Arsenopyrite (FeAsS) is the most common As-bearing sulfide mineral. Under oxidising conditions, such as those in mine waste systems, it breaks down to release acids of As and S into the environment, ...resulting in acid mine drainage with high concentrations of dissolved As. In this communication, current knowledge of arsenopyrite oxidation is reviewed based on a survey of the existing literature, which has focused on processes and reactions at the mineral surface. X-ray photoelectron spectroscopy (XPS) has shown that the oxidation of arsenopyrite in acid is more rapid than in air, water, or in alkaline solutions. Oxidation products reported by XPS include Fe(III) oxide, As(III), As(V), SO32- and SO42-. The elemental constituents of arsenopyrite oxidise at different rates, although there is no consensus as to which is the fastest or slowest to oxidise. Electrochemical studies have highlighted the formation of elemental S on the arsenopyrite surface, while XPS studies suggest that only oxy-anions of S form. Kinetic studies of arsenopyrite oxidation suggest that O2 and Fe3+ are the dominant inorganic agents causing arsenopyrite dissolution. The bacterially-mediated oxidation of arsenopyrite by acidophilic Fe- and S-oxidising bacteria such as Acidithiobacillus ferrooxidans and Acidithiobacillus caldus, is more extensive than abiotic oxidation. The literature pertaining to arsenopyrite oxidation is divided regarding the reaction stoichiometry, and the composition and layering of surface overlayers.
Neoadjuvant therapy is increasingly the standard of care in the management of locally advanced adenocarcinoma of the oesophagus and junction (AEG). In randomised controlled trials (RCTs), the MAGIC ...regimen of pre- and postoperative chemotherapy, and the CROSS regimen of preoperative chemotherapy combined with radiation, were superior to surgery only in RCTs that included AEG but were not powered on this cohort. No completed RCT has directly compared neoadjuvant or perioperative chemotherapy and neoadjuvant chemoradiation. The Neo-AEGIS trial, uniquely powered on AEG, and including comprehensive modern staging, compares both these regimens.
This open label, multicentre, phase III RCT randomises patients (cT2-3, N0-3, M0) in a 1:1 fashion to receive CROSS protocol (Carboplatin and Paclitaxel with concurrent radiotherapy, 41.4Gy/23Fr, over 5 weeks). The power calculation is a 10% difference in favour of CROSS, powered at 80%, two-sided alpha level of 0.05, requiring 540 patients to be evaluable, 594 to be recruited if a 10% dropout is included (297 in each group). The primary endpoint is overall survival, with a minimum 3-year follow up. Secondary endpoints include: disease free survival, recurrence rates, clinical and pathological response rates, toxicities of induction regimens, post-operative pathology and tumour regression grade, operative in-hospital complications, and health-related quality of life. The trial also affords opportunities for establishing a bio-resource of pre-treatment and resected tumour, and translational research.
This RCT directly compares two established treatment regimens, and addresses whether radiation therapy positively impacts on overall survival compared with a standard perioperative chemotherapy regimen Sponsor: Irish Clinical Research Group (ICORG).
NCT01726452 . Protocol 10-14. Date of registration 06/11/2012.
Mn-doped UO2 is under consideration for use as an accident tolerant nuclear fuel. We detail the synthesis of Mn-doped UO2 prepared via a wet co-precipitation method, which was refined to improve the ...yield of incorporated Mn. To verify the Mn-doped UO2 defect chemistry, X-ray absorption spectroscopy at the Mn K-edge was performed, in addition to X-ray diffraction, Raman spectroscopy and high-energy resolved fluorescence detection X-ray absorption near edge spectroscopy at the U M4-edge. It was established that Mn2+ directly substitutes for U4+ in the UO2 lattice, accompanied by oxygen vacancy (Ov) charge compensation. In contrast to other divalent-element doped UO2 materials, compelling evidence for U5+ in a charge compensating role was not found. This work furthers understanding of the structure and crystal chemistry of Mn-doped UO2, which could show potential advantages as a novel efficient advanced nuclear fuel.
Research and innovation is key to delivering UK Government's civil nuclear energy policy, in particular to accelerate reduction in the hazard, timescale and cost of legacy decommissioning and ...geological disposal of radioactive wastes. To address this challenge, a national centre of excellence, the HADES Facility, has been established to support research and innovation in High Activity Decommissioning Engineering & Science, as part of the wider network of UK National Nuclear User Facilities. Herein, we describe the development of this user facility, the current status of its capability, and functional equipment specifications. The unique capabilities of the HADES Facility, in the UK academic landscape, are emphasised, including: handling of weighable quantities of 99Tc and transuranics; quantitative electron probe microanalysis of radioactive materials; hot isostatic pressing of radioactive materials; and laboratory-based X-ray absorption and emission spectroscopy. An example case study of the application of the HADES capability is described, involving thermal treatment of a real radioactive ion exchange resin waste to produce a conceptual vitrified waste form.
The presence of phosphorus in borosilicate glass (at 0.1 – 1.3mol % P2O5) and in iron-phosphate glass (at 53mol % P2O5) stimulated the growth and metabolic activity of anaerobic bacteria in model ...systems. Dissolution of these phosphorus containing glasses was either inhibited or accelerated by microbial metabolic activity, depending on the solution chemistry and the glass composition. The breakdown of organic carbon to volatile fatty acids increased glass dissolution. The interaction of microbially reduced Fe(II) with phosphorus-containing glass under anoxic conditions decreased dissolution rates, whereas the interaction of Fe(III) with phosphorus-containing glass under oxic conditions increased glass dissolution. Phosphorus addition to borosilicate glasses did not significantly affect the microbial species present, however, the diversity of the microbial community was enhanced on the surface of the iron phosphate glass. Results demonstrate the potential for microbes to influence the geochemistry of radioactive waste disposal environments with implication for wasteform durability.
Vitrified radioactive waste is designed to immobilize long lived radionuclides for time periods up to 106 years until activity has decayed to safe levels. Radioactive elements are chemically incorporated in the glass network and so are released as the glass dissolves. It is, therefore, important to understand the durability of vitrified radioactive waste in subsurface environments to inform the safety case for their long-term disposal. This paper investigates glass-microbe interactions using non-active surrogates for radioactive waste glasses and relevant anaerobic microorganisms to build a mechanistic understanding of glass dissolution in complex natural environments.
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•Phosphorous released from nuclear waste type glasses stimulated microbial metabolism•Biofilms formed on the surface of glass that contained both iron and phosphorous•Microbial metabolism affected the rate of glass dissolution•An increase in glass dissolution was associated with microbial production of volatile fatty acids•A decrease in glass dissolution was associated with microbial reduction of Fe(III) to Fe(II).
Storage of 200L drums of PCM waste at the Sellafield site, UK. Display omitted
Four waste simulants, representative of Plutonium Contaminated Materials (PCMs) at the Sellafield site, were vitrified ...through additions of Ground Granulated Blast-furnace Slag (GGBS). Ce (as a Pu surrogate) was effectively partitioned into the slag product, enriched in an amorphous CaO–Fe2O3–Al2O3–SiO2 phase when other crystalline phases were also present. Ce L3 edge XANES data demonstrated Ce to be present as trivalent species in the slag fraction, irrespective of the waste type. Estimated volume reductions of ca. 80–95% were demonstrated, against a baseline of uncompacted 200L PCM waste drums. The dissolution behaviour of PCM slag wasteforms was investigated at 50°C in saturated Ca(OH)2 solution under N2 atmosphere, to simulate the hyperalkaline anoxic environment of a cementitious UK Geological Disposal Facility for Intermediate Level Waste (ILW). These experiments demonstrated the performance of the slag wasteforms to be comparable to that of other vitrified ILW materials considered potentially suitable for geological disposal.
Technetium and transuranic elements (TRUs) are long-lived radionuclides, produced as a result of nuclear power generation. Co-immobilisation of these radionuclides in a ceramic wasteform is ...attractive as they are problematic for vitrification and would reduce the demand on a future geological disposal facility. A range of zirconolite ceramics have been produced via an oxide route using the surrogates Mo and Ce with a view to the co-immobilisation of Tc and TRUs. The resultant materials were characterised by XRD, SEM-EDX, TEM and XAS. Final phase assemblage was found to be affected by target stoichiometry, the Ca precursor used, processing temperature and processing atmosphere. Through appropriate optimisation of processing conditions and target stoichiometry, the results of this study show co-immobilisation of Tc and TRUs is a promising approach.
The structure and dissolution behaviour of Na2O·CaO·(15–x)Al2O3·xB2O3·SiO2 and Na2O·MgO·(15–x)Al2O3·xB2O3·SiO2 glasses, relevant to compositions of UK nuclear waste glass, have been investigated ...using nuclear magnetic resonance (NMR) spectroscopy and static dissolution experiments using the PCT protocol. Structural data from 11B, 27Al and 29Si NMR analyses show that increasing the B2O3/(Al2O3 + B2O3) ratio of the alkali-alkaline-earth aluminoborosilicate glasses led to an overall decrease in the proportion of non-silicate tetrahedral species (IVAl + IVB) and a decrease in SiOX bonds (XB, Al). The Mg-containing glasses exhibited lower IVB fractions than their Ca-containing counterparts, which is thought to be due to the presence of IVMg tetrahedra in the network. The measured corrosion rates were similar for both Ca and Mg-containing glasses although unexpectedly some Ca-containing glasses exhibited higher corrosion losses than the Mg-containing ones for time periods up to 112 d. However, there was evidence of a greater tendency to rate resumption in the Mg containing than the Ca containing ones. Alteration products were found to contain Ca, Si and Al with the Ca containing glasses and Ca, Mg, Si and Al with the Mg containing glasses; Na was not detected in the alteration products although its presence cannot be ruled out based on the data obtained.
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.
Decommissioning of the damaged Chernobyl nuclear reactor Unit 4 is a top priority for the global community. Before such operations begin, it is crucial to understand the behaviour of the hazardous ...materials formed during the accident. Since those materials formed under extreme and mostly unquantified conditions, modelling alone is insufficient to accurately predict their physical, chemical and, predominantly, mechanical behaviour. Meanwhile, knowledge of the mechanical characteristics of those materials, such as their strength, is a priority before robotic systems are employed for retrieval and the force expected from them to be exerted is one of the key design questions. In this paper we target to measurement of the standard mechanical properties of the materials formed during the accident by testing small-scale, low radioactivity simulants. A combined methodology using Hertzian indentation, synchrotron X-ray tomography and digital volume correlation (DVC), was adopted to estimate the mechanical properties. Displacement fields around the Hertzian indentation, performed in-situ in a synchrotron, were measured by analysing tomograms with DVC. The load applied during the indentation, combined with full-field displacement measured by DVC was used to estimate the mechanical properties, such as Young's modulus and Poisson's ratio of these hazardous materials.
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•Chernobyl “lava-like” fuel-containing material (LFCM) can be classified as brittle.•Porosity varies depending on the type of the LFCM (brown or black).•The range of Young's modulus for the Chernobyl lavas varies between 5 GPa and 16 GPa.•The stiffness of brown lava is almost 2.5 time greater than that of black lava.
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