High level radioactive wastes are being vitrified at the Savannah River Site for long term disposal. Many of the wastes contain sulfate at concentrations that can be difficult to retain in borosilicate glass. This study involves efforts to optimize the composition of a glass frit for combination with the waste to improve sulfate retention while meeting other process and product performance constraints. The fabrication and characterization of several series of simulated waste glasses are described. The experiments are detailed chronologically, to provide insight into part of the engineering studies used in developing frit compositions for an operating high level waste vitrification facility. The results lead to the recommendation of a specific frit composition and a concentration limit for sulfate in the glass for the next batch of sludge to be processed at Savannah River.
This study was undertaken to investigate the effect of elevated sulfate and molybdenum concentrations in nuclear waste glasses. A matrix of 24 glasses was developed and the glasses were tested for acceptability based on visual observations, canister centerline-cooled heat treatments, and chemical composition analysis. Results from the chemical analysis of the rinse water from each sample were used to confirm the presence of SO2−4 and MoO3 on the surface of glasses as well as other components which might form water soluble compounds with the excess sulfur and molybdenum. A simple, linear model was developed to show acceptable concentrations of SO42− and MoO3 in an example waste glass composition. This model was constructed for scoping studies only and is not ready for implementation in support of actual waste vitrification. Several other factors must be considered in determining the limits of sulfate and molybdenum concentrations in the waste vitrification process, including but not limited to, impacts on refractory and melter component corrosion, effects on the melter off-gas system, and impacts on the chemical durability and crystallization of the glass product.
The U.S. Department of Energy (DOE), Office of Environmental Management (EM) is sponsoring an international, collaborative project to develop a fundamental model for sulfate solubility in nuclear waste glass. The solubility of sulfate has a significant impact on the achievable waste loading for nuclear waste forms both within the DOE complex and to some extent at U.K. sites. The development of enhanced borosilicate glass compositions with improved sulfate solubility will allow for higher waste loadings and accelerated cleanup missions. Much of the previous work on improving sulfate retention in waste glasses has been done on an empirical basis, making it difficult to apply the findings to future waste compositions despite the large number of glass systems studied. A more fundamental, rather than empirical, model of sulfate solubility in glass, under development at Sheffield Hallam University (SHU), could provide a solution to the issues of sulfate solubility. The model uses the normalized cation field strength index as a function of glass composition to predict sulfate capacity, and has shown early success for some glass systems. The objective of the current scope is to mature the sulfate solubility model to the point where it can be used to guide glass composition development for DOE waste vitrification efforts, allowing for enhanced waste loadings and waste throughput. A series of targeted glass compositions was selected to resolve data gaps in the current model. SHU fabricated these glasses and sent samples to the Savannah River National Laboratory (SRNL) for chemical composition analysis. SHU will use the resulting data to enhance the sulfate solubility model and resolve any deficiencies. In this report, SRNL provides chemical analyses for simulated waste glasses fabricated SHU in support of sulfate solubility model development. A review of the measured compositions revealed that there are issues with the B2O3 and Fe2O3 concentrations missing their targeted values by a significant amount for several of the study glasses. SHU is reviewing the fabrication of these glasses and the chemicals used in batching them to identify the source of these issues. The measured sulfate concentrations were all below their targeted values. This is expected, as the targeted concentrations likely exceeded the solubility limit for sulfate in these glass compositions. Some volatilization of sulfate may also have occurred during fabrication of the glasses. Measurements of the other oxides in the study glasses were reasonably close to their targeted values.
This report describes the results of studies related to the incorporation of sulfate in high level waste (HLW) borosilicate glass produced at the Savannah River Site (SRS) Defense Waste Processing Facility (DWPF). A group of simulated HLW glasses produced for earlier sulfate retention studies was selected for full chemical composition measurements to determine whether there is any clear link between composition and sulfate retention over the compositional region evaluated. In addition, the viscosity of several glasses was measured to support future efforts in modeling sulfate solubility as a function of predicted viscosity. The intent of these studies was to develop a better understanding of sulfate retention in borosilicate HLW glass to allow for higher loadings of sulfate containing waste. Based on the results of these and other studies, the ability to improve sulfate solubility in DWPF borosilicate glasses lies in reducing the connectivity of the glass network structure. This can be achieved, as an example, by increasing the concentration of alkali species in the glass. However, this must be balanced with other effects of reduced network connectivity, such as reduced viscosity, potentially lower chemical durability, and in the case of higher sodium and aluminum concentrations, the propensity for nepheline crystallization. Future DWPF processing is likely to target higher waste loadings and higher sludge sodium concentrations, meaning that alkali concentrations in the glass will already be relatively high. It is therefore unlikely that there will be the ability to target significantly higher total alkali concentrations in the glass solely to support increased sulfate solubility without the increased alkali concentration causing failure of other Product Composition Control System (PCCS) constraints, such as low viscosity and durability. No individual components were found to provide a significant improvement in sulfate retention (i.e., an increase of the magnitude necessary to have a dramatic impact on blending, washing, or waste loading strategies for DWPF) for the glasses studied here. In general, the concentrations of those species that significantly improve sulfate solubility in a borosilicate glass must be added in relatively large concentrations (e.g., 13 to 38 wt % or more of the frit) in order to have a substantial impact. For DWPF, these concentrations would constitute too large of a portion of the frit to be practical. Therefore, it is unlikely that specific additives may be introduced into the DWPF glass via the frit to significantly improve sulfate solubility. The results presented here continue to show that sulfate solubility or retention is a function of individual glass compositions, rather than a property of a broad glass composition region. It would therefore be inappropriate to set a single sulfate concentration limit for a range of DWPF glass compositions. Sulfate concentration limits should continue to be identified and implemented for each sludge batch. The current PCCS limit is 0.4 wt % SO42− in glass, although frit development efforts have led to an increased limit of 0.6 wt % for recent sludge batches. Slightly higher limits (perhaps 0.7-0.8 wt %) may be possible for future sludge batches. An opportunity for allowing a higher sulfate concentration limit at DWPF may lay lie in improving the laboratory experiments used to set this limit. That is, there are several differences between the crucible-scale testing currently used to define a limit for DWPF operation and the actual conditions within the DWPF melter. In particular, no allowance is currently made for sulfur partitioning (volatility versus retention) during melter processing as the sulfate limit is set for a specific sludge batch. A better understanding of the partitioning of sulfur in a bubbled melter operating with a cold cap as well as the impacts of sulfur on the off-gas system may allow a higher sulfate concentration limit to be establish ...
Radioactive wastes are generated from a wide range of sources, including the power industry, and medical and scientific research institutions, presenting a range of challenges in dealing with a diverse set of radionuclides of varying concentrations. Conditioning technologies are essential for the encapsulation and immobilisation of these radioactive wastes, forming the initial engineered barrier required for their transportation, storage and disposal. The need to ensure the long term performance of radioactive waste forms is a key driver of the development of advanced conditioning technologies.The Handbook of advanced radioactive waste conditioning technologies provides a comprehensive and systematic reference on the various options available and under development for the treatment and immobilisation of radioactive wastes. The book opens with an introductory chapter on radioactive waste characterisation and selection of conditioning technologies. Part one reviews the main radioactive waste treatment processes and conditioning technologies, including volume reduction techniques such as compaction, incineration and plasma treatment, as well as encapsulation methods such as cementation, calcination and vitrification. This coverage is extended in part two, with in-depth reviews of the development of advanced materials for radioactive waste conditioning, including geopolymers, glass and ceramic matrices for nuclear waste immobilisation, and waste packages and containers for disposal. Finally, part three reviews the long-term performance assessment and knowledge management techniques applicable to both spent nuclear fuels and solid radioactive waste forms.With its distinguished international team of contributors, the Handbook of advanced radioactive waste conditioning technologies is a standard reference for all radioactive waste management professionals, radiochemists, academics and researchers involved in the development of the nuclear fuel cycle. - Provides a comprehensive and systematic reference on the various options available and under development for the treatment and immobilisation of radioactive wastes - Explores radioactive waste characterisation and selection of conditioning technologies including the development of advanced materials for radioactive waste conditioning - Assesses the main radioactive waste treatment processes and conditioning technologies, including volume reduction techniques such as compaction
With the imminent startup, in the United States, of facilities for vitrification of high-level nuclear waste, a document has been prepared that compiles the scientific basis for understanding the alteration of the waste glass products under the range of service conditions to which they may be exposed during storage, transportation, and eventual geologic disposal. A summary of selected parts of the content of this document is provided. Waste glass alterations in a geologic repository may include corrosion of the glass network due to groundwater and/or water vapor contact. Experimental testing results are described and interpreted in terms of the underlying chemical reactions and physical processes involved. The status of mechanistic modeling, which can be used for long-term predictions, is described and the remaining uncertainties associated with long-term simulations are summarized.
