Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium.

Swapping of an oxygen atom of water with that of a pentavalent actinide dioxide cation, AnO2+ also called an "actinyl", requires activation of an An-O bond. It was previously found that such oxo exchange in the gas phase occurs for the first two actinyls, PaO2+ and UO2+, but not the next two, NpO2+ and PuO2+. The An-O bond dissociation energies (BDEs) decrease from PaO2+ to PuO2+, such that the observation of a parallel decrease in the An-O bond reactivity is intriguing. To elucidate oxo exchange, we here extend experimental studies to AmO2+, americyl(V), and CmO2+, curyl(V), which were produced in remarkable abundance by electrospray ionization of Am3+ and Cm3+ solutions. Like other AnO2+, americyl(V) and curyl(V) adsorb up to four H2O molecules to form tetrahydrates AnO2(H2O)4+ with the actinide hexacoordinated by oxygen atoms. It was found that AmO2+ does not oxo-exchange, whereas CmO2+ does, establishing a "turn" to increasing the reactivity from americyl to curyl, which validates computational predictions. Because oxo exchange occurs via conversion of an actinyl(V) hydrate, AnO2(H2O)+, to an actinide(V) hydroxide, AnO(OH)2+, it reflects the propensity for actinyl(V) hydrolysis: PaO2+ hydrolyzes and oxo-exchanges most easily, despite the fact that it has the highest BDE of all AnO2+. A reexamination of the computational results for actinyl(V) oxo exchange reveals distinctive properties and chemistry of curyl(V) species, particularly CmO(OH)2+

Processes for metal extraction

This report describes the processing of plutonium at Los Alamos National Laboratory (LANL), and operation illustrating concepts that may be applicable to the processing of lunar materials. The toxic nature of plutonium requires a highly closed system for processing lunar surface materials

Influence of diluent alkyl substitution on the extraction of Am(III) and Eu(III) by a 6,6’-bis(1,2,4-triazin-3-yl)-2,2’-bipyridine ligand dissolved in alkylated cyclohexanone Diluents

Several alkylated cyclohexanones were investigated as potential diluents for the selective extraction of Am(III) from Eu(III) from nitric acid solutions by the CyMe4-BTBP ligand. No significant extraction of either of the metal ions was observed for these diluents themselves. In the extractions from 1 M HNO3, 3-methylcyclohexanone and 4-methylcyclohexanone gave comparable results to cyclohexanone whereas in the extractions from 4 M HNO3, 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone all gave superior results. For the monomethylated diluents, DAm and SFAm/Eu decreased in the order of alkyl substitution 2 > 4 ~ 3. However, alkyl substitution of cyclohexanone significantly slows down the extraction kinetics compared to cyclohexanone, and the position of alkyl substitution was found to play an important role in the solvents properties. 3-Methylcyclohexanone was identified as the most promising of the diluent

Discovery of Isotopes of the Transuranium Elements with 93 <= Z <= 98

One hundred and five isotopes of the transuranium elements neptunium, plutonium, americium, curium, berkelium and californium have so far been observed; the discovery of these isotopes is discussed. For each isotope a brief summary of the first refereed publication, including the production and identification method, is presented.Comment: To be published in Atomic Data and Nuclear Data Table

Gas core reactors for actinide transmutation and breeder applications

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

Optimisation and application of ICP-MS and alpha-spectrometry for determination of isotopic ratios of depleted uranium and plutonium in samples collected in Kosovo

The determination of environmental contamination with natural and artificial actinide isotopes and evaluation of their source requires precise isotopic determination of actinides, above all uranium and plutonium. This can be achieved by alpha spectrometry or by inductively coupled plasma mass spectrometry (ICP-MS) after chemical separation of actinides. The performance of a sector-field ICP-MS (ICP-SFMS) coupled to a low-flow micronebulizer with a membrane desolvation unit, "Aridus'', was studied with respect to precise isotopic measurements of uranium and plutonium at the ultratrace level. The UH+/U+ formation rate was about 3x10(-5) and a sensitivity for U-238 of up to 4x10(9) counts s(-1) ppm(-1) was achieved. The limit of quantification (LOQ, 10s) for U-236 and Pu-239 using the experimental arrangement described above was 0.6 pg l(-1) in aqueous solution and 0.13 pg g(-1) in soil, respectively. ICP-SFMS was used in comparison to alpha spectrometry to measure the U and Pu concentrations and isotopic compositions in two soil samples and in one penetrator collected in Kosovo. ICP-MS permitted the determination of U and Pu isotope ratios including the U-236 abundance and Pu-240/Pu-239 ratio at ultratrace levels in soil samples of up to 0.1 g. Depleted uranium (U-235/U-238= 0.00202 +/-0.00001) was determined in one penetrator and one soil sample. Pu concentrations of (5.5 +/-0.1) x 10(-13) g g(-1) and (4.4 +/-0.5) x 10(-13) g g(-1) (Pu-240/Pu-239=0.35 +/-0.10 and 0.27 +/-0.07, respectively) were found in both soil samples from Kosovo. Besides plutonium, U-236 (3.1x10(-5) g g(-1)) and Am-241 (1.7x10(-12) g g(-1)) were also detected in the penetrator sample, which indicates the previous existence of neutron-related processes and points to a possible presence of spent reactor uranium in munitions. However, the most probable plutonium contamination sources in analyzed soil samples from Kosovo are mixed fallout including spent reactor fuel due to the Chernobyl nuclear power plant accident in 1986 and plutonium due to nuclear weapon tests. Additional plutonium contamination could not be determined in the Kosovo soil sample containing depleted uranium with a detection limit of about 10(-13) g g(-1)