Theoretical study of Pu and Am tetracarbide molecules

The electronic structure and ground‐state molecular properties of Pu and Am tetracarbides have been investigated by relativistic multireference calculations using CASSCF/CASPT2 theory as well as by density functional theory in conjunction with relativistic pseudopotentials. The CASSCF/CASPT2 treatment has been extended by spin–orbit coupling effects for selected species using the CAS state‐interaction method. The five atoms can form various structural isomers, from which 12 ones have been identified in our study. The electronic ground state in both molecules corresponds to a planar fan‐type structure of C_2v symmetry, in which the actinide atom is connected to a bent C₄ moiety. The other structures are much higher in energy, the ones computed in this study appear between 250 and 1050 kJ/mol. The bonding characteristics in the most relevant structures have been analyzed on the basis of the valence molecular orbitals and natural bond orbital analysis. The most stable structures have been characterized by their spectroscopic (vibrational and electron) properties. © 2014 Wiley Periodicals, Inc.     

Pu and Am sorption to the Baltic Sea bottom sediments

Sorption of Am and Pu isotopes to bottom sediments of the Baltic Sea has been studied under natural and laboratory conditions. Data obtained from sequential extraction, sorption of Am(III), Pu(IV) and Pu(V) as well as oxidation state distribution experiments have shown that Pu(V) sorption mechanism includes a very fast Pu(V) reduction (reaction rate ≤ 2.33 × 10^?3 s^?1) to Pu(IV) by humic substances and/or by Fe(II) to Pu(IV) and partly to Pu(III). Following reduction Pu isotopes were bound to various components of bottom sediments via ion exchange and surface complexation reactions and a slow incorporation into the crystalline structure of Fe minerals. Kinetics experiments showed that the sorption of Pu(V), Pu(IV) and Am(III) to bottom sediments from natural seawater was controlled by the inert layer diffusion process.     

Study of Am and Pu behavior in alkaline media

The redox chemical behavior of americium and plutonium species in alkaline media has been studied, mainly two dis/reproportionation reactions: 2 Pu(VI) = Pu(V) + Pu(VII) and Am(III) + Am(V) = 2Am(IV). It was found that Am(VI) is readily reduced by the simple action of water, and that radiolysis has no effect. This is a marked departure from the behavior of Am in other media, where alpha particle self-irradiation generates redox active species that affect the Am oxidation state. An Am(VII) compound has been synthesized. All results are interesting for the treatment of alkaline high-level radioactive wastes. To cite this article: A.P. Nikonov et al., C. R. Chimie 7 (2004).

Résumé

Étude du comportement de Am et Pu en milieu alcalin. Le comportement redox de Am et Pu a été étudié en milieu alcalin, notamment les dismutations 2 Pu(VI) = Pu(V) + Pu(VII) et 2 Am(IV) = Am(III) + Am(V). Am(VI) est rapidement réduit par l’eau et la radiolyse n’a pas d’effet, contrairement à ce qui se produit dans d’autres milieux. Des indications ont été obtenues sur un composé de Am(VII). Les résultats obtenus sont intéressants pour le traitement des déchets nucléaires encore entreposés en milieu basique. Pour citer cet article : A.P. Nikonov et al., C. R. Chimie 7 (2004).     

Thermogravimetric study of the oxidation behaviour of uranium dicarbide

Systematic studies were carried out on the oxidation behaviour of uranium dicarbide in air in the temperature range 25 °C to 700 °C employing thermogravimetry, evolved gas detection X-ray diffraction and chemical analysis. The mechanistic aspects were investigated and the oxidation was found to proceed through reaction processes involving oxidation of uranium to-UO₃ with release of chemically bound carbon, reaction of released carbon leading to the formation of CO₂ which gets liberated stepwise, decomposition of-UO₃ to U₃O₈ and oxidation of free carbon to CO₂. Examination of the thermoanalytical behaviour of sintered graphite, UO₃, mixtures of graphite with UO₃ and with U₃O₈ supported the above findings.

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Zusammenfassung Das Oxydationsverhalten von Urandikarbid in Luft im Temperaturbereich zwischen 25 und 700 °C wurde mittels Thermogravimetrie, Gasprodukteanalyse, Röntgendiffraktion und chemischer Analyse systematisch untersucht. Studien des Mechanismus ergaben, daß die Oxydation über Teilschritte abläuft, die folgende Schritte beinhalten: Oxydation von Uran zu-UO₃ unter Freisetzung chemisch gebundenen Kohlenstoffes, Reaktion des freigesetzten Kohlenstoffes unter Bildung von CO₂, das schrittweise entweicht, Zerfall von-UO₃ zu U₃O₈ und Oxydation von freiem Kohlenstoff zu CO₂. Diese Feststellungen wurden durch Untersuchung des thermoanalytischen Verhaltens gesinterter Graphit- und UO₃-Proben sowie Mischproben von Graphit mit UO₃ bzw. U₃O₈ bekräftigt.

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, , 25–700°. , , -UO₃ , , , -UO₃ U₃O₈ . ë , UO₃, UO₃ U₃O₈ .

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The authors wish to thank Dr. M. K. Ahmed for his help in O/U measurements and Dr. P. R. Vasudeva Rao for useful advices during the course of the work.     

Sediment sample preparation for the determination of Pu and Am isotopes

Summary Sediment samples from the Romanian sector of the Danube River and the Black Sea coast were analyzed for Pu and Am. Three different ways of bringing the samples into solution were tested: acid attack, microwave digestion and alkaline fusion. A conventional anion-exchange resin was used to separate plutonium from other radionuclides and several variants were tried to improve the separation of americium. The preparation of thin sources for alpha-spectrometry was tested through electrodeposition and coprecipitation with Nd(III). Discussion and recommendations for the dissolution step, the americium separation and preparation of alpha sources are made.     

Determination of 238Pu, 239+240Pu and 241Am in air filters

The aim of this work is to present the method for sequential plutonium and americium activity determination in air filters using chromatographic radionuclide separation and alpha spectrometry measurement. The developed method may be employed for the purposes of workplace monitoring and as an indicator of the need of introducing the individual monitoring as well as a useful complementation of individual monitoring. Basic parameters describing the developed method such as values of chemical recoveries and minimum detectable activities for plutonium and americium isotopes have been determined. Applied counting efficiency was obtained using Monte Carlo calculation method.

     

Determination of239,240Pu and241Am in environmental samples

An accurate and reliable method has been developed and routinely carried out for the sequential determination of^239,240Pu and²⁴¹Am in environmental samples. After suitable pretreatment.^239,240Pu and²⁴¹Am are separated from other elements by means of the anion exchange resin method. Americium-241 is purified by coprecipitation with calcium oxalate and then ion exchanged in mixed media of the mineral acid-methanol. In the analysis,²⁴²Pu (or²³⁶Pu) and²⁴⁴Cm are used as chemical yield monitors. The recoveries of the yield monitors in the analyses of some kinds of environmental samples were 7080% for plutonium and 7686% for curium. The concentration of^239,240Pu in the coastal sea water were 7.022 Bq/l and that of²⁴¹Am was 1.26.3 Bq/l. The mean concentrations of^239,240Pu in the edible parts of the marine products ranged from 0.22 to 7.4 mBq/kg · fresh and those of²⁴¹Am ranged from 0.11 to 2.6 mBq/kg · fresh.     

Sorption of Cs,Pu and Am on clay minerals

Performance assessment of radioactive waste disposal requires modeling of long-term migration of radionuclides through the engineered barriers and the geological environment. The chemical complexity of sorption-desorption processes is usually reduced to integrated parameter distribution coefficients (K _d ). There are a great number of publications on K _d determination, however, the existing data on K _d of radionuclides on different geological materials are for general understanding only and are not very useful for performance assessment, since changes of the geological conditions result in variability of K _d values by two orders of magnitude. In order to obtain realistic sorption data sets for safety relevant radionuclides present in a cement/concrete based repository some preliminary studies were carried out. The development of sorption database for the near-surface repository was started with measurements of cesium, plutonium and americium K _d values. Several experiments were performed in order to determine the chemical composition of cement water which could originate from infiltration of precipitation and from contact of groundwater with concrete. More than 100 batch sorption experiments were conducted with two clay samples. Cs, Pu and Am K _d values were determined for rainwater, groundwater and cement-water of different chemical compositions. Cs, Pu, Am K _d values ranged from 450 to 9700, from 15000 to 21000 and 15000 to 80000 ml/g, respectively. Changes in the geochemical conditions resulted in the variability of Cs, Pu and Am K _d values.     

Radioanalytical approach to determine 238Pu, 239+240Pu, 241Pu and 241Am in soils

The simultaneous determination of multiple actinide isotopes in samples where total quantity is limited can sometimes present a unique challenge for radioanalytical chemists. In this study, re-determination of ²³⁸Pu, ^239+240Pu, and ²⁴¹Am for soils collected and analyzed approximately three decades ago was the goal, along with direct determination of ²⁴¹Pu. The soils had been collected in the early 1970’s from a shallow land burial site for radioactive wastes called the Subsurface Disposal Area (SDA) at the Idaho National Lab (INL), analyzed for ²³⁸Pu, ^239+240Pu, and ²⁴¹Am, and any remaining soils after analysis had been archived and stored. We designed an approach to reanalyze the ²³⁸Pu, ^239+240Pu, and ²⁴¹Am and determine for the first time ²⁴¹Pu using a combination of traditional and new radioanalytical methodologies. The methods used are described, along with estimates of the limits of detection for gamma-and alpha-spectrometry, and liquid scintillation counting. Comparison of our results to the earlier work documents the ingrowth of ²⁴¹Am from ²⁴¹Pu, and demonstrates that the total amount of ²⁴¹Am activity in these soil samples is greater than would be expected due to ingrowth from ²⁴¹Pu decay.     

Effect of industrial pollution on the distribution of Pu and Am in soil and on soil-to-plant transfer of Pu and Am in a pine forest in SW Finland

The effect of industrial pollution on the behavior of plutonium and americium was evaluated in a pine forest in the vicinity of a Cu-Ni smelter in SW Finland. Soil and vegetation were sampled at distances of 0.5, 2, 4 and 8 km from the smelter. The vertical distribution of plutonium and americium was studied in litter, organic layer and mineral layers. The amount of Pu and Am in the litter layer increased and that in the organic layer decreased towards the smelter. Concentrations of plutonium and americium in different vegetation species decreased in the order mushrooms > lichens (Cladina spp., Cetraria islandica) > Empetrum nigrum > Vaccinium vitis-idaea.     

Distribution of Pu and Am in different parts of mango trees

Study of plutonium and americium in the mango leaves and the distribution of their concentration in different parts of the mango fruit were performed. The generally observed trend is leaves > cotyledon > shell > fresh. These results suggest that the contamination of mango fruits by Pu and Am will not pose any radiation risk because the edible portion of the mango has the lowest activity.     

A Rapid Fecal Bioassay Method for Pu/Am

Fecal radiobioassay is a sensitive tool to estimate intake of radionuclides, especially for insoluble or poorly absorbed actinides. To increase efficiency and reduce turnaround time, improvements were introduced in the sample digestion step of a fecal bioassay method to rapidly detect Pu and Am. The acid- and microwave-digestion of the spiked fecal samples (5–10 g) were effectively completed in 1 h. The turnaround time for the sample analysis was minimized to 6 h. The average recoveries for Pu and Am were 35% and 60% for artificial fecal samples, respectively. Much better recoveries for Pu and Am were obtained for natural fecal samples. Observed relative biases for Pu and Am were marginally in the range of -0.25 to +0.50. The relative precision values for both radionuclides were, however, within the performance index of 0.4. This rapid fecal method is a potential candidate for an acceptable quantitative radiobioassay and screening method for the suspected Pu/Am exposures.     

Host phase of239,240Pu and241Am in deep-sea sediment

Host phases of fallout^239,240Pu and²⁴¹Am were studied in the surface sediments obtained in 1994 from abyssal basins of relatively small area of the western North Pacific. An analytical procedure involving sequential chemical extraction was employed for partitioning the host phases of the nuclides in sediment into five fractions: (1) exchangeable (2) bound to carbonate, (3) bound to hydrous Fe-Mn oxides, (4) bound to organic matter and (5) residual. Decrease of total^239,240Pu concentration with decreasing association of^239,240Pu with organic matter, high²⁴¹Am/^239,240Pu activity ratio in carbonate phase and somewhat high proportion of oxidized^239,240Pu in leachable phases suggest a possibility of post-depositional diagenetic remobilization of Pu from sediment to water column.     

Field study of the migration of 237Np, 238Pu and 241Am in a weak loess aquifer

Summertime urban PM_2.5 was collected on cellulose filters in downtown Toronto, using a customized air sampler (635 l/min). Mass concentrations for up to 19 trace elements/ions were measured by ICP-AES, INAA and IC. Source apportionment was performed on these results including additional carbon and total mass concentrations using positive matrix factorization (PMF). PMF factors exhibited trends that indicated soil (18%), stationary (19%), secondary (48%), and vehicle (15%) sources. Potential source contribution function (PSCF) analysis identified probable sources of the stationary and secondary PM_2.5 as originating from the south and southwest of Toronto.     

Fusion and chemical separation of Am,Pu and Sr from barite-concrete

Journal of Radioanalytical and Nuclear Chemistry - The goal of this study was to omit the hazardous hydrofluoric acid for silica removal before fusion of barite-concrete. Furthermore, the goal was...     

Simultaneous liquid scintillation determination of239Pu and241Am in tissue

A liquid scintillation counting method for the simultaneous determination of Pu and Am, with a two-phase cocktail, has been applied to the analysis of a tissue sample from an accidental exposure incident. The sample contained²³⁹Pu,²⁴¹Pu, and²⁴¹Am. In addition to analysis by two liquid scintillation counting techniques, analysis of the sample was performed by -spectroscopy and ZnS scintillation techniques, and the results were compared. The presence of²⁴¹Pu interfered with the liquid scintillation determination of²⁴¹Am when the two-phase cocktail was used, but the results were in agreement sufficient to be useful in determining what course of treatment, if any, might be necessary for the patient.     

Study of 137Cs, 90Sr, 239,240Pu, 238Pu and 241Am behavior in the Chernobyl soil

The vertical distribution of ¹³⁷Cs, ⁹⁰Sr, ^239,240Pu, ²³⁸Pu and ²⁴¹Am was determined in soil samples collected from the Chernobyl exclusion zone in 1994. The results show very close distribution profiles for all radionuclides, with about 90% of the total activity of each nuclide lying between the surface and the fourth centimeter. Sequential extraction methods were used to determine the association of radionuclides in soil. The data on vertical distribution of radionuclide species were used to calculate their vertical migration parameters.     

Low level Pu and Am estimation in liquid waste from nuclear reactor

Estimation of very low amount up to pico-gram of Am and Pu in the liquid waste of U–Pu fuel cycle of the irradiated U fuel from the nuclear reactor has been carried out using combined method of α- and γ-ray spectrometric techniques. ²⁴¹Am was estimated by γ-ray spectrometry from a plancheted source. In spite of the same α energy of 5.49 MeV for ²⁴¹Am and ²³⁸Pu, the amount ²³⁸Pu was estimated by α spectrometry from the same plancheted source after subtracting amount of the ²⁴¹Am obtained from γ-ray spectrometry. The amount of Am and Pu obtained by this technique is found to be superior compared to other techniques even in the presence of Th, U and fission products.