Magnox Waste Research Articles

Temperature dependent lithium isotope fractionation during glass dissolution

Understanding the mechanisms by which borosilicate glasses corrode in contact with aqueous solutions remains a challenge to the safety case for the geological disposal of vitrified high-level nuclear waste. Here, lithium isotope fingerprinting techniques were applied to the leachates of a simulant Magnox waste glass to probe the mechanisms of aqueous corrosion at both short and long timescales (6 hours to 464 days). Experiments took place at 40 and 90 °C to assess the consistency of the dissolution mechanisms across a range of commonly employed temperatures and the legitimacy of applying higher temperature experimental datasets to understand glass corrosion within a disposal facility at lower temperatures.Two competing release mechanisms were observed for lithium (diffusion and hydrolysis), and the relative proportions of these mechanisms changed through time. Leachates initially had lower δ7Li values than the pristine glass (−2.7‰ at 40 °C and −1.1‰ at 90 °C relative to the pristine glass) at both temperatures due to lithium leaching incongruently through diffusive processes. The greater offset between solution and solid at lower temperatures indicates a larger rate of diffusion (incongruent dissolution) relative to the rate of hydrolysis (congruent dissolution) at lower temperatures. The fraction of lithium released through diffusion relative to the fraction of lithium released through hydrolysis then increased at both temperatures with time up to 126 days, increasing from 0.47 and 0.22 at 6 hours to 0.66 and 0.41 at 126 days at 40 and 90 °C respectively. Subsequently, the fractions of lithium released through diffusion sharply decreased to 0.36 at 40 °C and 0.22 at 90 °C after 464 days, consistent with network hydrolysis coupled with secondary phase precipitation later controlling the long-term release of Li at both temperatures. Throughout the duration of the experiments (464 days) the δ7Li values in solution increased to 9.0‰ at 40 °C and 10.0‰ at 90 °C due to the formation of talc and montmorillonite phases at 40 °C and additional smectite phases at 90 °C. Further, no evidence for the formation of a diffusive barrier to the transport of Li within the alteration layers became apparent during the later stages of dissolution at either temperature. However, the fraction of lithium leached through diffusion was still significant throughout all stages of dissolution. Lithium isotope ratios in solution were correlated with the transition from a system which was increasingly dominated by lithium diffusion as the dissolution rate slowed to one which was controlled by hydrolysis coupled with secondary phase precipitation at long durations. Alongside elemental ratios in solution, these results were consistent with the same set of mechanisms governing dissolution across the temperature range studied.

The use of a CZT detector with robotic systems

This work is focused on the use of a CZT detector for a radiation mapping with an industrial robotic arm. Measurements were carried out within the RadioRoSo experiment (Radioactive Waste Robotic Sorter), under the umbrella of EU FP7 project ECHORD++. In tests with a dual-arm robot and standard point sources of 137Cs and 60Co, a Magnox waste was mimicked. Thereafter, for relevant measurement geometries and selected shielding materials, full energy peak efficiencies were calculated using the MCNP transport code. Simulated FEP efficiency values were used for minimum detectable activity assessments for expected measurement conditions. Obtained results would be also applicable for cases of shielded lost/orphan point-like sources.

Relating Magnox and international waste glasses

Magnox and international radioactive waste glasses observe significantly different aqueous dissolution behaviours. Previously, the effects of Li on the kinetics of dissolution and B network of analogues of a complex Magnox waste glass were investigated (Li-Mg-EM). Here, an “International Simple Glass” with Li substituted for Na at two ratios (Li-ISG) was fabricated to compare the aqueous durability of Magnox and international glasses. 11B MAS-NMR, 23Na MAS-NMR, 6Li1H CP-NMR and SEM studies are presented. The IIIB/IVB ratio and the role of Na in the pristine glasses varied insignificantly with the Li:Na ratio. Further, the B network of Li-ISG was shown to leach congruently. Li, Na and Mg-containing secondary phases were present for Li-Mg-EM, whilst no precipitates were observed for Li-ISG. Li in ISG was shown to be detrimental but further substitution of Li improved long-term aqueous durability, which was attributed to a LiNa mixed alkali effect for Li-ISG but not Li-Mg-EM.

Evaluating the temperature dependence of Magnox waste glass dissolution

Before vitrified waste can be safely disposed of, a comprehensive understanding of the effects of temperature on wasteform aqueous durability must be acquired. In the experiments herein, a Magnox waste glass of 25 wt% simulant waste loading was leached in static batch experiments at 40, 70, 80 and 90 °C to investigate the Arrhenius dependence of dissolution. Results from ICP-OES/MS, EDX, SEM and XRD analyses are discussed in terms of the roles of the glass species within Magnox waste glasses.Here we show that changing the dissolution temperature changed the rate of hydrolysis relative to interdiffusion. At higher temperatures, the initial release of sodium deviated from Arrhenius-type behaviour and instead displayed an almost flat Arrhenius plot; demonstrating changes in temperature affect sodium differently to other glass species. Whilst the activation energies of the lithium and boron releases were in the range of a mixed reaction, the higher activation energy of sodium at lower temperatures combined with its non-Arrhenius behaviour suggested the dissolution processes of lithium and sodium differed. These observations were attributed to the preference of sodium to charge compensate the boron network.

Impacts of lithium on Magnox waste glass dissolution

The safe storage of vitrified waste demands a thorough understanding of the effects of wasteform composition on chemical durability. One of the major compositional differences between UK glass and international glasses is the presence of Li. Based upon a 25 wt% loading UK Magnox waste glass, two seven-component analogues of molar Li:Na 1.0 and 1.5 were leached to investigate the effects of Li on chemical durability. A comprehensive 11B nuclear magnetic resonance study then took place to investigate the B network before and after dissolution.Here we show that the proportion of IIIB to IVB units did not evolve as the Li:Na ratio was varied; suggesting that Na preferentially charge compensates the B network. However, the B network was shown to leach incongruently at 90 °C. Despite Li being shown to be detrimental to durability during the earlier dissolution regimes, the residual rates of alteration implied excess Li contents had no long-term effects on chemical durability. The observed incongruent dissolution of the B network and initially decreased chemical durability could be attributed to Li preferentially modifying the Si network, thereby promoting glass hydration and B network dissolution whilst the Na compensated IVB units were less affected than IIIB units.

The effect of magnesium on the local structure and initial dissolution rate of simplified UK Magnox waste glasses

A series of simplified glasses were prepared to mimic the United Kingdom's Magnox radioactive waste glasses and determine the separate effect of the presence of Mg on the glass structure and the initial dissolution rate. These glasses had an alkaline earth (Ca/Mg) content of 6.5 mol% and relative ratios of Si, B and Na similar to 25 wt% waste loaded Magnox waste glass simulant. Each simplified glass had similar macroscopic properties, differing only in Ca/Mg ratio. 25Mg magic angle spinning nuclear magnetic resonance (MAS NMR) spectra of the simplified Mg endmember (MgEM) glass (with no Ca) and the full-component simulant glass were similar, consistent with the similar Mg local environments in both glasses. 11B MAS NMR spectra of the series of simplified glasses showed a systematic increase in the amount of three-coordinated boron ([3]B) with increasing amounts of Mg. A clear change in the charge balancing of four-coordinated boron ([4]B) by Mg compared with Ca is observed. However, 11B NMR measurements of the leached material showed that the additional [3]B was not preferentially leached from the Mg containing samples. Despite the structural changes in the glass induced by Ca/Mg substitution, initial dissolution rates (r0) remained invariant, within error, with Ca/Mg ratio. This indicates that the poorer aqueous durability of Mg-containing Magnox waste glass measured experimentally in long-term leaching experiments, compared with SON68 glass containing Ca, is not caused by a primary structural effect in the glass.

Alteration layer formation of Ca- and Zn-oxide bearing alkali borosilicate glasses for immobilisation of UK high level waste: A vapour hydration study

The UK high level nuclear waste glass modified with CaO/ZnO was investigated using the vapour phase hydration test, performed at 200 °C, with the aim of understanding the impact of the modification on the chemical composition and microstructure of the alteration layer. Experiments were undertaken on non-modified and CaO/ZnO-modified base glass, with or without 25 wt% of simulant Magnox waste calcine. The modification resulted in a dramatic reduction in gel layer thickness and also a reduction in the reaction rate, from 3.4 ± 0.3 g m−2 d−1 without CaO/ZnO modification to 0.9 ± 0.1 g m−2 d−1 with CaO/ZnO. The precipitated phase assemblage for the CaO/ZnO-modified compositions was identified as hydrated Ca- and Zn-bearing silicate phases, which were absent from the non-modified counterpart. These results are in agreement with other recent studies showing the beneficial effects of ZnO additions on glass durability.

The Effect of Composition on Short- and Long-term Durability of UK HLW Glass

An understanding of the aqueous durability of glass is essential for determining the dissolution and release of radionuclides from vitrified nuclear waste in a geological disposal facility over short and long timescales. There are many factors that determine the rate of glass dissolution in aqueous solution, and environmental factors such as temperature and pH will be significant. However, in terms of glass properties, the composition has the biggest influence on aqueous durability.The majority of High Level Waste (HLW) worldwide has been immobilised using borosilicate glass, although within this family there are significant compositional variations between different countries depending on the composition of the waste being vitrified. For example, the French R7T7 HLW glass contains calcium, while the Magnox waste glass produced in the UK contains significant quantities of magnesium, which results in different dissolution behavior.This paper summarizes the main compositional variations in UK vitrified HLW and identifies the key similarities and differences in composition that affect short- and long-term glass durability in aqueous solution. The effect of a number of key elements is discussed along with the current state of the art understanding of how they impact on the glass dissolution mechanisms.

Chemical durability of vitrified wasteforms: effects of pH and solution composition

AbstractVitrification is used for the immobilization and conditioning of high-level waste (HLW) arising from the reprocessing of spent nuclear fuel in the UK. Vitrification is also under consideration for the immobilization of certain intermediate-level wastes (ILW), where there may be advantages of volume reduction and removal of uncertainties in long-term waste behaviour, compared to encapsulation in a cement grout. This paper gives an overview of recent work into the chemical durability of UK vitrified wasteforms to inform the technical specification for the disposal facilities for these waste products and the treatment of their long-term behaviour in post-closure performance assessment. This has included: (1) measurements of the initial glass dissolution rates of a simulated HLW Magnox waste glass in a range of groundwater types representative of potential UK host geologies and in simulated high pH near-field porewaters relevant to potential disposal concepts, using Product Consistency Test type-B (PCT-B) at 40°C; and (2) durability testing of three simulant ILW glasses in a saturated calcium hydroxide buffered solution to simulate conditions in cement-based disposal vaults, using PCT-B tests at 50°C.The experimentally defined initial rate of HLW Magnox waste glass dissolution in a range of simulated groundwater compositions appears to be similar regardless of the ionic strength and major element composition of the solution. The release of caesium from HLW Magnox waste glass appears to be sensitive to solution composition. Caesium is selectively retained in the glass compared to other soluble components in the two low ionic strength solutions, but is released at similar rates to other soluble components in the three groundwaters and Ca(OH)2 solution. Whether this change in caesium retention is an ionic strength effect or is related to changes in the nature of the surface alteration layer formed on the glass, has yet to be established. For HLW Magnox waste glass, dissolution is accelerated at high pH in NaOH solution, however, the presence of calcium acts to mitigate the effects of high pH, at least initially. In Ca(OH)2 solution, calcium is found to react with all the glasses studied leading to the formation of calcium-containing alteration products. The initial dissolution behaviour in Ca(OH)2 solution varies with glass composition and in particular appears to be sensitive to the boron content.

Role of ion exchange in the corrosion of nuclear waste glasses

ABSTRACTThe ion exchange phase of corrosion of nuclear waste glasses was modelled using Doremus' theory of interdiffusion and numerically analysed for British Magnox waste and Russian K-26 glasses. It is shown that even in non-silica -saturated conditions the ion exchange phase plays a significant role in the overall radionuclide release inventory particularly for short-lived radionuclides.

Simulation of Self-Irradiation of High-Sodium Content Nuclear Waste Glasses

AbstractAlkali-borosilicate glasses are widely used in nuclear industry as a matrix for immobilisation of hazardous radioactive wastes. Durability or corrosion resistance of these glasses is one of key parameters in waste storage and disposal safety. It is influenced by many factors such as composition of glass and surrounding media, temperature, time and so on. As these glasses contain radioactive elements most of their properties including corrosion resistance are also impacted by self-irradiation.The effect of external gamma-irradiation on the short-term (up to 27 days) dissolution of waste borosilicate glasses at moderate temperatures (30¢X to 60¢XC) was studied. The glasses studied were Magnox Waste glass used for immobilisation of HLW in UK, and K-26 glass used in Russia for ILW immobilisation. Glass samples were irradiated under ×-source (Co-60) up to doses 1 and 11 MGy. Normalised rates of elemental release and activation energy of release were measured for Na, Li, Ca, Mg, B, Si and Mo before and after irradiation. Irradiation up to 1 MGy results in increase of leaching rate of almost all elements from both MW and K-26 with the exception of Na release from MW glass. Further irradiation up to a dose of 11 MGy leads to the decrease of elemental release rates to nearly initial value. Another effect of irradiation is increase of activation energies of elemental release.

Crystallisation Within Simulated High Level Waste Borosilicate Glass

AbstractThe devitrification products of two simulated high level radioactive waste (HLW) glasses have been investigated. Magnox waste glass contained RuO2 as its primary crystal phase, Pd-Te inclusions, a Cr-, Fe- and Ni-rich spinel phase, a Si- and lanthanide-rich phase and also a Zr-rich phase which incorporated Ce and Gd. Upon heat treatment the glass developed a zektzerite-type phase, CeO2, a strontium molybdate (containing Nd and La) as well as a Si-rich phase. 75/25 glass, comprising a blend of reprocessing waste derived from UO2 and Magnox fuels, contained RuO2 as its primary crystalline phase, CeO2 and a Si- and Ru-rich phase. Heat treatment of this glass resulted in the growth of the CeO2 crystals, the development of a strontium molybdate (containing Nd and La) and a Si- and lanthanide-containing phase. A sodium lanthanum molybdate with a powellite-type structure formed on the surface of both glasses after heat treatment in air.

A Study of Magnox Waste Glass Under Conditions of High Temperature, Very Deep, Geological Disposal

ABSTRACTThe behaviour of a simulant Magnox waste glass was investigated under the likely conditions of high temperature, very deep, geological disposal, viz. 760°C and 0.15GPa. Under these conditions partial crystallisation of the glass is observed with the formation of LnBSiO5 (Ln = Y, La, Pr, Ce, Nd, Sm and Gd), LiNaZrSi6O15 and a palladium (ruthenium) telluride phase. The significance of these findings is discussed in the context of the high temperature, very deep, geological disposal scheme.

Fission Product Immobilisation in Secondary Phases Formed During Magnox Waste Glass Dissolution at 60 °C: Experimental Results and Modelling.

ABSTRACTDissolution of a complex, simulated Magnox Waste (MW) glass in batch dissolution experiments at 60 °C over a period of 56 days is accompanied by extensive development of secondary gels. Gel development has been followed using a range of chemical, spectroscopic and physical means. Initially, a surface layer comprising (hydr)oxides of Fe, Zr and the lanthanides develops at the glass surface. Aluminosilicate gels containing Si, Al, Mg, Sr, Cs and Rb develop in systems where sufficient quantities of glass derived solutes accumulate in the leachate. These gels are hydrous and readily soluble in acidic oxalate solutions. Solution chemistry data is consistent with the development of Cs,Sr-bearing aluminosilicates, silica gel and (hydr)oxides of hydrolysis prone waste components. The experimental results are compared with the predictions of a model that considers kinetically constrained glass dissolution and the precipitation of secondary phases, including a Cs,Sr-bearing aluminosilicate gel.

Vapour Phase Hydration of Magnox Waste Glass

ABSTRACTVapour phase hydration studies of simulant Magnox waste glass have been undertaken at 200°C, over periods of 5 – 25 days. Electron microscopy studies reveal a thin uniform hydration layer (∼10 μm thick) on 5, 10 and 25 day specimens. The formation of isolated surface alteration products occurs between 5 and 10 days at 200°C. The formation of extensive surface alteration products, in the form of a magnesium sodium aluminosilicate, is observed only in the case of the 25 day specimen. The significance of these observations in the context of the composition of Magnox waste glass, is discussed.

The kinetics and mechanisms of simulated British Magnox waste glass dissolution as a function of pH, silicic acid activity and time in low temperature aqueous systems

Dissolution of a simulated British Magnox waste glass is governed by two pH-dependent processes. At low pH, dissolution is governed by reactions occurring predominantly at non-Si sites and residual Si-rich gels develop at the glass surface as B, Al and modifier cations are selectively leached. Here, extensive proton promoted hydrolysis of BO and AlO bonds is coupled with hydration and ion exchange processes. Hydrolysis of siloxane bonds governs the rate of dissolution at high pH and the glass dissolves congruently as the silicate network breaks down extensively. Differences in the surface chemistries and morphologies of glass samples reacted in strongly acidic and highly alkaline media reflect the net effects of these processes. The rate of the congruent dissolution process is influenced by the activity of silicic acid. The results are compared with published data for other glass formulations and are discussed in the context of proposed kinetic dissolution models.

The Effects of Silicic Acid, Aluminate Ion Activity And Hydrosilicate Gel Development on the Dissolution Rate of a Simulated British Magnox Waste Glass

AbstractThe dissolution rate of a simulated Magnox waste glass has been investigated in single-pass flow-through experiments designed to investigate the role of Al and Si in the dissolution process. The results indicate that both Al and Si species suppress the rate of dissolution. These effects may be modelled using a combined Al/Si affinity term in a conventional glass dissolution rate law. Aluminium species may also play an inhibitory role when present at relatively high solution activities. In Si-rich alkaline media, the concentration of aluminium is controlled to very low levels by the development of secondary aluminosilicate phases. Removal of Al by secondary phase precipitation results in dissolved Al activities below that required to reach ‘saturation’ with respect to the glass.

Corrosion Behaviour of British Magnox Waste Glass in Pure Water

ABSTRACTThe corrosion behaviour of Magnox Waste (MW) glass in deionized water has been investigated under the aegis of the Japanese-Swedish-Swiss (JSS) project. The studies carried out at PSI and BNFL included static leaching and corrosion layer characterization. The results were used by HMI to derive the modelling parameters for the MW glass with the PHREEQE/GLASSOL codes. The silica concentration was found to strongly influence the corrosion rate of the glass. The MW glass selectively retains Cs due to the formation of a Cs-Mg-Al-Si-O-rich layer on its surface.

Hot-Pressed Barium Sulphate Ceramic Waste Forms for Direct Immobilisation of Medium Level Magnox Waste

ABSTRACTA possible method of treatment for Magnox cladding waste is by dissolution in nitric acid and precipitation of barium sulphate-based floc with which radioactive ions are co-precipitated. The floc could then be immobilised in a matrix material such as cement or bitumen to give the waste form, or alternatively can be converted directly into a waste form by hot pressing.This paper describes the direct conversion of barium sulphate floc, containing simulated radwaste, into a synthetic, ceramic version of the natural mineral barite by a hot-pressing route. By variation of the parameters pressure, temperature and time, optimum conditions for consolidation of the floc to > 90% theoretical density on a laboratory scale are found to be 22.5 MPa, 900°C for 10 minutes. Using a pressure of 15 MPa, at 900°C for 30 min., hot-pressed billets of BaSO4 have been made on a 5 kg scale. In going from the Magnox waste to the hot-pressed barium sulphate a volume reduction factor ∼ 18 is achieved. The principal phases in the product are found to be BaSO4 , MgO and Fe3O4, and the degree of consolidation achieved depends on the MgO content.The leaching behaviour of the hot-pressed materials in 100°C, 3 day Soxhlet tests also depends on the MgO content, and on the consequent level of open porosity. If there is porosity accessible to the leach water, MgO at the internal surfaces is converted to Mg(OH)2, which deposits within the pores, and a weight gain is registered in the Soxhlet test. If, however, there is no open porosity, a weight loss occurs, and leach rates ∼ 4 × 10−7 kg/m2/sec are found. In contrast, pure BaSO4, hot-pressed to similar densities, shows no variation in leaching behaviour over a wide range of o en porosities, and gives Soxhlet leach rates ∼ 8 × 10−8 kg/m2/sec.