Solution composition and particle size effects on the dissolution and solubility of a ThO2 microstructural analogue for UO2 matrix of nuclear fuel

The objective of this study was to investigate the dissolution rate of ThO2 which was synthesised to approximate, as closely as possible, the microstructure of UO2 in a nuclear fuel matrix. The optimal sintering temperature for ThO2 pellets was found to be 1750 ℃, which produced pellets with a microstructure similar to UO2 nuclear fuel pellets, with randomly oriented grains ranging in size from 10 to 30 μm. Dissolution was conducted using ThO2 particles of different size fractions (80 to 160 μm and 2 to 4 mm) in the presence and absence of carbonate, in solutions with pH from 2 to 8 and at 80 ℃. Dissolution rates were calculated from Th released from the solid phase to solution. Particles of ThO2 were also leached with 1 M HNO3 at 80 ℃ in order to investigate the morphological changes at the particle surfaces. The concentration of Th was found to be ≥ 10–9 mol/L at pH ≤ 4, lower than the theoretical solubility of crystalline ThO2. At higher pH values, from 4 to 8, the measured concentrations (10−10 to 10–12 mol/L) were between the theoretical solubility of ThO2 and Th(OH)4. Grain boundaries were shown to exert an influence on the dissolution of ThO2 particles. Using high resolution aqueous solution analysis, these data presented here extend the current understanding of Th solubility in solutio

Evolution of phase assemblage of blended magnesium potassium phosphate cement binders at 200 degrees and 1000 degrees C

The fire performance of magnesium potassium phosphate cement (MKPC) binders blended with fly ash (FA) and ground granulated blast furnace slag (GBFS) was investigated up to 1000°C using X-ray diffraction, thermogravimetric analysis and SEM techniques. The FA/MKPC and GBFS/MKPC binders dehydrate above 200°C to form amorphous KMgPO4, concurrent with volumetric and mass changes. Above 1000°C, additional crystalline phases were formed and microstructural changes occurred, although no cracking or spalling of the samples was observed. These results indicate that FA/MKPC and GBFS/MKPC binders are expected to have satisfactory fire performance under the fire scenario conditions relevant to the operation of a UK or other geological disposal facility

Interactions between Simulant Vitrified Nuclear Wastes and high pH solutions: A Natural Analogue Approach

This study details the characterization of a glass sample exposed to hyperalkaline water and calcium-rich sediment for an extended time period (estimated as 2-70 years) at a lime (CaO) waste site in the UK. We introduce this site, known as Peak Dale, in reference to its use as a natural analogue for nuclear waste glass dissolution in the high pH environment of a cementitious engineered barrier of a geological disposal facility. In particular, a preliminary assessment of alteration layer chemistry and morphology is described and the initiation of a long-term durability assessment is outlined

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

Characterisation of a complex CaZr0.9Ce0.1Ti2O7 glass–ceramic produced by hot isostatic pressing

The behaviour of Ce-containing zirconolites in hot isostatically pressed (HIPed) materials is complex, characterised by redox interactions between the metallic HIP canister that result in reduction of Ce4+ to Ce3+. In this work, a glass–ceramic of composition 70 wt.% CaZr0.9Ce0.1Ti2O7 ceramic in 30 wt.% Na2Al2Si6O16 glass was produced by HIP (approx. 170 cm3 canister) to examine the extent of the material–canister interaction. A complex material with six distinct regions was produced, with the extent of Ce reduction varying depending on the distance from the canister. Notably, the innermost bulk regions (those approximately 7 mm from the canister) contained only Ce4+, demonstrating that a production-scale HIPed glass–ceramic would indeed have a bulk region unaffected by the reducing environment induced by a ferrous HIP canister despite the flow of glass at the HIP temperature. Each of the six regions was characterised by XRD (including Rietveld method refinements), SEM/EDX and linear combination fitting of Ce L3-edge XANES spectra. Regions in the lower part of the canister were found to contain a significantly higher fraction of Ce4+ compared to the upper regions. Though zirconolite-2M was the major crystalline phase observed in all regions, the relative abundances of minor phases (including sphene, baddeleyite, rutile and perovskite) were higher in the outermost regions, which comprised a significantly reduced Ce inventory

Synthesis, characterisation and preliminary corrosion behaviour assessment of simulant Fukushima nuclear accident fuel debris

Nuclear fuel debris generated at the Fukushima Daiichi nuclear power plant during the loss of coolant accident in 2011, still resides within the reactor units, constantly cooled by water. Until it is retrieved, the fuel debris will corrode, releasing radioactive elements into the coolant water and the ground surrounding the reactors. To predict the corrosion behaviour of these materials, and to establish parameters for experiments with U-containing and real fuel debris, the corrosion of two surrogate fuel debris materials, with a composition of Ce(1-x)ZrxO2 (x = 0.2 and 0.4), was investigated. Materials were synthesised by a wet chemistry route and pellets were sintered at 1700°C in air atmosphere. Due to the slow corrosion kinetics, aggressive conditions were applied, and corrosion experiments were performed in 9 mol.L^-1 HNO3 under static conditions. The incorporation of Zr into the structure of Ce reduced the normalised dissolution rate; from (3.75 ± 0.15) × 10-6 g.m-2.d-1 to (4.96 ± 0.28) × 10^-6 g.m^-2.d^-1 for RL(Ce) of Ce0.8Zr0.2O2 and Ce0.6Zr0.4O2, respectively

International validation of a urinary biomarker panel for identification of active lupus nephritis in children.

Conventional markers of juvenile-onset systemic lupus erythematosus (JSLE) disease activity fail to adequately identify lupus nephritis (LN). While individual novel urine biomarkers are good at detecting LN flares, biomarker panels may improve diagnostic accuracy. The aim of this study was to assess the performance of a biomarker panel to identify active LN in two international JSLE cohorts.Novel urinary biomarkers, namely vascular cell adhesion molecule-1 (VCAM-1), monocyte chemoattractant protein 1 (MCP-1), lipocalin-like prostaglandin D synthase (LPGDS), transferrin (TF), ceruloplasmin, alpha-1-acid glycoprotein (AGP) and neutrophil gelatinase-associated lipocalin (NGAL), were quantified in a cross-sectional study that included participants of the UK JSLE Cohort Study (Cohort 1) and validated within the Einstein Lupus Cohort (Cohort 2). Binary logistic regression modelling and receiver operating characteristic curve analysis [area under the curve (AUC)] were used to identify and assess combinations of biomarkers for diagnostic accuracy.A total of 91 JSLE patients were recruited across both cohorts, of whom 31 (34 %) had active LN and 60 (66 %) had no LN. Urinary AGP, ceruloplasmin, VCAM-1, MCP-1 and LPGDS levels were significantly higher in those patients with active LN than in non-LN patients [all corrected p values (p c) < 0.05] across both cohorts. Urinary TF also differed between patient groups in Cohort 2 (p c = 0.001). Within Cohort 1, the optimal biomarker panel included AGP, ceruloplasmin, LPGDS and TF (AUC 0.920 for active LN identification). These results were validated in Cohort 2, with the same markers resulting in the optimal urine biomarker panel (AUC 0.991).In two international JSLE cohorts, urinary AGP, ceruloplasmin, LPGDS and TF demonstrate an 'excellent' ability for accurately identifying active LN in children

Influence of young cement water on the corrosion of the International Simple Glass

Understanding the corrosion of nuclear waste glass is critical to predicting its safe disposal within a geological facility. The corrosion mechanisms and kinetics of the International Simple Glass, a simplified version of high-level nuclear waste glass, was shown to be significantly influenced by a high pH cement solution representative of disposal conditions. We provide the first microscopic characterisation of the porous, Zr-rich aluminoalkali-silica gel corrosion layer that was observed. Ca, Na and K from the cement solution were incorporated into the corrosion layer to charge compensate Si, Al and Zr species; the incorporation of Al was postulated to result in precipitation of an aluminosilicate-rich gel with large voids, facilitating rapid transport of species through the gel layer and significantly enhancing the corrosion rate. Precipitation of Al-containing zeolite and phyllosilicate phases was also observed, indicating that cementitious solutions may promote the detrimental ‘rate resumption’ stage of glass corrosion

Short communication : the dissolution of UK simulant vitrified high-level-waste in groundwater solutions

Dissolution of a simulant UK nuclear waste glass containing Mg, Ca and Zn was investigated over 35 d at 50 °C in water and simulant groundwater solutions. The dissolution rates were influenced subtly by the groundwater composition, following the trend, from least to most durable: clay > water > granite ≈ saline. Solutions were rapidly silica saturated but boron dissolution rates continued to increase. This is hypothesised to be due to the formation of secondary Mg-silicate precipitates, preventing the formation of a passivating silica gel layer and allowing glass dissolution to proceed at close to the maximum rate