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Results of the Short-Term Analyses of the Salt (Macro) Batch 5 Tank 41H Qualification Sample (Resample)

Savannah River National Laboratory (SRNL) analyzed samples from Tank 41H in November 2021 in support of qualification of Salt Waste Processing Facility (SWPF) Salt Batch 5. This document reports the short-term results of the analyses of samples of Tank 41H. Analysis of the Tank 41H Salt Batch 5 sample indicates that the material does not display any unusual characteristics or observations, such as floating solids, the presence of large amounts of solids, or unusual colors. Further sample results will be reported in a future document. This report satisfies part of Deliverable 3 of the Technical Task Request (TTR). After a data review it was found that the original results reported in the revision 0 of this document were actually from Salt Batch 4 (Tank 21H). A new set of samples was sent for analysis to satisfy deliverable 3 of the TTR. The results from the original analyses have been replaced with the recent analyses of the actual Salt Batch 5 sample.

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Results of Long-Term Analyses of the Salt (Macro) Batch 5 Tank 41h Qualification Sample (Resample)

Savannah River National Laboratory (SRNL) analyzed samples from Tank 41H in support of qualification of Salt Water Processing Facility (SWPF) Salt Batch 5. This document reports the long-term results of the analyses of samples of Tank 41H. Analysis of the Tank 41H Salt Batch 5 sample indicated that the material does not display any unusual characteristics or observations, such as floating solids, the presence of large amounts of solids, or unusual colors. This memo satisfies Deliverable 3 of the Technical Task Request (TTR). After a data review it was found that the original results reports in the revision 0 of this document were actually from Salt Batch 4 (Tank 21H). A new set of samples was sent for analysis to satisfy Deliverable 3 of the TTR. The results from the original analyses have been replaced with the recent analyses of the actual Salt Batch 5 sample.

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Results of the Analyses of the SRNL Solvent Components

At the request of the Savannah River Mission Completion (SRMC), personnel at Savannah River Site (SRS) performed analyses on the remaining solvent components that are being stored at the Savannah River National Laboratory (SRNL). This was done to determine if the remaining stock of materials were still suitable for use for the Salt Waste processing Facility (SWPF). Two drums of Modifier, two drums BOBCalix, four drums of MAXCalix, and four jars of TiDG*HCl were analyzed. All were found to be of acceptable purity for use.

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Results of the Short-Term Analyses of the Salt (Macro) Batch 5 Tank 41H Qualification Sample (Resample)

Savannah River National Laboratory (SRNL) analyzed samples from Tank 41H in November 2021 in support of qualification of Salt Waste Processing Facility (SWPF) Salt Batch 5. This document reports the short-term results of the analyses of samples of Tank 41H. Analysis of the Tank 41H Salt Batch 5 sample indicates that the material does not display any unusual characteristics or observations, such as floating solids, the presence of large amounts of solids, or unusual colors. Further sample results will be reported in a future document. This report satisfies part of Deliverable 3 of the Technical Task Request (TTR). After a data review it was found that the original results reported in the revision 0 of this document were actually from Salt Batch 4 (Tank 21H). A new set of samples was sent for analysis to satisfy deliverable 3 of the TTR. The results from the original analyses have been replaced with the recent analyses of the actual Salt Batch 5 sample.

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Results of Long-Term Analyses of the Salt (Macro) Batch 5 Tank 41H Qualification Sample (Resample)

Savannah River National Laboratory (SRNL) analyzed samples from Tank 41H in support of qualification of Salt Waste Processing Facility (SWPF) Salt Batch 5. This document reports the long-term results of the analyses of samples of Tank 41H. Analysis of the Tank 41H Salt Batch 5 sample indicates that the material does not display any unusual characteristics or observations, such as floating solids, the presence of large amounts of solids, or unusual colors. This memo satisfies Deliverable 3 of the Technical Task Request (TTR). After a data review it was found that the original results reported in the revision 0 of this document were actually from Salt Batch 4 (Tank 21H). A new set of samples were sent for analysis to satisfy Deliverable 3 of the TTR. The results from the original analyses have been replaced with the recent analyses of the actual Salt Batch 5 sample.

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Results of Long-Term Analyses of the Salt (Macro) Batch 11 Tank 21H Qualification Sample

Savannah River National Laboratory (SRNL) analyzed samples from Tank 21H in support of qualification of Salt Waste Processing Facility (SWPF) Salt Batch 11. This document reports the long-term results of the analyses of the sample of Tank 21H. Analysis of this sample indicates that the material does not display any unusual characteristics or observations, such as visually apparent solids. However, the sample was dark colored. This report satisfies Deliverable 3 of the Technical Task Request (TTR).

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Results of Long-Term Analyses of the Salt (Macro) Batch 11 Tank 21H Qualification Sample

Savannah River National Laboratory (SRNL) analyzed samples from Tank 21H in support of qualification of Salt Waste Processing Facility (SWPF) Salt Batch 11. This document reports the long-term results of the analyses of the sample of Tank 21H. Analysis of this sample indicates that the material does not display any unusual characteristics or observations, such as visually apparent solids. However, the sample was dark colored. This report satisfies Deliverable 3 of the Technical Task Request (TTR). This revision adds a further triplicate analysis for 129 I content.

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Results of Long-Term Analyses of the Salt (Macro) Batch 13 Tank 42H Qualification Sample

Savannah River National Laboratory (SRNL) analyzed samples from Tank 42H in support of qualification of Salt Waste Processing Facility (SWPF) Salt Batch 13. This document reports the long-term results of the analyses of the sample of Tank 42H. Analysis of this sample indicates that the material does not display any unusual characteristics or observations, such as visually apparent solids. This report satisfies Deliverable 3 of the Technical Task Request (TTR).

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Results of Analyses of Boric Acid Samples from the Salt Waste Processing Facility

Savannah River National Laboratory (SRNL) analyzed boric acid samples from the Salt Waste Processing Facility (SWPF). This document reports the results of these analyses. Analysis of these samples indicates that the material does not display any unusual characteristics or observations, such as visually apparent solids. The characteristics of both samples was as expected.

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Results of Long-Term Analyses of the Salt (Macro) Batch 14 Tank 21H Qualification Sample

Savannah River National Laboratory (SRNL) analyzed samples from Tank 21H in support of qualification of Salt Waste Processing Facility (SWPF) Salt Batch 14. This document reports the long-term results of the analyses of the sample of Tank 21H. Analysis of this sample indicates that the material does not display any unusual characteristics or observations, such as visually apparent solids. This report satisfies Deliverable 3 of the Technical Task Request (TTR).

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Selection of Glasses to Confirm the 0.65 Weight Percent Sulfate Solubility Limit for Sludge Batch 10

In preparation for Sludge Batch 10 (SB10) processing, projections of sulfate (SO 4 2- ) in glass at 36% waste loading (WL) were calculated in May 2020 for Tank 40 blend projections representing 0.7M and 0.85M Na wash endpoints. The projected SO 4 2- ) concentrations for either sludge-only (SO) or coupled processing with the Salt Waste Processing Facility (SWPF) were either near or exceeded the current Sludge Batch 9 (SB9) limit of 0.65 weight percent (wt.%). Four nominal glass compositions were selected based on SO and coupled processing for the 0.85M Na wash endpoint Tank 40 blend projection to conduct an initial evaluation of the SB10 sulfate solubility behavior. A sulfate salt phase was absent from each of the prepared glasses, which provided preliminary results that supported the 0.65 wt.% SO 4 2- ) limit for SB10.

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Evaluation Of Glass Density to Support the Estimation of Fissile Mass Loadings in Sludge Batch 10 Glasses

Per a directive from the Department of Energy Savannah River Operations Office (DOE-SR) in 2008, the fissile mass loading concentration must remain below 897 g/m 3 in each high-level waste (HLW) glass canister produced by the Defense Waste Processing Facility (DWPF). To support Sludge Batch 5 (SB5) processing, the Savannah River National Laboratory (SRNL) developed a technical basis that facilitates the evaluation of fissile mass loading of the glass product. The calculation is based on the iron (Fe) concentration in the glass as determined by measurements from the Slurry Mix Evaporator acceptability analysis as well as the glass density. In April 2022, a subsequent DOE-SR directive increased the fissile mass loading limit to 2500 g/m 3 beginning with Sludge Batch 11. Thus, the 897 g/m 3 limit still applies to Sludge Batch 10 (SB10) processing. For SB5 through initial Sludge Batch 9 (SB9) processing prior to coupled operation with the Salt Waste Processing Facility (SWPF), SRNL provided DWPF a bounding glass density value that was based on a statistical evaluation of density measurements. To eliminate the need for experimental work, a composition-based density model for HLW glasses was developed at SRNL in 2019. The objective of this report is to present the bounding glass density determined with the composition-based density model for SB10 sludge-only (SO) and coupled processing.

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Measurement Acceptance Region (MAR) Assessment Results Based on Confirmation Sample Sludge Batch 10 Projections

The Defense Waste Processing Facility (DWPF) is currently preparing to initiate processing of Sludge Batch 10 (SB10), which is comprised of material from Tanks 11H, 13H, 15H, 26F, 40H (heel only), and Alternate Feed Stock-2 and Sodium Reactor Experiment material from H-Canyon. Frit 473 was recommended for sludge-only (SO) and coupled processing with the Salt Waste Processing Facility (SWPF) based on previous assessments of SB10 projections with the DWPF Product Composition Control System (PCCS) glass property models and their associated Measurement Acceptance Region (MAR) constraints. Savannah River Mission Completion (SRMC) subsequently pursued Wash Cycle Y to further reduce the total sulfur in the sludge batch and increase processing flexibility at DWPF. In October 2022, SRMC System Planning provided an updated SB10 Tank 40H blend baseline projection based on the Tank 51 confirmation sample results. Due to the reduced Na concentration relative to previous SB10 projections, two additional projections based on the addition of 7,000 gallons of caustic were provided in November 2022.

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Evaluation of the 0.65 Weight Percent Sulfate Solubility Limit for Sludge Batch 10 Based on November 2022 Projections

The Defense Waste Processing Facility (DWPF) is currently preparing to initiate processing of Sludge Batch 10 (SB10), which is comprised of material from Tanks 11H, 13H, 15H, 26F, 40H (heel only), and Alternate Feed Stock-2 and Sodium Reactor Experiment material from H-Canyon. Frit 473 was recommended for sludge-only (SO) and coupled processing with the Salt Waste Processing Facility (SWPF) based on previous assessments of SB10 projections with the DWPF Product Composition Control System glass property models and their associated Measurement Acceptance Region constraints. Savannah River Mission Completion (SRMC) subsequently pursued Wash Cycle Y to further reduce the total sulfur in the sludge batch and increase processing flexibility at DWPF. In October 2022, SRMC System Planning provided an updated SB10 Tank 40H blend baseline projection based on the Tank 51 confirmation sample results. Due to the reduced Na concentration relative to previous SB10 projections, two additional projections based on the addition of 7,000 gallons of caustic were provided in November 2022.

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Summary of Savannah River Site FY22 Salt Waste Qualification Data

The Savannah River National Laboratory analyzed samples from Savannah River Site Waste Tank 41H, 21H and 42H to support qualification of Salt Waste Processing Facility (SWPF) Waste Batches 5, 6, and 7 for processing (the FY22 Salt Batch Qualification samples). None 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 Mission Completion (Liquid Waste Operations subcontractor) as External Sample Results LIMS Reports and the Tank 41H (Salt Batch 5 sample) was also summarized in two separate technical reports. The analytical results (both rapid and long term) are now summarized and discussed in this technical report.

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Application of Process Chemical Modeling to Optimize Radioactive Waste Disposal at the Savannah River Site - 24242

The Technical Optimization Model (TOM) is used by Savannah River Mission Completion (SRMC) to carry out facility-wide material balance and validate chemistrydependent processes for the purpose of their System Plan.The TOM simulates material movement and chemical reactions at the Tank Farm (TF), Salt Waste Processing Facility (SWPF) and Defense Waste Processing Facility (DWPF).

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Plutonium Solubility and Supernate Concentration for Neutralized Fast Critical Assembly Discards to Savannah River Site Tank Waste

The Savannah River Site (SRS) plans to dissolve non-irradiated stainless steel (SS)-clad bundles of Fast Critical Assembly (FCA) materials in eighteen batches.1 FCA dissolution is currently underway in the 6.3D dissolver by simultaneous chemical and electrolytic dissolution, which is required to generate the harsh conditions necessary for dissolution of metal-oxide (MOX) and non-aluminum spent nuclear fuels (NASNFs).2 Nitric acid and potassium fluoride are used to promote chemical dissolution.2 Gadolinium will be added during processing as a thermal neutron poison for criticality control. There are no plans for recovering plutonium from this waste stream. After FCA dissolution, the acidic (HNO3/KF) “discards” containing the dissolved metals will be neutralized by addition of 50 wt% sodium hydroxide to a final free hydroxide concentration of 1.2 M.1 Neutralization will precipitate a slurry of insoluble solids, predominantly metal oxides/hydroxides of plutonium, uranium, and SS components. Small fractions of the SS components, Pu, U, and Gd will remain dissolved in the supernate. The neutralized slurry will be composited to existing radioactive waste storage tanks within the SRS Concentration, Storage, and Transfer Facilities (CSTF) containing other similar sludge batch (SB) materials.1 The fate of soluble plutonium and freshly-precipitated, colloidal plutonium from this process are of concern since the total Pu can challenge the waste acceptance criteria (WAC) at the downstream SRS Liquid Waste (LW) facility. Supernate decants including the neutralized FCA discards (nFCAd) within the CSTF will be composited with salt batch (StB) materials and transferred to the SRS Salt Waste Processing Facility (SWPF), where total plutonium is also of concern.

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Conceptual Model Testing Related to SDU 6 Drainwell Observations

From its inception in the early 1950s through the end of the Cold War in the early 1990s, the Savannah River Site (SRS) produced nuclear materials for national defense in five reactors. Additionally, irradiated reactor fuel and target tubes were dissolved in nitric acid to recover plutonium and uranium using the PUREX (Plutonium Uranium Reduction EXtraction) process. Liquid waste from these chemical separations processes was then stored onsite in 51 underground tanks. Eight waste storage tanks have been operationally closed (i.e. cleaned and grouted) and the remaining tanks hold a mixture of liquids, insoluble solids, and precipitated salts (SRMC-LWP-2022-00001), the latter generated by evaporating water from the liquid waste. Waste is currently being retrieved from tanks and separated into 1) high-radioactivity, low-volume, and 2) low-radioactivity, high-volume components, principally through the Salt Waste Processing Facility (SWPF) (SRMC-LWP-2023-00001). The former waste stream is vitrified in the Defense Waste Processing Facility (DWPF), stored onsite, and destined for offsite disposal in a deep geologic repository. The latter stream is mixed with dry cementitious materials in the Saltstone Production Facility (SPF) and the wet slurry placed in onsite Saltstone Disposal Units (SDUs) within the Saltstone Disposal Facility (SDF), where it hardens into a cement waste form termed saltstone. A low-infiltration surface cover system will be placed over the SDF at closure, where SDUs will then be in the subsurface post-closure (SRR-CWDA-2019-00001).

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