Synthesis and Characterization of Brannerite Wasteforms for the Immobilization of Mixed Oxide Fuel Residues

A possible method for the reduction of civil Pu stockpiles is the reuse of Pu in mixed oxide fuel (MOX). During MOX fuel production, residues unsuitable for further recycle will be produced. Due to their high actinide content MOX residues require immobilization within a robust host matrix. Although it is possible to immobilize actinides in vitreous wasteforms; ceramic phases, such as brannerite (UTi2O6), are attractive due to their high waste loading capacity and relative insolubility. A range of uranium brannerites, formulated GdxU1-xTi2O6, were prepared using a mixed oxide route. Charge compensation of divalent and trivalent cations was expected to occur via the oxidation of U4+ to higher valence states (U5+ or U6+). Gd3+ was added to act as a neutron absorber in the final Pu bearing wasteform. X-ray powder diffraction of synthesised specimens found that phase distribution was strongly affected by processing atmosphere (air or Ar). In all cases prototypical brannerite was formed accompanied by different secondary phases dependent on processing atmosphere. Microstructural analysis (SEM) of the sintered samples confirmed the results of the X-ray powder diffraction. The preliminary results presented here indicate that brannerite is a promising host matrix for mixed oxide fuel residues

On the existence of AgM9(VO4)(6)I (M = Ba, Pb)

The syntheses of the reported compounds AgM9(VO4)6I (M ¼ Ba, Pb) were reinvestigated. Stoichiometric amounts of AgI with either M3(VO4)2 (M ¼ Ba, Pb) or PbO and V2O5 were reacted in the solid-state at elevated temperatures in air or in flame-sealed quartz vessels. The resulting products were characterized by X-ray diffraction, scanning electron microscopy with energy dispersive X-ray analysis, and thermal analyses. Results show that, for all reaction conditions, the target AgM9(VO4)6I (M ¼ Ba, Pb) phases could not be isolated. Instead, heterogeneous phase distributions of primarily M3(VO4)2 (M ¼ Ba, Pb) and AgI were obtained. These findings demonstrate that AgI incorporation into single phase, iodine-deficient apatite derivatives for the immobilization of iodine-129 are not feasible under such conditions. This conclusion is important for the conditioning of iodine-129 in advanced reprocessing flowsheets, where iodine is typically sequestered as AgI

Synthesis of simulant ‘lava-like’ fuel containing materials (LFCM) from the Chernobyl reactor Unit 4 meltdown

A preliminary investigation of the synthesis and characterization of simulant ‘lava-like’ fuel containing materials (LFCM), as low activity analogues of LFCM produced by the melt down of Chernobyl Unit 4. Simulant materials were synthesized by melting batched reagents in a tube furnace at 1500 °C, under reducing atmosphere with controlled cooling to room temperature, to simulate conditions of lava formation. Characterization using XRD and SEM-EDX identified several crystalline phases including ZrO2, UOx and solid solutions with spherical metal particles encapsulated by a glassy matrix. The UOX and ZrO2 phase morphology was very diverse comprising of fused crystals to dendritic crystallites from the crystallization of uranium initially dissolved in the glass phase. This project aims to develop simulant LFCM to assess the durability of Chernobyl lavas and to determine the rate of dissolution, behavior and evolution of these materials under shelter conditions

Ce and U speciation in wasteforms for thermal treatment of plutonium bearing wastes, probed by L3 edge XANES

X-ray absorption spectroscopy was applied to understand the speciation of elements relevant to the immobilisation and disposal of radioactive plutonium bearing wastes, utilizing Ce as a Pu surrogate. Ce L3 XANES (X-ray Absorption Near Edge Structure) characterisation of a crystallised glass material produced by cold crucible plasma vitrification, at demonstration scale, evidenced incorporation as Ce3+ within the glass phase, providing an important validation of laboratory scale studies. U and Ce L3 XANES investigation of brannerite ceramics, U0.9Ce0.1Ti2O6, synthesized under oxidizing, neutral and reducing conditions, established the charge compensation mechanism as incorporation of Ce3+ through formation of U5+ and/or U6+ In each of these examples, X-ray Absorption Spectroscopy has provided a pivotal understanding of element speciation in relation to the mechanism of incorporation within the host wasteform intended for geological disposal

Use of WetSEM® capsules for convenient multimodal scanning electron microscopy, energy dispersive X-ray analysis, and micro Raman spectroscopy characterisation of technetium oxides

SEM–EDX and Raman spectroscopy analysis of radioactive compounds is often restricted to dedicated instrumentation, within radiological working areas, to manage the hazard and risk of contamination. Here, we demonstrate application of WetSEM® capsules for containment of technetium powder materials, enabling routine multimodal characterisation with general user instrumentation, outside of a controlled radiological working area. The electron transparent membrane of WetSEM® capsules enables SEM imaging of submicron non-conducting technetium powders and acquisition of Tc Lα X-ray emission, using a low cost desktop SEM–EDX system, as well as acquisition of good quality μ-Raman spectra using a 532 nm laser

Synthesis and characterisation of the hollandite solid solution Ba1.2-xCsxFe2.4-xTi5.6+xO16 for partitioning and conditioning of radiocaesium

The geological disposal of high level radioactive waste requires careful budgeting of the heat load produced by radiogenic decay. Removal of high-heat generating radionuclides, such as 137 Cs, reduces the heat load in the repository allowing the remaining high level waste to be packed closer together therefore reducing demand for repository space and the cost of the disposal of the remaining wastes. Hollandites have been proposed as a possible host matrix for the long-term disposal of Cs separated from HLW raffinate. The incorporation of Cs into the hollandite phase is aided by substitution of cations on the B-site of the hollandite structure, including iron. A range of Cs containing iron hollandites were synthesised via an alkoxide-nitrate route and the structural environment of Fe in the resultant material characterised by Mössbauer and X-ray Absorption Near Edge Spectroscopy. The results of spectroscopic analysis found that Fe was present as octahedrally co-ordinated Fe (III) in all cases and acts as an effective charge compensator over a wide solid solution range

Larval mortality rates and population dynamics of Lesser Sandeel (Ammodytes marinus) in the northwestern North Sea

Intense fishing of a stock of sandeels (Ammodytes marinus) on the sand banks off the Firth of Forth, northeast Scotland, during the 1990s led to a decline in catch per unit effort to uneconomic levels and collateral failures of piscivorous seabird breeding success at nearby colonies. A prohibition on fishing in 1999 was followed by a short-term recovery of stock biomass, but then a sustained decline to very low levels of abundance. Demographic survey data show that despite the decline in stock, recruit abundance was maintained implying an increasing larval survival rate, and that the stock decline was not due to recruitment failure. To verify this hypothesis we analysed a 10-year long data set of weekly catches of sandeel larvae at a nearby plankton monitoring site to determine the patterns of larval mortality and dispersal. We found that the loss rate of larvae up to 20 d age decreased over time, corresponding with the trend in survival rate implied by the stock demography data. The pattern of loss rate in relation to hatchling abundance implied that mortality may have been density dependent. Our study rules out increased larval mortality as the primary cause of decline in the sandeel stock

Synthesis and characterization of iodovanadinite using PdI2, an iodine source for the immobilisation of radioiodine

The synthesis of a palladium-containing iodovanadinite derivative, hypothetically “PdPb9(VO4)6I2”, was attempted using PdI2 as a source of iodine in searching for a novel waste form for radioiodine. Stoichiometric amounts of Pb3(VO4)2 and PdI2 were batched and reacted at elevated temperatures in sealed vessels. Batched material was also subjected to high-energy ball-milling (HEBM) in order to reduce reaction time and the potential for iodine volatilization during subsequent reaction at 200–500 °C. The resulting products were characterized using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, IR spectroscopy, thermal analysis and Pd K XANES. Results showed that PdI2 can function as a sacrificial iodine source for the formation of iodovanadinite, prototypically Pb10(VO4)6I2, however, the incorporation of Pd into this phase was not definitively observed. The sacrificial reaction mechanism involved the decomposition of PdI2 to Pd metal and nascent I2, with the latter incorporated into the iodovanadinite Pb10(VO4)6I2 phase. In comparison to processing using standard solid state reaction techniques, the use of HEBM prior to high temperature reaction generates a more homogeneous end-product with better iodine retention for this system. Overall, the key novelty and importance of this work is in demonstrating a method for direct immobilisation of undissolved PdI2 from nuclear fuel reprocessing, in a composite wasteform in which I-129 is immobilised within a durable iodovandinite ceramic, encapsulating Pd metal

Synthesis, characterisation and corrosion behaviour of simulant Chernobyl nuclear meltdown materials

Understanding the physical and chemical properties of materials arising from nuclear meltdowns, such as the Chernobyl and Fukushima accidents, is critical to supporting decommissioning operations and reducing the hazard to personnel and the environment surrounding the stricken reactors. Relatively few samples of meltdown materials are available for study, and their analysis is made challenging due to the radiation hazard associated with handling them. In this study, small-scale batches of low radioactivity (i.e., containing depleted uranium only) simulants for Chernobyl lava-like fuel-containing materials (LFCMs) have been prepared, and were found to closely approximate the microstructure and mineralogy of real LFCM. The addition of excess of ZrO2 to the composition resulted in the first successful synthesis of high uranium–zircon (chernobylite) by crystallisation from a glass melt. Use of these simulant materials allowed further analysis of the thermal characteristics of LFCM and the corrosion kinetics, giving results that are in good agreement with the limited available literature on real samples. It should, therefore, be possible to use these new simulant materials to support decommissioning operations of nuclear reactors post-accident

An investigation of iodovanadinite wasteforms for the immobilisation of radio-iodine and technetium

99Tc and 129I are two long-lived, highly soluble and mobile fission products that pose a long-term hazard. A proposed wasteform for the disposal of radio-iodine is iodovanadinite (Pb5(VO4)3I), an apatite-structured vanadate. In this investigation, a suite of potential iodovanadinite wasteforms designed for the co-disposal of Tc and I or the sole disposal of I were synthesised via hot isostatic pressing (with Mo as a surrogate for Tc). It was found that direct synthesis from oxide and iodide precursors was possible using hot isostatic pressing (HIPing). Increasing overpressure during HIPing was found to improve the density of the final product. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses indicated that the use of AgI as the source of iodine affected the formation of the target iodovanadinite phase and produced unfavourable phase assemblages. Here, we report the direct synthesis of Pb5(VO4)3I in a single step by hot isostatic pressing