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Thermal properties and Thermodynamic Equilibrium Modeling of Cementitious Waste Forms

INTRODUCTION Cementitious matrices are used in the US DOE complex and worldwide to solidify aqueous radioactive, hazardous, mixed salt solutions, and sludges to meet low-level radioactive waste (LLW) disposal requirements. Blended formulations are used for most waste form mix designs. Substitution of pozzolans for Class F fly ash has the potential to alter the processing properties and stabilization properties of the resulting waste forms because they add chemical and mineralogical complexity to the final material. The Savannah River Site saltstone waste form was selected as the test case material. CemGEMS software was chosen as the model for predicting hydrated cementitious phases assemblages and phase evolution. Isothermal calorimetry was used as the method for evaluating processing and properties of fresh, uncured waste forms. The test cases consisted of reference case saltstone, and five natural pozzolan substituted saltstone mixes.

Bustamante, Michael E. [Savannah River National La↗

Results for the First Quarter Calendar Year 2021 Tank 50 Salt Solution Sample

Tank 50 aqueous waste is analyzed on a quarterly basis and the results are compared to the Waste Acceptance Criteria (WAC) of the Z-Area Saltstone Production Facility (SPF). The information from this characterization will be used by Savannah River Remediation (SRR) for the transfer of aqueous waste from Tank 50 to SPF, where the waste will be treated and disposed in the Saltstone Disposal Facility. This Technical Report compares results, where applicable, to SPF WAC Limits and Targets. A memorandum reporting the average Cs-137 value and comparison to WAC Limits has been previously issued.

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Tank 50 Salt Solution Sample (2QCY21)

In this Technical Report, the chemical and radionuclide contaminant results from the Second Quarter Calendar Year 2021 (CY21) sample of Tank 50 salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Remediation (SRR) for the transfer of aqueous waste from Tank 50 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 Tank 50 sample was obtained. The chemical and radionuclide contaminant results from the characterization of the Second Quarter CY21 sampling of Tank 50 were requested by SRR personnel via a Task Technical Request (TTR) and details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP). This Technical Report is part of Deliverable 2 relating to Task 1 from the SRR request. Data pertaining to the regulatory limits for Resource Conservation and Recovery Act (RCRA) metals per Task 2 from the SRR request, will be obtained semi-annually for the 1QCY21 and 3QCY21 Tank 50 samples.

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Results for the September Bimonthly Calendar Year 2021 Tank 50 Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the 2021 September bimonthly sample of Tank 50 salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Remediation (SRR) for the transfer of aqueous waste from Tank 50 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 Tank 50 sample was obtained. The chemical and radionuclide contaminant results from the characterization of the 2021 September bimonthly sampling of Tank 50 were requested by SRR personnel via a Task Technical Request (TTR) and details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP). This Technical Report is the TTR deliverable relating Salt Solution Analysis from the SRR request.

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Results for the Third Quarter Calendar Year 2021 Tank 50 Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the Third Quarter Calendar Year 2021 (CY21) sample of Tank 50 salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Remediation (SRR) for the transfer of aqueous waste from Tank 50 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 Tank 50 sample was obtained. The chemical and radionuclide contaminant results from the characterization of the Third Quarter CY21 sampling of Tank 50 were requested by SRR personnel via a Task Technical Request (TTR) and details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP). This Technical Report is part of Deliverable 2 relating to Task 1 from the SRR request. Data pertaining to the regulatory limits for Resource Conservation and Recovery Act (RCRA) metals per Task 2 from the SRR request, will be obtained semi-annually for the 1QCY21 and 3QCY21 Tank 50 samples.

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Results for the Second Quarter Calendar Year 2021 Tank 50 Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the Second Quarter Calendar Year 2021 (CY21) sample of Tank 50 salt solution are presented in tabulated form. The information from this characterization will be used by Savannah River Remediation (SRR) for the transfer of aqueous waste from Tank 50 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 Tank 50 sample was obtained. The chemical and radionuclide contaminant results from the characterization of the Second Quarter CY21 sampling of Tank 50 were requested by SRR personnel via a Task Technical Request (TTR) and details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP). This Technical Report is part of Deliverable 2 relating to Task 1 from the SRR request. Data pertaining to the regulatory limits for Resource Conservation and Recovery Act (RCRA) metals per Task 2 from the SRR request, will be obtained semi-annually for the 1QCY21 and 3QCY21 Tank 50 samples.

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Results for the January 2022 Semiannual Tank 50 Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the January 2022 Semiannual sample of Tank 50 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 Tank 50 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 Tank 50 sample was obtained. The chemical and radionuclide contaminant results from the characterization of the January 2022 semiannual sampling of Tank 50 were requested by SRMC personnel via a Task Technical Request (TTR) and details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP). This Technical Report is part of Deliverable 2 relating to Task 1 from the SRMC request. Data pertaining to the regulatory limits for Resource Conservation and Recovery Act (RCRA) metals per Task 2 from the RMC request, will be obtained semiannually for the January 2022 and July 2022 Tank 50 samples.

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Results for the March Bimonthly Calendar Year 2022 Tank 50 Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the 2022 March bimonthly sample of Tank 50 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 Tank 50 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 Tank 50 sample was obtained. The chemical and radionuclide contaminant results from the characterization of the 2022 March bimonthly sampling of Tank 50 were requested by SRMC personnel via a Task Technical Request (TTR) and details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP). This Technical Report is the TTR deliverable relating Salt Solution Analysis from the SRMC request.

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Results for the July 2022 Semiannual Tank 50 Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the July 2022 Semiannual sample of Tank 50 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 Tank 50 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 Tank 50 sample was obtained. The chemical and radionuclide contaminant results from the characterization of the July 2022 semiannual sampling of Tank 50 were requested by SRMC personnel via a Task Technical Request (TTR) and details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP). This Technical Report is part of Deliverable 2 relating to Task 1 from the SRMC request. Data pertaining to the regulatory limits for Resource Conservation and Recovery Act (RCRA) metals per Task 2 from the SRMC request, will be obtained semiannually for the January 2022 and July 2022 Tank 50 samples.

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Results for the Fourth Quarter Calendar Year 2022 Salt Solution Sample for Performance Assessment Analyses

In this Technical Report, the chemical and radionuclide contaminant results from the fourth quarter calendar year 2022 salt solution sample for Performance Assessment (PA) analyses 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 to Tank 50 and 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 salt solution sample was obtained. The chemical and radionuclide contaminant results from the characterization of the fourth quarter calendar year 2022 sampling of salt solution sent to Z area were requested by SRMC personnel via a Technical Task Request (TTR). Details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP). This Technical Report is the TTR deliverable relating Salt Solution Analysis from the SRMC request.

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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 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 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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Increased Fissile Loading Flowsheet Review

A request was made by H-Canyon Process Engineering to assess the impact of blending dissolved, neutralized Spent Nuclear Fuel (SNF) with future sludge batches and their impact on downstream processing facilities including the Concentration, Storage and Transfer Facilities (CSTF), the Salt Waste Processing Facility (SWPF), the Defense Waste Processing Facility (DWPF), Saltstone, and the Effluent Treatment Facility (ETF). The purpose of this change is to accelerate the deinventory of SNF which is currently stored in the L-Area Disassembly Basin. The addition of SNF increases the mass of fissiles in each future sludge batch, due to their high enrichment. This high enrichment has the potential to complicate the programs to eliminate criticality events in the downstream processing facilities and will increase the number of canisters produced by DWPF because of the SNF mass increase. A separate report addressed the impacts to glass. The review and subsequent calculations were based on average predicted compositions of Accelerated Basin Deinventory (ABD) slurry, average compositions for predicted future sludge batches, average past salt batches and average past recycle batches to predict the feeds that will be processed in SWPF, DWPF, Saltstone, the 2H evaporator and ETF. Each of the processes was evaluated for potential issues.

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Characterization of SDU 6 Sump Water Samples

This report details results from characterization of the Saltstone Disposal Unit 6 (SDU 6) East Sump water samples. In March of 2022, Saltstone Radiation Protection Department (RPD) personnel reported SDU 6 East Sump beta/gamma radiation levels at ~ 33 dpm/mL (~ 15 pCi/mL) beta/gamma in excess of the water sampling limit of 16 dpm/mL (7.2 pCi/mL). Replicate samples obtained from the SDU 6 East Sump were sent to the Savannah River National Laboratory (SRNL) for analysis to include pH, limited anions, toxic metals and radionuclides. Subsequent sump samples associated with SDU 7 that has not yet been filled with any radioactive material were also analyzed at SRNL for both nitrate and nitrite.

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Results for the September Bimonthly Calendar Year 2022 Tank 50 Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the 2022 September bimonthly sample of Tank 50 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 Tank 50 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 Tank 50 sample was obtained. The chemical and radionuclide contaminant results from the characterization of the 2022 September bimonthly sampling of Tank 50 were requested by SRMC personnel via a Task Technical Request (TTR). Details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP). This Technical Report is the TTR deliverable relating Salt Solution Analysis from the SRMC request. The following facts pertaining to the WAC are drawn from the analytical results, including analytical uncertainty, provided in this report. 1) WAC LIMITS and TARGETS were met for all analyzed chemical and radioactive contaminants for which the detection limits are below the WAC LIMITS and TARGETS; 2) Measured average concentrations of nitrate, nitrite and total mercury are approximately 24%, 9% and 12% of the WAC LIMITS, respectively; 3) Measured average concentrations of Tc-99 and I-129 are approximately 19% and 20% of the WAC LIMITS, respectively; 4) All other radionuclide average concentrations are at 4% or less of the WAC LIMITS and TARGETS.

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Results for the January 2023 Semiannual Tank 50 Salt Solution Sample

In this Technical Report, the chemical and radionuclide contaminant results from the January 2023 Semiannual sample of Tank 50 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 Tank 50 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 Tank 50 sample was obtained.1 The chemical and radionuclide contaminant results from the characterization of the January 2023 semiannual sampling of Tank 50 were requested by SRMC personnel via a Task Technical Request (TTR)2 and details of the testing are presented in the Savannah River National Laboratory (SRNL) Task Technical and Quality Assurance Plan (TTQAP).3 This Technical Report is part of Deliverable 2 relating to Task 1 from the SRMC request.2 Data pertaining to the regulatory limits for Resource Conservation and Recovery Act (RCRA) metals per Task 2 from the SRMC request will be obtained semiannually for the January 2023 and July 2023 Tank 50 samples.

Crawford, Charles L.↗