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At least 19 records

Organic Acid-Assisted Thermal Dehalogenation of Halide Salt Nuclear Wastes: From Waste Salts to Borosilicate Glass

Only a handful of high-halide salt waste forms have been demonstrated for vitrification-based immobilization strategies for halide-salt nuclear waste streams (e.g., pyroprocessing wastes, molten salt reactor wastes) and they all have low waste loading potential and most have low chemical durabilities for high-alkali streams. An alternative approach to direct salt immobilization is salt partitioning prior to waste form fabrication and one option for partitioning is halide removal (called dehalogenation). Removing the halogen fraction through dehalogenation can significantly reduce the waste volume required for disposal in the primary waste form. Furthermore, when dehalogenation is performed using organic acids, the dehalogenation reagent can decompose during high-temperature vitrification, reducing waste loading limitations in the waste form. In the current work, different organic acids (i.e., oxalic, formic, acetic, oxamic, and citric) were evaluated for dehalogenation efficiency of a simple chloride salt simulant (7.19% LaCl 3 , 53.77% LiCl, and 39.04% KCl, by mole) and a more complex chloride salt simulant called ERV3 (electrorefiner version 3) at 150 °C–300 °C and using H + /Cl – molar ratios of 1:1, 2:1, and 3:1. Additionally, a borosilicate glass waste form called TARS (or the average of refined specifications) was formulated, produced, and characterized for dehalogenated ERV3.

Amorphous materials↗

Road Map for Developing Iron Phosphate Waste Forms for Salt Wastes

In this report, issues that must be addressed to advance the technology readiness level of phosphate glass waste forms being developed to immobilize high-level radioactive salt waste streams are identified, the states of understanding various technical aspects of formulation, processing, and performance are summarized, and approaches supporting further development are recommended. Processing results in dehalogenation of the waste salt, capture of the gaseous halide-bearing species, and immobilization of the residual salt components in a phosphate glass waste form. The approach is suitable for high-level salt waste from electrochemical reprocessing and molten salt reactors. The technology has been demonstrated for chloride-based salts and may also be suitable for the treatment and immobilization of fluoride-based and iodide-bearing waste salts. Aspects of the process requiring further development are identified and approaches recommended.

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Assessment of lead tellurite glass for immobilizing electrochemical salt wastes from used nuclear fuel reprocessing

This paper provides an overview of research evaluating the use of lead tellurite glass as a waste form for salt wastes from electrochemical reprocessing of used nuclear fuel. The efficacy of using lead tellurite glass to immobilize three different salt compositions was evaluated: a LiCl-Li2O oxide reduction salt containing fission products from oxide fuel, a LiCl-KCl eutectic salt containing fission products from metallic fuel, and SrCl2. Physical and chemical properties of glasses made with these salts were characterized with X-ray diffraction, bulk density measurements, differential thermal analysis, chemical durability tests, scanning and transmission electron microscopies, and energy-dispersive X-ray spectroscopy. These glasses were found to accommodate high salt concentrations and have high densities, but further development is needed to improve chemical durability. (C) 2017 Published by Elsevier B.V.

Riley, Brian J.↗

Summary of Savannah River Site FY21 Salt Waste Qualification Data and Characterization Data from Salt Waste Batches Processed Since 2008

The Savannah River National Laboratory analyzed samples from Savannah River Site Waste Tank 41H and 21H to support qualification of Salt Waste Processing Facility Waste Batches 3 and 4 (the FY21 Salt Batch Qualification samples) for processing. Neither of the samples displayed any unusual or unexpected characteristics such as large amounts of solids, floating solids, or unusual color. Characterization of these samples confirmed similar chemical composition and characteristics to previous salt waste batches. These results were initially provided to Savannah River Remediation (Liquid Waste Operations Sub-contractor) as External Sample Results LIMS Reports. The analytical results (both expedited and routine) are now summarized and discussed in this technical report.

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Saltstone Waste Characterization Analysis - Salt Waste Processing Facility (SWPF) Waste Stream (Q4 CY2020)

The Saltstone Production and Disposal Facility is designed and permitted by the state of South Carolina Department of Health and Environmental Control (SCDHEC) to treat and dispose of low-level radioactive and hazardous liquid waste (salt solution) remaining from the processing of radioactive material at the Savannah River Site (SRS). Low-level waste (LEW) aqueous streams from the Effluent Treatment Project (ETP) and decontaminated solutions from the Tank Closure Cesium Removal Unit (TCCR) and the Salt Waste Processing Facility (SWPF) are stored in Tank 50 until the LEW can be transferred to the Saltstone Facility for treatment and disposal. In the past, decontaminated solution from the Modular Caustic Side Solvent Extraction Unit (MCU) was stored in Tank 50 until the LEW could be transferred to the Saltstone Facility for treatment and disposal. MCU is currently in a suspended operations state. LEW that meets the Waste Acceptance Criteria (WAC) can be transferred, stored, and treated in the Saltstone Production Facility (SPF) for subsequent disposal as saltstone grout in the Saltstone Disposal Facility (SDF). Sampling will be conducted as new waste streams are identified for treatment and disposal at the Saltstone Industrial Wastewater Treatment Facility (IWTF) and Z-Area Industrial Solid Waste Landfill (ISWLF), Facility ID# 025500-1603, General Condition B.9 or every six years in accordance with South Carolina (SC) Regulation 61-107.19 Parti C, “Solid Waste Management: Solid Waste Landfills and Structural Fill - General Requirements.”

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Designing Advanced Ceramic Waste Forms for Electrochemical Processing Salt Waste

This report describes the scientific basis underlying the approach being followed to design and develop “advanced” glass-bonded sodalite ceramic waste form (ACWF) materials that can (1) accommodate higher salt waste loadings than the waste form developed in the 1990s for EBR-II waste salt and (2) provide greater flexibility for immobilizing extreme waste salt compositions. This is accomplished by using a binder glass having a much higher Na 2 O content than glass compositions used previously to provide enough Na+ to react with all of the Cl– in the waste salt and generate the maximum amount of sodalite. The phase compositions and degradation behaviors of prototype ACWF products that were made using five new binder glass formulations and with 11-14 mass% representative LiCl/KCl-based salt waste were evaluated and compared with results of similar tests run with CWF products made using the original binder glass with 8 mass% of the same salt to demonstrate the approach and select a composition for further studies. About twice the amount of sodalite was generated in all ACWF materials and the microstructures and degradation behaviors confirmed our understanding of the reactions occurring during waste form production and the efficacy of the approach. However, the porosities of the resulting ACWF materials were higher than is desired. These results indicate the capacity of these ACWF waste forms to accommodate LiCl/KCl-based salt wastes becomes limited by porosity due to the low glass-to-sodalite volume ratio. Three of the new binder glass compositions were acceptable and there is no benefit to further increasing the Na content as initially planned. Instead, further studies are needed to develop and evaluate alternative production methods to decrease the porosity, such as by increasing the amount of binder glass in the formulation or by processing waste forms in a hot isostatic press. Increasing the amount of binder glass to eliminate porosity will decrease the waste loading from about 12% to 10% on a mass basis, but this will not significantly impact the waste loading on a volume basis. It is likely that heat output will limit the amount of waste salt that can be accommodated in a waste canister rather than the salt loading in an ACWF, and that the increase from 8 mass% to about 10 mass% salt loadings in ACWF materials will be sufficient to optimize these waste forms. Although the waste salt composition used in this study contained a moderate amount of NaCl, the test results suggest waste salts with little or no NaCl can be accommodated in ACWF materials by using the new binder glass, albeit at waste loadings lower than 8 mass%. The higher glass contents that will be required for ACWF materials made with salt wastes that do not contain NaCl are expected to result in much lower porosities in those waste forms.

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Ion Exchange of LiCl-KCl in H-Y Zeolite for Dechlorination of Electro-refiner Salt Waste Forms

The present study focuses on the aim to significantly reduce the volume of electro-refiner waste salt (primarily LiCl-KCl) via dechlorination during waste form production. The target waste form will be zeolite loaded with metallic elements from the salt bound together by glass. Since the presence of I-129 and possibly Cl-36 will have a significant effect on long-term dose associated with the waste form, the ability to separate these halides and either recycle or dispose of them in special engineered waste forms is deemed attractive. A new method has been proposed to achieve this dechlorination involving the ion-exchange reaction between molten chloride ER salt and the protonated Y zeolite. Halides such as Cl and I should off-gas as HCl or HI, which can then be separated and decomposed into Cl{sub 2} and I{sub 2}, respectively. The Cl{sub 2} gas can either be captured and disposed of, or recycled to the electrometallurgical process. Initial experiments have been completed to determine the optimal zeolite drying temperature and to demonstrate ion exchange with non-optimized conditions. Further study in the future will strive to improve the kinetics of the ion-exchange reaction and to maximize the removal of the chlorine.

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Evaluation of Iron‐Phosphate Glass–Ceramic Waste Form for Electrorefiner Salt Waste Simulant Dechlorinated With Phosphoric Acid

The importance of glass and glass–ceramic nuclear waste forms has been reaffirmed in recent years by the growing interest in nuclear power as a reliable energy source. Determination of processing methods for the disposal of halide-containing wastes will be essential for the advancement of nuclear technologies such as non-aqueous fuel reprocessing. Phosphate-based dechlorination and subsequent vitrification of radioactive salt waste into an iron-phosphate waste form have been identified as a potential processing scheme for electrochemical processing waste. The impact of H 3 PO 4 -based dechlorination of complex salt mixtures on the vitrification process and structure of the final iron-phosphate waste form has not yet been investigated. In this work, iron-phosphate glass–ceramics were made from simulant salt waste (48LiCl–33KCl–19NaCl mol%) dechlorinated with the H3PO4-based method. The glass-forming region was compared to that of traditionally prepared Na 2 O–Fe 2 O 3 –P 2 O 5 systems. For a candidate glass-forming composition, the processing scheme presented here was determined to favor Fe 3+ species. The O/P molar ratio was consistent for the candidate composition when dechlorinated at 400°C and 600°C in air and argon environments, indicating glass network connectivity was maintained despite variations in processing parameters. The results presented here validate processing schemes requiring iron-phosphate waste form synthesis following H 3 PO 4 -based dechlorination.

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Perovskite-Derived Cs 2 SnCl 6 –Silica Composites as Advanced Waste Forms for Chloride Salt Wastes

Advanced materials and processes are required to separate halides and fission products from complex salt waste streams associated with the chemical reprocessing of used nuclear fuels and molten salt reactor technologies for immobilization into chemically durable waste forms. Here, in this work, we explore an innovative concept using metal-halide perovskites as advanced host phases to incorporate Cs and Cl with very high waste loadings. Wet chemistry-synthesized Cs 2 SnCl 6 powders from CsCl salt solutions are successfully encapsulated into a silica matrix to form a composite using low-temperature spark plasma sintering with tunable Cs and Cl loadings up to 31 wt.% and 26 wt.%, respectively. Chemical durability testing of the composite waste forms by semi-dynamic leaching experiments demonstrates that incongruent leaching mechanism dominated. The metal-halide perovskite-silica composite waste forms display exceptional chemical durability with the long-term release rates of Cs and Cl comparable to or outperforming the state-of-the-art waste form materials but with significantly higher waste loadings. The scalable synthesis of the metal-halide perovskite from wet-chemistry processes opens up new opportunities in designing perovskite-glass composite waste forms for salt wastes with very high waste loadings and exceptional chemical durability for the sustainable development of advanced fuel cycles and next-generation reactor technologies.

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Results for the April 2024 Semiannual Salt Waste Processing Facility Decontaminated Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the April 2024 Semiannual sample of the Salt Waste Processing Facility (SWPF) Decontaminated Salt Solution (DSS) salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Mission Completion (SRMC) for the transfer of aqueous waste from SWPF to the Saltstone Production Facility (SPF) where the waste will be treated and disposed in the Saltstone Disposal Facility. This Technical Report compares results, where applicable, to SPF Waste Acceptance Criteria (WAC) LIMITS and TARGETS that were established at the time the SWPF DSS sample was obtained.1 The April 2024 Semiannual sample of the SWPF DSS is a composite from the six months of SWPF processing during the First Quarter Fiscal Year 2024 (1QFY2024) and the Second Quarter Fiscal Year 2024 (2QFY2024). The following facts pertaining to the WAC are drawn from the analytical results provided in this report. WAC TARGETS and LIMITS were met for all analyzed chemical and radioactive contaminants for which the detection limits are below the WAC TARGETS and LIMITS. Nitrosamines were not detected in the SWPF DSS salt solution sample above the instrument detection limits of <1 mg/L. The minimum detection limit (<3.33E-01 pCi/mL) is reported for 94 Nb as determined from the minimum detectable activity associated with the radiochemical method used for this radionuclide. The reported detection limit is above the requested SRMC target minimum detection limit concentration. However, the minimum detection limit reported for the April 2024 semiannual SWPF DSS sample for 94 Nb is lower than the estimated detection limit of 4.38E-01 pCi/mL initially established by SRNL in 2009. Thus, per guidance from SRMC, 2 SRNL continues to achieve as low as practical detection limits for this radionuclide.

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Results for the October 2023 Semiannual Salt Waste Processing Facility Decontaminated Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the October 2023 Semiannual sample of the Salt Waste Processing Facility (SWPF) Decontaminated Salt Solution (DSS) salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Mission Completion (SRMC) for the transfer of aqueous waste from SWPF to the Saltstone Production Facility (SPF) where the waste will be treated and disposed in the Saltstone Disposal Facility. This Technical Report compares results, where applicable, to SPF Waste Acceptance Criteria (WAC) LIMITS and TARGETS that were established at the time the SWPF DSS sample was obtained. The October 2023 Semiannual sample of the SWPF DSS is a composite from the six months of SWPF processing during the Third Quarter Fiscal Year 2023 (3QFY2023) and the Fourth Quarter Fiscal Year 2023 (4QFY2023).

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Results for the April 2025 Semiannual Salt Waste Processing Facility Decontaminated Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the April 2025 Semiannual sample of the Salt Waste Processing Facility (SWPF) Decontaminated Salt Solution (DSS) salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Mission Completion (SRMC) for the transfer of aqueous waste from SWPF to the Saltstone Production Facility (SPF) where the waste will be treated and disposed in the Saltstone Disposal Facility. This Technical Report compares results, where applicable, to SPF Waste Acceptance Criteria (WAC) LIMITS and TARGETS that were established at the time the SWPF DSS sample was obtained. The April 2025 Semiannual sample of the SWPF DSS is a composite from the six months of SWPF processing during the First Quarter Fiscal Year 2025 (1QFY2025) and the Second Quarter Fiscal Year 2025 (2QFY2025).

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Results for the October 2025 Semiannual Salt Waste Processing Facility Decontaminated Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the October 2025 Semiannual sample of the Salt Waste Processing Facility (SWPF) Decontaminated Salt Solution (DSS) salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Mission Completion (SRMC) for the transfer of aqueous waste from SWPF to the Saltstone Production Facility (SPF) where the waste will be treated and disposed in the Saltstone Disposal Facility. This Technical Report compares results, where applicable, to SPF Waste Acceptance Criteria (WAC) LIMITS and TAR GETS that were established at the time the SWPF DSS sample was obtained. 1 The October 2025 Semiannual sample of the SWPF DSS is a composite from one month of SWPF processing during the Third Quarter Fiscal Year 2025 (3QFY2025) and two months of SWPF processing during the Fourth Quarter Fiscal Year 2025 (4QFY2025).

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Synergy in Materials: Leveraging Phosphosilicate Waste Forms for Electrochemical Salt Waste

Here, waste forms containing glassy and crystalline phosphate and silicate phases were produced to immobilize salt waste simulants from pyroprocessing and characterized by using Raman spectroscopy, Mössbauer spectroscopy, X-ray diffraction, scanning electron microscopy, heat capacity, and chemical durability measurements. In this work, a phosphosilicate waste form is presented to leverage the benefits of both borosilicate glasses and iron phosphate glasses. To improve waste loading, prior to immobilization, salt simulants were successfully dechlorinated using ammonium dihydrogen phosphate, mixed with a borosilicate frit (5–30 wt %) and Fe 2 O 3 , and vitrified. Additions of 2.5–15 wt % borosilicate glass (NBS3) improved normalized release rates for Cs relative to iron-phosphates without NBS3, resulting in chemical durabilities similar to high-level waste borosilicate glass reference materials. The release rates of the alkalis (i.e., Li, Na, K, Cs) were the lowest with the addition of 5 wt % NBS3. Although Sr was not specifically targeted in this study, evidence exists that it preferentially partitioned with Si to form an amorphous droplet phase within the iron phosphate glass matrix.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

October 2025 Semiannual Composite Salt Waste Processing Facility Decontaminated Salt Solution Toxicity Characteristic Leaching Procedure Results

The aqueous waste from the Salt Waste Processing Facility is sampled semiannually for transfers to the Saltstone Disposal Facility. Salt solution is treated at the Saltstone Production Facility and disposed of in the Saltstone Disposal Facility. Per request of customer, X-TTR-Z-00027, Revision 0, one Saltstone Processing Facility Decontaminated Salt Solution and Z area premix material for the October 2025 semiannual Toxicity Characteristic Leaching Procedure sample. The sample contained 60:40 (by weight) of slag and fly ash (referred to as the “Cement-Free grout sample”). Results from the technical report support Task 2: ‘Grout Leaching Analyses’ of the Task Technical Request prepared by Savannah River Mission Completion. At 51 days cured, the Saltstone sample was collected and shipped to a certified laboratory for analysis using the Toxicity Characteristic Leaching Procedure. The October 2025 Semiannual Cement-Free grout sample met 61 79.268.48 requirements for a non-hazardous waste form with respect to the Resource Conservation and Recovery Act metals and Underlying Hazardous Constituents and met the Saltstone Production Facility Waste Acceptance Criteria that was in effect at the time of the sample collection at the Salt Waste Processing Facility.

Hsieh, Madison [Savannah River National Laboratory↗

Investigation of Undissolved Solids from Salt Waste Processing Facility (SWPF) Salt Batches Collected via Filtration

SRNL researchers performed six experiments wherein 0.1 μm-grade stainless steel filters were used to filter samples pulled from salt batches 6, 9B, and 11B, without the addition of monosodium titanate. Three of these experiments were performed to collect filterable solids from each salt batch and characterize trapped solids via scanning electron microscopy. The remaining three experiments were performed to collect and then dissolve the same solids using 3.5 M nitric acid (similar to that employed in the Salt Waste Processing Facility) for characterization via Inductively-coupled plasma atomic emission spectroscopy.

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