅)₂U(F)(O-2,6-iPr₂C₆H₃), U(F)(O-2,6-tBu₂C₆H₃)₃, U(F)[N(SiMe₃)₂]₃ (C₅Me₅)₂UF₂(L) (L = O=PMe₃, O=PPh₃, O=PCy₃), and (C₅Me₅)₂U(F)(=N-2,6-iPr₂C₆H₃)) from their corresponding chloride, bromide, and iodide analogues. From these reactions, the new (C₅Me₅)₂UF₂(L) (L = O=PPh₃, O=PCy₃) uranium fluoride complexes were isolated and characterized by NMR spectroscopy and X-ray crystallography.

Alpha-decay-induced fracturing in zircon - The transition from the crystalline to the metamict state

NASA Technical Reports Server (NTRS)

Chakoumakos, Bryan C.; Murakami, Takashi; Lumpkin, Gregory R.; Ewing, Rodney C.

1987-01-01

Zonation due to alpha-decay damage in a natural single crystal of zircon from Sri Lanka is discussed. The zones vary in thickness on a scale from one to hundreds of microns. The uranium and thorium concentrations vary from zone to zone such that the alpha decay dose is between 0.2 x 10 to the 16th and 0.8 x 10 to the 16th alpha-events per milligram. The transition from the crystalline to the aperiodic metamict state occurs over this dose range. At doses greater than 0.8 x 10 to the 16th alpha events/mg there is no evidence for long-range order. This type of damage will accumulate in actinide-bearing, ceramic nuclear waste forms. The systematic pattern of fractures would occur in crystalline phases that are zoned with respect to actinide radionuclides.

The role of the [CpM(CO)2](-) chromophore in the optical properties of the [Cp2ThMCp(CO)2](+) complexes, where M = Fe, Ru and Os. A theoretical view.

PubMed

Cantero-López, Plinio; Le Bras, Laura; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

2015-12-14

The chemical bond between actinide and the transition metal unsupported by bridging ligands is not well characterized. In this paper we study the electronic properties, bonding nature and optical spectra in a family of [Cp2ThMCp(CO)2](+) complexes where M = Fe, Ru, Os, based on the relativistic two component density functional theory calculations. The Morokuma-Ziegler energy decomposition analysis shows an important ionic contribution in the Th-M interaction with around 25% of covalent character. Clearly, charge transfer occurs on Th-M bond formation, however the orbital term most likely represents a strong charge rearrangement in the fragments due to the interaction. Finally the spin-orbit-ZORA calculation shows the possible NIR emission induced by the [FeCp(CO)2](-) chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.

Fission Fragment characterization with FALSTAFF at NFS

NASA Astrophysics Data System (ADS)

Doré, D.; Farget, F.; Lecolley, F.-R.; Ledoux, X.; Lehaut, G.; Materna, T.; Pancin, J.; Panebianco, S.

2013-03-01

The Neutrons for Science (NFS) facility will be one of the first installations of the SPIRAL2 facility. NFS will be composed of a time-of-flight baseline and irradiation stations and will allow studying neutron-induced reactions for energies going from some hundreds of keV up to 40 MeV. Continuous and quasi-monoenergetic energy neutron beams will be available. Taking advantage of this new installation, the development of an experimental setup for a full characterization of actinide fission fragments in this energy domain has been undertaken. To achieve this goal a new detection system called FALSTAFF (Four Arm cLover for the STudy of Actinide Fission Fragments) in under development. In this paper, the characteristics of the NFS facility will be exposed and the motivations for the FALSTAFF experiment will be presented. The experimental setup will be described and the expected resolutions based on realistic GEANT4 simulations will be discussed.

Room temperature electrodeposition of actinides from ionic solutions

DOEpatents

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

2017-04-25

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

Nuclear Decay Data Evaluations at IFIN-HH, Romania

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

Luca, A., E-mail: aluca@nipne.ro

2014-06-15

An IAEA Coordinated Research Project (CRP) on Updated Decay Data Library for Actinides was implemented during the period 2005-2012. The author participated in the CRP, as a representative of the Horia Hulubei National Institute of Physics and Nuclear Engineering (IFIN-HH), the Radionuclide Metrology Laboratory. Decay data for five actinide nuclides were evaluated by the author, according to the procedures and rules of the international cooperation Decay Data Evaluation Project (DDEP): {sup 236}U, {sup 234}Th, {sup 228}Ra, {sup 211}Bi and {sup 211}Po. The most important results, conclusions and some recommendations of the evaluator are presented. The IFIN-HH involvement in several newmore » international and national research projects in the field is briefly mentioned; new evaluations and experimental determination of some nuclear decay data (photon absolute emission probability, half-life) for nuclear medicine applications are foreseen.« less

Post-irradiation examinations of THERMHET composite fuels for transmutation

NASA Astrophysics Data System (ADS)

Noirot, J.; Desgranges, L.; Chauvin, N.; Georgenthum, V.

2003-07-01

The thermal behaviour of composite targets dedicated to minor actinide transmutation was studied using THERMHET (thermal behaviour of heterogeneous fuel) irradiation in the SILOE reactor. Three inert matrix fuel designs were tested (macro-mass, jingle and microdispersion) all with a MgAl 2O 4 spinel inert matrix and around 40% weight of UO 2 to simulate minor actinide inclusions. The post-irradiation examinations led to a new interpretation of the temperature measurement by thermocouples located in the central hole of the pellets. A major change in the micro-dispersed structure was detected. The examinations enabled us to understand the behaviour of the spinel during the different stages of irradiation. They revealed an amorphisation at low temperature and then a nano re-crystallisation at high temperature of the spinel in the micro-dispersed case. These results, together with those obtained in the MATINA irradiation of an equivalent structure, show the importance of the irradiation temperature on spinel behaviour.

Simultaneous Thermal Analysis of Remediated Nitrate Salt Surrogates

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

Wayne, David Matthew

The actinide engineering and science group (MET-1) have completed simultaneous thermal analysis and offgas analysis by mass spectrometry (STA-MS) of remediated nitrate salt (RNS) surrogates formulated by the high explosives science and technology group (M-7). The 1.0 to 1.5g surrogate samples were first analyzed as received, then a new set was analyzed with 100-200mL 10M HNO 3 +0.3 MHF added, and a third set was analyzed after 200 mL of a concentrated Pu-AM spike (in 10M HNO 3 +0.3 MHF) was added. The acid and spike solutions were formulated by the actinide analytical chemistry group (C-AAC) using reagent-grade HNO 3more » and HF, which was also used to dissolve a small quantity of mixed, high-fired PuO 2/ AmO 2 oxide.« less

Delocalization and occupancy effects of 5f orbitals in plutonium intermetallics using L3-edge resonant X-ray emission spectroscopy

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

Booth, C. H.; Medling, S. A.; Jiang, Yu

2014-06-24

Although actinide (An) L3 -edge X-ray absorption near-edge structure (XANES) spectroscopy has been very effective in determining An oxidation states in insulating, ionically bonded materials, such as in certain coordination compounds and mineral systems, the technique fails in systems featuring more delocalized 5f orbitals, especially in metals. Recently, actinide L3-edge resonant X-ray emission spec- troscopy (RXES) has been shown to be an effective alternative. This technique is further demonstrated here using a parameterized partial unoccupied density of states method to quantify both occupancy and delocalization of the 5f orbital in ?-Pu, ?-Pu, PuCoGa5 , PuCoIn5 , and PuSb2. These newmore » results, supported by FEFF calculations, highlight the effects of strong correlations on RXES spectra and the technique?s ability to differentiate between f-orbital occupation and delocalization.« less

Calcium and zinc DTPA administration for internal contamination with plutonium-238 and americium-241.

PubMed

Kazzi, Ziad N; Heyl, Alexander; Ruprecht, Johann

2012-08-01

The accidental or intentional release of plutonium or americium can cause acute and long term adverse health effects if they enter the human body by ingestion, inhalation, or injection. These effects can be prevented by rapid removal of these radionuclides by chelators such as calcium or zinc diethylenetriaminepentaacetate (calcium or zinc DTPA). These compounds have been shown to be efficacious in enhancing the elimination of members of the actinide family particularly plutonium and americium when administered intravenously or by nebulizer. The efficacy and adverse effects profile depend on several factors that include the route of internalization of the actinide, the type, and route time of administration of the chelator, and whether the calcium or zinc salt of DTPA is used. Current and future research efforts should be directed at overcoming limitations associated with the use of these complex drugs by using innovative methods that can enhance their structural and therapeutic properties.

Preparation and X-Ray diffraction studies of curium hydrides

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

Gibson, J.K.; Maire, R.G.

Curium hydrides were prepared by reaction of curium-248 metal with hydrogen and characterized by X-ray powder diffraction. Several of the syntheses resulted in a hexagonal compound with average lattice parameters of a/sub 0/ = 0.3769(8) nm and c/sub 0/ = 0.6732(12) nm. These products are considere to be CmH/sub 3//sup -//sub 8/ by analogy with the behavior of lanthanide-hydrogen and lighter actinide-hydrogen systems. Face-centered cubic products with an average lattice parameter of a/sub 0/ = 0.5322(4) nm were obtained from other curium hydride preparations. This parameter is slightly smaller than that reported previously for cubic curium dihydride, CmH /SUB 2-x/more » (B.M. Bansal and D. Damien. Inorg. Nucl. Chem. Lett. 6 603, 1970). The present results established a continuation of typical heavy trivalent lanthanidelike behavior of the transuranium actinide-hydrogen systems through curium.« less

Preparation and X-ray diffraction studies of curium hydrides

NASA Astrophysics Data System (ADS)

Gibson, J. K.; Haire, R. G.

1985-10-01

Curium hydrides were prepared by reaction of curium-248 metal with hydrogen and characterized by X-ray powder diffraction. Several of the syntheses resulted in a hexagonal compound with average lattice parameters of a0 = 0.3769(8) nm and c0 = 0.6732(12) nm. These products are considered to be CmH 3-δ by analogy with the behavior of lanthanide-hydrogen and lighter actinide-hydrogen systems. Face-centered cubic products with an average lattice parameter of a0 = 0.5322(4) nm were obtained from other curium hydride preparations. This parameter is slightly smaller than that reported previously for cubic curium dihydride, CmH 2+ x (B. M. Bansal and D. Damien, Inorg. Nucl. Chem. Lett., 6, 603, 1970). The present results established a continuation of typical heavy trivalent lanthanide-like behavior of the transuranium actinide-hydrogen systems through curium.

Synthesis of Actinide Fluoride Complexes Using Trimethyltin Fluoride as a Mild and Selective Fluorinating Reagent

DOE PAGES

Kagan, Benjamin D.; Lichtscheidl, Alejandro G.; Erickson, Karla A.; ...

2017-11-07

Trimethyltin fluoride (Me₃SnF) is a mild and selective reagent for the installation of actinide fluoride bonds as demonstrated by the room temperature synthesis of a variety of organometallic and inorganic thorium(IV), uranium(IV), and uranium(V) fluoride complexes ((1,2,4-tBu₃C₅H₂)₂ThF₂, (C₅Me₅)₂U(F)(O-2,6-iPr₂C₆H₃), U(F)(O-2,6-tBu₂C₆H₃)₃, U(F)[N(SiMe₃)₂]₃ (C₅Me₅)₂UF₂(L) (L = O=PMe₃, O=PPh₃, O=PCy₃), and (C₅Me₅)₂U(F)(=N-2,6-iPr₂C₆H₃)) from their corresponding chloride, bromide, and iodide analogues. From these reactions, the new (C₅Me₅)₂UF₂(L) (L = O=PPh₃, O=PCy₃) uranium fluoride complexes were isolated and characterized by NMR spectroscopy and X-ray crystallography.

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.

Status of the Neutron Capture Measurement on 237Np with the DANCE Array at LANSCE

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

Esch, E.-I.; Bond, E.M.; Bredeweg, T. A.

2005-05-24

Neptunium-237 is a major constituent of spent nuclear fuel. Estimates place the amount of 237Np bound for the Yucca Mountain high-level waste repository at 40 metric tons. The Department of Energy's Advanced Fuel Cycle Initiative program is evaluating methods for transmuting the actinide waste that will be generated by future operation of commercial nuclear power plants. The critical parameter that defines the transmutation efficiency of actinide isotopes is the neutron fission-to-capture ratio for the particular isotope in a given neutron spectrum. The calculation of transmutation efficiency therefore requires accurate fission and capture cross sections. Current 237Np evaluations available for transmutermore » system studies show significant discrepancies in both the fission and capture cross sections in the energy regions of interest. Herein we report on 237Np (n,{gamma}) measurements using the recently commissioned DANCE array.« less

A survey on uncertainty in bioassay measurements carried out within the OMINEX project.

PubMed

Hurtgen, C; Cossonnet, C

2003-01-01

One of the topics covered by the OMINEX (Optimisation of Monitoring for Internal Exposure) project was to look at the bioassay measurements performed in the European laboratories. Questionnaires on bioassay measurements by alpha spectrometry or inductively coupled plasma-mass spectrometry (ICP-MS) were sent to European laboratories. The main objective was to collect information on analytical procedures and on the uncertainties associated with bioassay results. Alpha spectrometry is the technique most often used for the determination of alpha emitters, such as actinides in biological samples. ICP-MS is not used much as yet for routine measurements of actinides in biological samples, but is very sensitive for measurements of long-lived radionuclides. The different parameters influencing the uncertainties on the results and the minimum detectable amount have been investigated. Optimum conditions for achieving low result uncertainties and high sensitivity are given for alpha spectrometry and ICP-MS.

Microscopic analysis of octupole shape transitions in neutron-rich actinides with relativistic energy density functional

NASA Astrophysics Data System (ADS)

Xu, Zhong; Li, Zhi-Pan

2017-12-01

Quadrupole and octupole deformation energy surfaces, low-energy excitation spectra, and electric transition rates in eight neutron-rich isotopic chains - Ra, Th, U, Pu, Cm, Cf, Fm, and No - are systematically analyzed using a quadrupole-octupole collective Hamiltonian model, with parameters determined by constrained reflection-asymmetric and axially-symmetric relativistic mean-field calculations based on the PC-PK1 energy density functional. The theoretical results of low-lying negative-parity bands, odd-even staggering, average octupole deformations ⟨β 3⟩, and show evidence of a shape transition from nearly spherical to stable octupole-deformed, and finally octupole-soft equilibrium shapes in the neutron-rich actinides. A microscopic mechanism for the onset of stable octupole deformation is also discussed in terms of the evolution of single-nucleon orbitals with deformation. Supported by National Natural Science Foundation of China (11475140, 11575148)

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

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.

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.

Physical nature of longevity of light actinides in dynamic failure phenomenon

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

Uchaev, A. Ya., E-mail: uchaev@expd.vniief.ru; Punin, V. T.; Selchenkova, N. I.

It is shown in this work that the physical nature of the longevity of light actinides under extreme conditions in a range of nonequilibrium states of t ∼ 10{sup –6}–10{sup –10} s is determined by the time needed for the formation of a critical concentration of a cascade of failure centers, which changes connectivity of the body. These centers form a percolation cluster. The longevity is composed of waiting time t{sub w} for the appearance of failure centers and clusterization time t{sub c} of cascade of failure centers, when connectivity in the system of failure centers and the percolation clustermore » arise. A unique mechanism of the dynamic failure process, a unique order parameter, and an equal dimensionality of the space in which the process occurs determine the physical nature of the longevity of metals, including fissionable materials.« less

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

RAPID SEPARATION METHOD FOR EMERGENCY WATER AND URINE SAMPLES

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

Maxwell, S.; Culligan, B.

2008-08-27

The Savannah River Site Environmental Bioassay Lab participated in the 2008 NRIP Emergency Response program administered by the National Institute for Standards and Technology (NIST) in May, 2008. A new rapid column separation method was used for analysis of actinides and {sup 90}Sr the NRIP 2008 emergency water and urine samples. Significant method improvements were applied to reduce analytical times. As a result, much faster analysis times were achieved, less than 3 hours for determination of {sup 90}Sr and 3-4 hours for actinides. This represents a 25%-33% improvement in analysis times from NRIP 2007 and a {approx}100% improvement compared tomore » NRIP 2006 report times. Column flow rates were increased by a factor of two, with no significant adverse impact on the method performance. Larger sample aliquots, shorter count times, faster cerium fluoride microprecipitation and streamlined calcium phosphate precipitation were also employed. Based on initial feedback from NIST, the SRS Environmental Bioassay Lab had the most rapid analysis times for actinides and {sup 90}Sr analyses for NRIP 2008 emergency urine samples. High levels of potential matrix interferences may be present in emergency samples and rugged methods are essential. Extremely high levels of {sup 210}Po were found to have an adverse effect on the uranium results for the NRIP-08 urine samples, while uranium results for NRIP-08 water samples were not affected. This problem, which was not observed for NRIP-06 or NRIP-07 urine samples, was resolved by using an enhanced {sup 210}Po removal step, which will be described.« less

Criticality safety strategy and analysis summary for the fuel cycle facility electrorefiner at Argonne National Laboratory West

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

Mariani, R.D.; Benedict, R.W.; Lell, R.M.

1996-05-01

As part of the termination activities of Experimental Breeder Reactor II (EBR-II) at Argonne National Laboratory (ANL) West, the spent metallic fuel from EBR-II will be treated in the fuel cycle facility (FCF). A key component of the spent-fuel treatment process in the FCF is the electrorefiner (ER) in which the actinide metals are separated from the active metal fission products and the reactive bond sodium. In the electrorefining process, the metal fuel is anodically dissolved into a high-temperature molten salt, and refined uranium or uranium/plutonium products are deposited at cathodes. The criticality safety strategy and analysis for the ANLmore » West FCF ER is summarized. The FCF ER operations and processes formed the basis for evaluating criticality safety and control during actinide metal fuel refining. To show criticality safety for the FCF ER, the reference operating conditions for the ER had to be defined. Normal operating envelopes (NOEs) were then defined to bracket the important operating conditions. To keep the operating conditions within their NOEs, process controls were identified that can be used to regulate the actinide forms and content within the ER. A series of operational checks were developed for each operation that will verify the extent or success of an operation. The criticality analysis considered the ER operating conditions at their NOE values as the point of departure for credible and incredible failure modes. As a result of the analysis, FCF ER operations were found to be safe with respect to criticality.« less

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

METHOD OF SEPARATING Pu FROM METATHESIZED BiPO$sub 4$ CARRIER

DOEpatents

Knox, W.J.; Thompson, S.G.

1960-05-31

A process is given for separating uranium, neptunium, and/or plutonium from a bismuth hydroxide carrier by selective dissolution of these actinides with nitric acid of a concentration of from 0.05 to 0.5N.

Two actinide-organic frameworks constructed by a tripodal flexible ligand: Occurrence of infinite ((UO{sub 2})O{sub 2}(OH){sub 3}){sub 4n} and hexanuclear (Th{sub 6}O{sub 4}(OH){sub 4}) motifs

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

Liang, Lingling; Zhang, Ronglan; Zhao, Jianshe, E-mail: jszhao@nwu.edu.cn

Two new actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H{sub 3}tci) under hydrothermal condition. The combination of H{sub 3}tci and uranyl nitrate hexahydrate in aqueous solution leads to the isolation of [(UO{sub 2}){sub 2}(H{sub 2}O){sub 4}]{sub 0.5}(tci){sub 2}(UO{sub 2}){sub 4}(OH){sub 4}·18H{sub 2}O (1), which contains two distinct UO{sub 2}{sup 2+} coordination environments. Four uranyl cations, linked through μ{sub 3}-OH respectively, result in the edge-sharing ribbons. Then, the layer structure is constructed by U-O clusters linked through other eight-coordinated uranyl unions, giving rise to a porous structure in the space. Topological analysis reveals thatmore » complex 1 belongs to a (4, 8)-connected net with a schläfli symbol of (3{sup 4.}2{sup 6.}3){sub 2}(3{sup 4.}4{sup 6.}5{sup 6.}6{sup 8.}7{sup 3.}8). Th{sub 3}(tci){sub 2}O{sub 2}(OH){sub 2}(H{sub 2}O){sub 3}·12H{sub 2}O (2) generated by the reaction of H{sub 3}tci and thorium nitrate tetrahydrate, possesses nine-fold coodinated Th(IV) centers with a monocapped square antiprismatic geometry. The hexamers “Th{sub 6}O{sub 4}(OH){sub 4}” motifs are connected together by the carboxylate groups, showing a three-dimensional structures. Complex 2 takes on an 8-connected architecture and the point symbol is (4{sup 24.}6{sup 4}). - Graphical abstract: Two new 3D actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H3tci) and their topological structures were displayed. The infinite ((UO{sub 2})O{sub 2}(OH){sub 3}){sub 4n} and hexanuclear (Th{sub 6}O{sub 4}(OH){sub 4}) motifs were found in the title actinides networks.« 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

An Approach for Validating Actinide and Fission Product Burnup Credit Criticality Safety Analyses--Criticality (keff) Predictions

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

Scaglione, John M; Mueller, Don; Wagner, John C

2011-01-01

One of the most significant 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. 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. U.S. Nuclear Regulatory Commission (NRC) staff have noted that the rationale for restricting their Interim Staff Guidance on burnup credit (ISG-8) to actinide-only ismore » based largely on the lack of clear, definitive experiments that can be used to estimate the bias and uncertainty for computational analyses associated with using burnup credit. To address the issue of validation, the NRC initiated a project with the Oak Ridge National Laboratory to (1) develop and establish a technically sound validation approach (both depletion and criticality) for commercial spent nuclear fuel (SNF) criticality safety evaluations based on best-available data and methods and (2) apply 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 purpose of this paper is to describe the criticality (k{sub eff}) validation approach, and resulting observations and recommendations. Validation of the isotopic composition (depletion) calculations is addressed in a companion paper at this conference. For criticality validation, the approach is to utilize (1) available laboratory critical experiment (LCE) data from the International Handbook of Evaluated Criticality Safety Benchmark Experiments and the French Haut Taux de Combustion (HTC) program to support validation of the principal actinides and (2) calculated sensitivities, nuclear data uncertainties, and the limited available fission product LCE data to predict and verify individual biases for relevant minor actinides and fission products. This paper (1) provides a detailed description of the approach and its technical bases, (2) describes the application of the approach for representative pressurized water reactor and boiling water reactor safety analysis models to demonstrate its usage and applicability, (3) provides reference bias results based on the prerelease SCALE 6.1 code package and ENDF/B-VII nuclear cross-section data, and (4) provides recommendations for application of the results and methods to other code and data packages.« less

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.

Nineteenth annual actinide separations conference: Conference program and abstracts

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

Bronson, M.

This report contains the abstracts from the conference presentations. Sessions were divided into the following topics: Waste treatment; Spent fuel treatment; Issues and responses to Defense Nuclear Facility Safety Board 94-1; Pyrochemical technologies; Disposition technologies; and Aqueous separation technologies.

Interaction with William Carnall

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

Judd, Brian R.

2005-02-15

A personal account is given of interaction with William T. Carnall during the period 1977-1988, when I made regular visits to the Argonne National Laboratory to discuss the theoretical background to the spectroscopic work he was carrying out on the lanthanides and actinides.

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

Complexation-assisted reduction: complexes of glutaroimide-dioxime with tetravalent actinides (Np( iv ) and Th( iv ))

DOE PAGES

Zhang, Zhicheng; Parker, Bernard F.; Lohrey, Trevor D.; ...

2018-01-01

Glutaroimide-dioxime forms strong complexes with Np( iv ) and Th( iv ) in aqueous solution and in crystals. The formation of Np( iv ) complexes from initial Np( v ) is interpreted by a complexation-assisted reduction mechanism.

Electron Spectroscopy: Ultraviolet and X-Ray Excitation.

ERIC Educational Resources Information Center

Baker, A. D.; And Others

1980-01-01

Reviews recent growth in electron spectroscopy (54 papers cited). Emphasizes advances in instrumentation and interpretation (52); photoionization, cross-sections and angular distributions (22); studies of atoms and small molecules (35); transition, lanthanide and actinide metal complexes (50); organometallic (12) and inorganic compounds (2);…

Complexation-assisted reduction: complexes of glutaroimide-dioxime with tetravalent actinides (Np( iv ) and Th( iv ))

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

Zhang, Zhicheng; Parker, Bernard F.; Lohrey, Trevor D.

Glutaroimide-dioxime forms strong complexes with Np( iv ) and Th( iv ) in aqueous solution and in crystals. The formation of Np( iv ) complexes from initial Np( v ) is interpreted by a complexation-assisted reduction mechanism.

Materials and Molecular Research Division annual report 1983

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

Searcy, A.W.; Muller, R.H.; Peterson, C.V.

1984-07-01

Progress is reported in the following fields: materials sciences (metallurgy and ceramics, solid-state physics, materials chemistry), chemical sciences (fundamental interactions, processes and techniques), actinide chemistry, fossil energy, electrochemical energy storage systems, superconducting magnets, semiconductor materials and devices, and work for others. (DLC)

Criticality safety strategy for the Fuel Cycle Facility electrorefiner at Argonne National Laboratory, West

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

Mariani, R.D.; Benedict, R.W.; Lell, R.M.

1993-09-01

The Integral Fast Reactor being developed by Argonne National Laboratory (ANL) combines the advantages of metal-fueled, liquid-metal-cooled reactors and a closed fuel cycle. Presently, the Fuel Cycle Facility (FCF) at ANL-West in Idaho Falls, Idaho is being modified to recycle spent metallic fuel from Experimental Breeder Reactor II as part of a demonstration project sponsored by the Department of Energy. A key component of the FCF is the electrorefiner (ER) in which the actinides are separated from the fission products. In the electrorefining process, the metal fuel is anodically dissolved into a high-temperature molten salt and refined uranium or uranium/plutoniummore » products are deposited at cathodes. In this report, the criticality safety strategy for the FCF ER is summarized. FCF ER operations and processes formed the basis for evaluating criticality safety and control during actinide metal fuel refining. In order to show criticality safety for the FCF ER, the reference operating conditions for the ER had to be defined. Normal operating envelopes (NOES) were then defined to bracket the important operating conditions. To keep the operating conditions within their NOES, process controls were identified that can be used to regulate the actinide forms and content within the ER. A series of operational checks were developed for each operation that wig verify the extent or success of an operation. The criticality analysis considered the ER operating conditions at their NOE values as the point of departure for credible and incredible failure modes. As a result of the analysis, FCF ER operations were found to be safe with respect to criticality.« less

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.

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.

Development and Testing of Diglycolamide Functionalized Mesoporous Silica for Sorption of Trivalent Actinides and Lanthanides

DOE PAGES

Shusterman, Jennifer A.; Mason, Harris E.; Bowers, Jon; ...

2015-09-03

Sequestration of trivalent actinides and lanthanides present in used nuclear fuel and legacy wastes is necessary for appropriate long-term stewardship of these metals, particularly to prevent their release into the environment. Organically modified mesoporous silica is an efficient material for recovery and potential subsequent separation of actinides and lanthanides because of its high surface area, tunable ligand selection, and chemically robust substrate. Here, we have synthesized the first novel hybrid material composed of SBA-15 type mesoporous silica functionalized with diglycolamide ligands (DGA-SBA). Because of the high surface area substrate, the DGA-SBA was found to have the highest Eu capacity reportedmore » so far in the literature of all DGA solid-phase extractants. The sorption behavior of europium and americium on DGA-SBA in nitric and hydrochloric acid media was tested in batch contact experiments. DGA-SBA was found to have high sorption of Am and Eu in pH 1, 1 M, and 3 M nitric and hydrochloric acid concentrations, which makes it promising for sequestration of these metals from used nuclear fuel or legacy waste. The kinetics of Eu sorption were found to be two times slower than that for Am in 1 M HNO 3. Additionally, the short-term susceptibility of DGA-SBA to degradation in the presence of acid was probed using 29Si and 13C solid-state NMR spectroscopy. Finally, the material was found to be relatively stable under these conditions, with the ligand remaining intact after 24 h of contact with 1 M HNO 3, an important consideration in use of the DGA-SBA as an extractant from acidic media.« less

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

PRELIMINARY DATA CALL REPORT ADVANCED BURNER REACTOR START UP FUEL FABRICATION FACILITY

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

S. T. Khericha

2007-04-01

The purpose of this report is to provide data for preparation of a NEPA Environmental Impact Statement in support the U. S. Department of Energy (DOE) Global Nuclear Energy Partnership (GNEP). One of the GNEP objectives is to reduce the inventory of long lived actinide from the light water reactor (LWR) spent fuel. The LWR spent fuel contains Plutonium (Pu) -239 and other transuranics (TRU) such as Americium-241. One of the options is to transmute or burn these actinides in fast neutron spectra as well as generate the electricity. A sodium-cooled Advanced Recycling Reactor (ARR) concept has been proposed tomore » achieve this goal. However, fuel with relatively high TRU content has not been used in the fast reactor. To demonstrate the utilization of TRU fuel in a fast reactor, an Advanced Burner Reactor (ABR) prototype of ARR is proposed, which would necessarily be started up using weapons grade (WG) Pu fuel. The WG Pu is distinguished by relatively highest proportions of Pu-239 and lesser amount of other actinides. The WG Pu will be used as the startup fuel along with TRU fuel in lead test assemblies. Because such fuel is not currently being produced in the US, a new facility (or new capability in an existing facility) is being considered for fabrication of WG Pu fuel for the ABR. This report is provided in response to ‘Data Call’ for the construction of startup fuel fabrication facility. It is anticipated that the facility will provide the startup fuel for 10-15 years and will take to 3 to 5 years to construct.« less

A Blueprint for GNEP Advanced Burner Reactor Startup Fuel Fabrication Facility

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

S. Khericha

2010-12-01

The purpose of this article is to identify the requirements and issues associated with design of GNEP Advanced Burner Reactor Fuel Facility. The report was prepared in support of providing data for preparation of a NEPA Environmental Impact Statement in support the U. S. Department of Energy (DOE) Global Nuclear Energy Partnership (GNEP). One of the GNEP objectives was to reduce the inventory of long lived actinide from the light water reactor (LWR) spent fuel. The LWR spent fuel contains Plutonium (Pu) -239 and other transuranics (TRU) such as Americium-241. One of the options is to transmute or burn thesemore » actinides in fast neutron spectra as well as generate the electricity. A sodium-cooled Advanced Recycling Reactor (ARR) concept was proposed to achieve this goal. However, fuel with relatively high TRU content has not been used in the fast reactor. To demonstrate the utilization of TRU fuel in a fast reactor, an Advanced Burner Reactor (ABR) prototype of ARR was proposed, which would necessarily be started up using weapons grade (WG) Pu fuel. The WG Pu is distinguished by relatively highest proportions of Pu-239 and lesser amount of other actinides. The WG Pu was assumed to be used as the startup fuel along with TRU fuel in lead test assemblies. Because such fuel is not currently being produced in the US, a new facility (or new capability in an existing facility) was being considered for fabrication of WG Pu fuel for the ABR. It was estimated that the facility will provide the startup fuel for 10-15 years and would take 3 to 5 years to construct.« less

Summary report for the FY-2015 SACSESS Collaboration

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

Peterman, Dean Richard; Mincher, Bruce Jay

2015-09-01

During FY-2015, a collaborative research program was established by the Department of Energy-Nuclear Energy (DOE-NE) Material Recovery and Waste Form Development program and the European Union (EU) Safety of Actinide Separation Processes (SACSESS) program. One component of this collaboration was the evaluation of the radiolytic stability of a Selective ActiNide Extraction (SANEX) separation which utilized a TODGA-based organic solvent and an aqueous phase containing the hydrophilic complexing reagent, SO3-Ph-BTP. To best simulate process conditions, this experiment was irradiated in the radiolysis/hydrolysis test loop located at the Idaho National Laboratory. The effect of irradiation on a SACSESS program iSANEX formulation containingmore » a TODGA-based organic phase and a BTP-based aqueous phase was investigated using irradiations at INL in static and test loop modes. When irradiated in contact with only the acidic aqueous phase, the TODGA organic solution maintained excellent extraction performance of americium, cerium and europium to a maximum absorbed dose of nearly 0.9 MGy. When the aqueous phase was changed to that containing the aqueous soluble BTP, the irradiated aqueous phase showed a dramatic color change, but this does not appear to have adverse effects on solvent extraction performance. Only minor increases in distribution ratios for both the lanthanides and actinide were measured, and the separation factors were essentially unchanged to a maximum absorbed dose of 174 kGy. The determination of the americium, cerium, and europium distribution ratios for the remaining SACSESS test loop samples will be completed in the near future. The analysis of stable metals concentration in the the irradiated aqueous and organic phases will be completed shortly.« less

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

Implementation of new integrated evaporation equipment for the preparation of 238U targets and improvement of the deposition process

NASA Astrophysics Data System (ADS)

Vanleeuw, D.; Lewis, D.; Moens, A.; Sibbens, G.; Wiss, T.

2018-05-01

Measurement of neutron cross section data is a core activity of the JRC-Directorate G for Nuclear Safety and Security in Geel. After a period of reduced activity and in line with a renewed interest for nuclear data required for GenIV reactors and waste minimization, the demand for high quality actinide targets increased. Physical vapour deposition by thermal evaporation is a key technique to prepare homogeneous thin actinide layers, but due to ageing effects the earlier in-house developed equipment can no longer provide the required quality. Because of a current lack of experience and human resources cooperation with private companies is required for the development of new deposition equipment directly integrated in a glove box. In this paper we describe the design, implementation and validation of the first commercial actinide evaporator in a glove box as well as the optimization of the deposition process. Highly enriched 238U3O8 was converted to 238UF4 powder and several deposition runs were performed on different substrates. The deposition parameters were varied and defined in order to guarantee physical and chemical stable homogeneous UF4 layers, even on polished substrates which was not longer feasible with the older equipment. The stability problem is discussed in view of the thin layer growth by physical vapour deposition and the influence of the deposition parameters on the layer quality. The deposits were characterized for the total mass by means of substitution weighing and for the areal density of 238U by means of alpha particle counting and thermal ionization mass spectrometry (TIMS). The quality of the layer was visually evaluated and by means of stereo microscopy and auto radiography.

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.

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