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Title: CHEMICAL ANALYSIS OF SIMULATED HIGH LEVEL WASTE GLASSES TO SUPPORT SULFATE SOLUBILITY MODELING

Abstract

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 developmentmore » 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 B{sub 2}O{sub 3} and Fe{sub 2}O{sub 3} 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« less

Authors:
;
Publication Date:
Research Org.:
SRS
Sponsoring Org.:
USDOE
OSTI Identifier:
1150629
Report Number(s):
SRNL-STI-2014-00342
DOE Contract Number:
DE-AC09-08SR22470
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; High level waste glass, sulfate retention

Citation Formats

Fox, K., and Marra, J. CHEMICAL ANALYSIS OF SIMULATED HIGH LEVEL WASTE GLASSES TO SUPPORT SULFATE SOLUBILITY MODELING. United States: N. p., 2014. Web. doi:10.2172/1150629.
Fox, K., & Marra, J. CHEMICAL ANALYSIS OF SIMULATED HIGH LEVEL WASTE GLASSES TO SUPPORT SULFATE SOLUBILITY MODELING. United States. doi:10.2172/1150629.
Fox, K., and Marra, J. Thu . "CHEMICAL ANALYSIS OF SIMULATED HIGH LEVEL WASTE GLASSES TO SUPPORT SULFATE SOLUBILITY MODELING". United States. doi:10.2172/1150629. https://www.osti.gov/servlets/purl/1150629.
@article{osti_1150629,
title = {CHEMICAL ANALYSIS OF SIMULATED HIGH LEVEL WASTE GLASSES TO SUPPORT SULFATE SOLUBILITY MODELING},
author = {Fox, K. and Marra, J.},
abstractNote = {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 B{sub 2}O{sub 3} and Fe{sub 2}O{sub 3} 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},
doi = {10.2172/1150629},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu Aug 14 00:00:00 EDT 2014},
month = {Thu Aug 14 00:00:00 EDT 2014}
}

Technical Report:

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  • 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 within the DOE complex. These wastes can contain relatively high concentrations of sulfate, which has low solubility in borosilicate glass. This is a significant issue for low-activity waste (LAW) glass and is projected to have a major impact on the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Sulfate solubility has also been amore » limiting factor for recent high level waste (HLW) sludge processed at the Savannah River Site (SRS) Defense Waste Processing Facility (DWPF). The low solubility of sulfate in glass, along with melter and off-gas corrosion constraints, dictate that the waste be blended with lower sulfate concentration waste sources or washed to remove sulfate prior to vitrification. The development of enhanced borosilicate glass compositions with improved sulfate solubility will allow for higher waste loadings and accelerate mission completion.The objective of the current scope being pursued by SHU is to mature the sulfate solubility model to the point where it can be used to guide glass composition development for DWPF and WTP, allowing for enhanced waste loadings and waste throughput at these facilities. A series of targeted glass compositions was selected to resolve data gaps in the model and is identified as Stage III. SHU fabricated these glasses and sent samples to 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 the Stage III, simulated HLW glasses fabricated by SHU in support of the sulfate solubility model development.« less
  • In this research program, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid (EDTA), N-(2- hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), and iminodiacetic acid (IDA)) over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high level waste tanks. The project is comprised of integrated research tasks that approach the problem of chemical speciation using macroscopic thermodynamic measurements of metal-ligand competition reactions, molecular modeling studies to identify structures or complexes of unusual stability, and mass spectrometry measurementsmore » of complex charge/mass ratio that can be applied to mixed metal-chelate systems. This fundamental information is then used to develop thermodynamic models which allows the prediction of changes in chemical speciation and solubility which can occur in response to changes in tank processing conditions. In this way we can both develop new approaches that address fundamental problems in aqueous speciation and at the same time provide useful and practical information needed for tank processing.« less
  • In this research program, Pacific Northwest National Laboratory and Florida State University are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents (ethylenediaminetetraacetic acid [EDTA], N-(2-hydroxyethyl)ethylenediaminetriacetic acid [HEDTA], nitrilotriacetic acid [NTA], iminodiacetic acid [IDA], citrate, and oxalate) over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high-level waste stored in tanks at Hanford and other U.S. Department of Energy (DOE) sites. The project comprises integrated research tasks that approach the problem of chemical speciation using macroscopic thermodynamic measurements of metal-ligand competition reactions, molecular modeling studies to identify structures ormore » complexes of unusual stability, and mass spectrometry measurements of complex charge/mass ratio that can be applied to mixed metalchelate systems. This fundamental information then is used to develop thermodynamic models designed to predict changes in chemical speciation and solubility resulting from various tank processing conditions. In this way we can develop new approaches that address fundamental problems in aqueous speciation and, at the same time, provide useful and practical information needed for tank waste processing.« less
  • In this project, Pacific Northwest National Laboratory (PNNL) and Florida State University (FSU) are investigating the speciation of Sr and Am/Cm in the presence of selected organic chelating agents over ranges of hydroxide, carbonate, ionic strength, and competing metal ion concentrations present in high-level waste (HLW) stored in tanks at Hanford and other U.S. Department of Energy (DOE) sites. The chelating agents that are being studied are EDTA (ethylenediaminetetraacetic acid), HEDTA (N-(2-hydroxyethyl)ethylenediaminetriacetic acid), NTA (nitrilotriacetic acid), IDA (iminodiacetic acid), citrate, and oxalate. The project comprises integrated research tasks that approach the problem of chemical speciation using macroscopic thermodynamic measurements ofmore » metal-ligand competition reactions, molecular modeling studies to identify structures or complexes of unusual stability, and mass spectrometry measurements of complex charge/mass ratio that can be applied to mixed metalchelate systems. This fundamental information then is used to develop thermodynamic models designed to predict changes in chemical speciation and solubility resulting from various tank processing conditions. In this way we can develop new approaches that address fundamental problems in aqueous speciation and, at the same time, provide useful and practical information needed for tank waste processing. Current strategies for reducing the total volume of radioactive tank waste requiring disposal at Hanford and other DOE sites call for the development of methods that can be used to selectively dissolve and remove non-radioactive elements, such as Al, P, and Cr, while retaining or precipitating the radioactive elements, including Sr and the actinide elements, in the tank sludge. This partitioning between solids and precipitates is fundamentally dependent on the chemical speciation of the elements present in the tank processing solutions. Of particular importance is separation of the radioactive and hazardous actinide elements and fission products from the sludge and supernatants, particularly from supernatants containing high concentrations of strong chelating agents that can act to dissolve the actinides and fission products as well as interfere with subsequent metal ion extraction processes. Specifically, the fundamental understanding of chemical speciation reactions gained from these studies will help us identify other potential mechanisms (e.g., competition, displacement, or other reactions) that could be used for removing Sr and Am/Cm from organic chelates present in the HLW.« less