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At least 325 records · Page 18

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).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The CELSS research program - A brief review of recent activities

The history of the Controlled Ecological Life Support System program, initiated by NASA in the late 1970s to explore the use of bioregenerative methods of life support, is reviewed. The project focused on examining the process involved in converting inorganic minerals and gases into life support materials using sunlight as the primary energy source. The research, planning, and technological development required by the CELSS program and conducted at NASA field centers, at various universities, and by commercial organizations are reviewed. Research activities at universities have focused upon exploring methods of reducing the size of the system, reducing system power requirements, understanding issues that are associated with its long-term stability, and identifying new technologies that might be useful in improving its efficiency. Research activities at Ames research center have focused on the use of common duckweed as a high biomass-producing plant, which is high in protein and on waste processing.

Macelroy, R. D.↗

Analysis of Glycolate in Radioactive Waste by Ion Chromatography (IC) and Proton Nuclear Magnetic Resonance (H NMR)

Here, in preparation for implementing the Nitric-Glycolic (NG) acid flowsheet for the Savannah River Site (SRS) Liquid Waste System (LWS), analytical methods for determining glycolate at low concentration, below 20 mg/L in radioactive samples, were developed to support system management and safety. To accommodate the wide range of LWS matrix conditions, two alternative methods were developed, refined, and demonstrated for glycolate analysis in radioactive waste samples: ion chromatography (IC) and a proton nuclear magnetic resonance (H NMR). Investigators validated IC and H NMR methods for glycolate analysis, defined the range of applicability, and demonstrated key supporting analytical protocols. The deployed IC method is applicable in low to moderate ionic strength samples and requires sample pretreatment using a Dionex OnGuard II H + cartridge. The deployed H NMR method is more labor intensive but provides options for a broader range of matrices. Based on the results, high quality glycolate analysis of the Defense Waste Processing Facility (DWPF) condensate in Tank 22 is feasible by IC down to approximately 12 mg/L. Using H NMR, glycolate may be determined to 8 mg/L or lower depending on the run time with the potential for broader applicability of the method to higher ionic strength conditions in other tanks of the SRS LWS.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

A Review of the Literature on the Radiolytic Stability of the Next-Generation Solvent

The Original Caustic-Side Solvent Extraction (CSSX) solvent (based on the BOBCalixC6 extractant) currently in use at the Salt Waste Processing Facility (SWPF) is set to be replaced by the Next-Generation Solvent (NGS, based on the MaxCalix extractant). Current SWPF flammability safety controls use G-values for volatile gases obtained from radiolysis studies with the Original CSSX solvent. A review of past irradiation tests of both solvent systems was performed to assess the radiolytic stability of NGS with respect to flammable gas generation from radiolysis.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of DWPF Melter Primary Off-Gas Line Pluggage Deposits

This report details results from characterization of the Defense Waste Processing Facility (DWPF) melter off-gas pluggage deposits collected in late calendar year 2021 from the outlet of the jumper immediately preceding the quencher. DWPF requested through a technical assistance request characterization of the melter off-gas deposits by X-Ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDAX), chemical analysis and both aqueous and organic leaching of the solids.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Extraction, Scrub, and Strip Test Results for the IBC BOBCalix Solvent Samples

A second vendor for solvent extraction components has been chosen for use at the Salt Waste Processing Facility (SWPF). IBC Advanced Technologies (IBC) has provided samples of their BOBCalix, as well as complete solvent. These samples were tested for quality assurance purposes to ensure their use at SWPF is acceptable. Two Extraction, Scrub, and Strip (ESS) tests were performed on solvent samples from IBC. The purpose of testing these samples was to determine if the solvents are displaying the correct extraction and stripping behavior with cesium.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

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.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Investigation of Mercury Compound Partitioning Through the Solvent Extraction System

Savannah River National Laboratory (SRNL) has been requested by Savannah River Mission Completion (SRMC)/ Salt Waste Processing Facility (SWPF) personnel to investigate the potential routes for titanium and mercury accumulations within the SWPF Flowsheet. This report documents work performed to examine how various forms of mercury can migrate through the multiple flowsheets of a solvent extraction system. This entailed 29 single stage distribution tests, a multi-stage Extraction-Scrub-Strip (ESS) test, and a detailed speciation analysis of several salt batch feed samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effects of Bedrock Landsliding on Cosmogenically Determined Erosion Rates

The successful quantification of long-term erosion rates underpins our understanding of landscape. formation, the topographic evolution of mountain ranges, and the mass balance within active orogens. The measurement of in situ-produced cosmogenic radionuclides (CRNs) in fluvial and alluvial sediments is perhaps the method with the greatest ability to provide such long-term erosion rates. In active orogens, however, deep-seated bedrock landsliding is an important erosional process, the effect of which on CRN-derived erosion rates is largely unquantified. We present a numerical simulation of cosmogenic nuclide production and distribution in landslide-dominated catchments to address the effect of bedrock landsliding on cosmogenic erosion rates in actively eroding landscapes. Results of the simulation indicate that the temporal stability of erosion rates determined from CRN concentrations in sediment decreases with increased ratios of landsliding to sediment detachment rates within a given catchment area, and that larger catchment areas must be sampled with increased frequency of landsliding in order to accurately evaluate long-term erosion rates. In addition, results of this simulation suggest that sediment sampling for CRNs is the appropriate method for determining long-term erosion rates in regions dominated by mass-wasting processes, while bedrock surface sampling for CRNs is generally an ineffective means of determining long-term erosion rates. Response times of CRN concentrations to changes in erosion rate indicate that climatically driven cycles of erosion may be detected relatively quickly after such changes occur, but that complete equilibration of CRN concentrations to new erosional conditions may take tens of thousands of years. Simulation results of CRN erosion rates are compared with a new, rich dataset of CRN concentrations from the Nepalese Himalaya, supporting conclusions drawn from the simulation.

Niemi, Nathan↗

System Design Techniques for Reducing the Power Requirements of Advanced life Support Systems

The high power requirement associated with overall operation of regenerative life support systems is a critical Z:p technological challenge. Optimization of individual processors alone will not be sufficient to produce an optimized system. System studies must be used in order to improve the overall efficiency of life support systems. Current research efforts at NASA Ames Research Center are aimed at developing approaches for reducing system power and energy usage in advanced life support systems. System energy integration and energy reuse techniques are being applied to advanced life support, in addition to advanced control methods for efficient distribution of power and thermal resources. An overview of current results of this work will be presented. The development of integrated system designs that reuse waste heat from sources such as crop lighting and solid waste processing systems will reduce overall power and cooling requirements. Using an energy integration technique known as Pinch analysis, system heat exchange designs are being developed that match hot and cold streams according to specific design principles. For various designs, the potential savings for power, heating and cooling are being identified and quantified. The use of state-of-the-art control methods for distribution of resources, such as system cooling water or electrical power, will also reduce overall power and cooling requirements. Control algorithms are being developed which dynamically adjust the use of system resources by the various subsystems and components in order to achieve an overall goal, such as smoothing of power usage and/or heat rejection profiles, while maintaining adequate reserves of food, water, oxygen, and other consumables, and preventing excessive build-up of waste materials. Reductions in the peak loading of the power and thermal systems will lead to lower overall requirements. Computer simulation models are being used to test various control system designs.

Finn, Cory↗

Solid-State Recrystallization Pathways of Sodium Aluminate Hydroxy Hydrates

Crystallization of Al-bearing solid phases from highly alkaline Na 2 O:Al 2 O 3 :H 2 O solutions commonly necessitates an Al 3+ coordination change from tetrahedral to octahedral, but intermediate coordination states are often difficult to isolate. Here, a similar Al 3+ coordination change process is examined during the solid-state recrystallization of sodium oxohydroxoaluminate hydrate (MSA) to nonasodium bis(hexahydroxy aluminate) trihydroxide hexahydrate (NSA) at ambient temperature. While the MSA structure contains solely polymerized tetrahedral Al 3+ , the NSA structure is a molecular aluminate salt solely based upon monomeric octahedral Al 3+ . Spontaneous recrystallization of MSA and excess sodium hydroxide hydrate into NSA over 3 days of reaction time was clearly evident in X-ray diffractograms and in Raman spectra. In situ 27 Al multiple quantum MAS NMR spectroscopy showed no evidence of intermediate aluminates, suggesting that intermediates, such as pentacoordinate Al 3+ , are short-lived and require more highly time resolved spectroscopies to detect. Such research is advancing upon detailed mechanistic understanding of Al 3+ coordination change mechanisms in these highly alkaline systems, with relevance to aluminum refining, corrosion sciences, and nuclear waste processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of the Potential for Precipitation of Solids during Storage of Non-Aluminum SNF Solutions

Non-aluminum clad spent nuclear fuels (NASNF) stored in the L-Area basin will be dissolved in H-Canyon using the 6.3D electrolytic dissolver. The solutions will be stored in either the hot or warm canyon until the preparation of a sludge batch for the Defense Waste Processing Facility. Spent nuclear fuel solutions could be stored for 1-2 years before transfer to the H-Area Tank Farm depending on the interval between sludge batches. The solution level in the storage tanks will be maintained; therefore, precipitation of solids due to evaporation is not an issue. However, the precipitation of solids from completely dissolved SNF due to solution instabilities has been observed during intermediate storage of solutions generating hydrated oxides.The presence of fissile material in these solids is generally associated with zirconium molybdate, which is known to act as a host lattice for Pu and can carry the actinides upon precipitation. The formation of zirconium molybdate solids which carry fissile material is a potential concern for the storage of NASNF solutions. To address this concern, the Savannah River National Laboratory performed a literature review to identify knowledge gaps which may require experimental work to determine if the formation of solids is a concern during storage of these solutions. Based on the literature review, the precipitation of zirconium molybdate solids from the Campaign 1 NASNF solutions during intermediatestorage is expected. This conclusion is supported by the identification of zirconium molybdate solids found on the H-Canyon 6.1D Dissolver MK-12 insert spacer. The formation of the zirconium molybdate solids is attributed to hydrolysis and radiolytic processes in the nitric acid solution. As the molybdate solids form, U and Pu can substitute for Zr in the crystal lattice resulting in co-precipitation. Generally, the Pu substitutes directly into the crystal lattice during precipitation while the U associated with the molybdate solids more likely absorbs from the solution. The U in the NASNF solutions is present as uranyl nitrate, a 2+ cation which will not substitute as easily into the molybdate crystal lattice for the Zr 4+ ion.

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SRNL Sludge Batch 10 Qualification SRAT and SME Off-Gas Results

Savannah River National Laboratory (SRNL) completed a small-scale demonstration of the Defense Waste Processing Facility (DWPF) Chemical Process Cell (CPC) utilizing the nitric-glycolic acid (NGA) flowsheet to support Sludge Batch 10 (SB10) qualification. The demonstration utilized a Tank 51 slurry sample washed by SRNL (with added H-canyon material). The purpose of this document is to report the observed off-gas results from the demonstration. With the NGA flowsheet, DWPF has a CPC hydrogen generation limit of 2.4×10 -2 lb/h. The peak observed rate was nearly 90 times less than that limit during SRNL testing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

M-Star ® Software Test and Verification

Savannah River Mission Completion (SRMC) currently manages the risk for retained hydrogen in the Defense Waste Processing Facility (DWPF) vessels by implementing a Retained Hydrogen Program. The current program relies on Sludge Batch (SB) 8 Gas Chromatograph data and on conservative assumptions concerning gas release and retention to determine allowable vessel Quiescent time (Q-time). The authors identified M-Star ® CFD as a software that could simulate processes such as fluid flow, heat transfer, species transport, chemical reactions, particle transport, and retained hydrogen gas release. Preliminary simulation results suggest that more realistic assumptions on gas retention and release may be feasible for the DWPF retained hydrogen program. Because of the desire to use the M-Star ® software to perform analyses that support nuclear safety, SRMC has requested Savannah River National Laboratory (SRNL) to upgrade the software classification level of M-Star ® CFD from level D to level A to perform analyses that support nuclear safety.

08 HYDROGEN↗

Ion Chromatography (IC) Round Robin Analyses of Low Glycolate Concentrations in Recycle Collection Tank (RCT) Post Permanganate Treatment Simulant

This work is a demonstration of Ion Chromatography (IC) analysis of low concentrations of glycolate in chemical simulant designed to mimic the matrix in the Recycle Collection Tank (RCT) at the Defense Waste Processing Facility (DWPF) after sodium permanganate oxidation treatment. The IC method was previously developed [1] and this report covers the results of round robin testing with three analytical laboratories located at the Savannah River Site (SRS). The laboratories are termed the Sensing & Metrology (S&M) laboratory at the Savannah River National Laboratory (SRNL), the Processing Science Analytical Laboratory (PSAL) at SRNL, and the DWPF laboratory at SRS. Each laboratory received four samples: (1) 200 mL of 21.3 mg/L glycolate in RCT post permanganate strike sulfite quenched simulant, (2) 200 mL of 38.0 mg/L glycolate in RCT post permanganate strike sulfite quenched simulant, (3) 200 mL of 54.9 mg/L glycolate in RCT post permanganate strike sulfite quenched simulant, and (4) 600 mL of RCT post permanganate strike sulfite quenched simulant to use for matrix matched blanks.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Uranium Solubility and Supernate Enrichment Testing for Accelerated Basin De-Inventory Discards to Concentration, Storage, and Transfer Facilities

After future Accelerated Basin De-inventory (ABD) enriched uranium discards into sludge batches (SB), portions of supernate decants during SB preparation will be blended into salt batches (StB) and the resulting feeds must meet the nuclear safety requirements for the Salt Waste Processing Facility (SWPF). During previous SB10 sampling and testing, which involved H-Canyon material containing enriched uranium being mixed with Tank 51 sludge shortly after the H-Canyon stream was neutralized, it was identified that the uranium isotopic enrichment in the supernate deviated from the uranium isotopic enrichment in the slurry. The higher uranium isotopic enrichment in the supernate introduced the risk of challenging the feed requirements of SWPF. The ABD material added to SB11 was isotopically diluted with depleted uranium, mitigating any downstream impacts. However, H-Canyon desires to eliminate or minimize future depleted uranium additions in order to meet the mission schedule.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Probing the pH Effect on Boehmite Particles in Water Using Vacuum Ultraviolet Single-Photon Ionization Mass Spectrometry

Boehmite has been widely used in theoretical research and industry, especially for hazardous material processing. For the liquid-phase treating process, the interfacial properties of boehmite are believed to be affected by pH conditions, which change its physicochemical behavior. However, molecular-level detection on cluster ions is challenging when using bulk approaches. Herein we employ in situ vacuum ultraviolet single-photon ionization mass spectrometry (VUV SPI-MS) coupled with a vacuum-compatible microreactor system for analysis at the liquid–vacuum interface (SALVI) to investigate the solute molecular composition of boehmite under different pH conditions for the first time. The mass spectral results show that more complex clustering of solute molecules exists at the solid–liquid (s–l) interface than conventionally perceived in a “simple” aqueous solution. Besides solute ions, such as boehmite molecules and fragments, the composition and appearance energies of these newly discovered solvated cluster ions are determined by VUV SPI-MS in different pH solutions. We offer new results for the pH-dependent effect of boehmite and provide insights into a more detailed solvation mechanism at the s–l interface. By comparing the key products under different pH conditions, fundamental understanding of boehmite dissolution is revealed to assist the engineering design of waste processing and storage solutions.

SALVI↗

Gandolinium poison solubility testing for the downstream impacts from accelerated basin de-inventory

The Accelerated Basin De-inventory (ABD) Program at the Savannah River Site (SRS) is designed to accelerate the de-inventory of L-Basin and accelerate the Spent Nuclear Fuel (SNF) Disposition mission. Spent fuel will be dissolved in H-Canyon without recovery of uranium. The dissolver solutions will be temporarily stored, pH-adjusted to excess hydroxide (which will facilitate precipitation of metal oxides/hydroxides), transferred to the Concentration, Storage, and Transfer Facility (CSTF), and subsequently immobilized in the Defense Waste Processing Facility (DWPF) during planned sludge batch campaigns. ABD accelerates basin closure, significantly reduces programmatic risk, and greatly reduces the lifecycle budget requirements for the site by eliminating the need for a SNF drying and packaging capability. The ABD approach represents a significant change to the clean-up approach for the SRS. However, the increased fissile loading in sludge batches, due to the dissolver solutions, requires investigation to ensure fissile limits are efficiently and safely managed; higher fissile loadings in the glass are projected to be two to three times higher than the current fissile concentration limit of 897 g/m 3 and will be addressed in a future report.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗