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At least 127 records · Page 7

Predicting Saturated Hydraulic Conductivity over Time for Degrading Saltstone Vault Concrete - 20376

At the Savannah River Site (SRS), low-level liquid tank waste is mixed with cementitious materials to produce a solid, monolithic waste form referred to as saltstone. The liquid saltstone mixture is pumped into massive concrete structures referred to as saltstone disposal units (SDUs) for curing and long-term storage. SDUs are vaults made of high performance concrete forming a barrier between saltstone and the surrounding environment. Predicting the long-term performance of SDU vault concrete, as well as the saltstone material itself, is critical to understanding the potential releases of radionuclides to the surrounding environment as described in the Saltstone Disposal Facility (SDF) performance assessment (PA). The hydraulic conductivity profile for SDU vault concrete was conservatively assumed to degrade linearly from the initial saturated hydraulic conductivity of the intact concrete over a long period of time. The initial hydraulic properties of saturated SDU vault concrete have been measured, and the final hydraulic properties of degraded vault concrete are assumed to be the same as the porous backfill material that will surround the vault after closure. The assumed final condition of the vault concrete is also conservative in that it provides a greater estimate of water penetration through the vault than would generally be expected. Therefore, insights that provide more realistic but conservative estimates as to how degradation processes may change the hydraulic properties of the SDU vault concrete, the time dependent relationship of the vault concrete hydraulic properties to degradation (and thus time), and the final hydraulic properties of the vault concrete provides useful additions to the SDF PA. This paper focuses on the assumption that the saltstone vault concrete saturated hydraulic conductivity would decrease linearly as a function of degradation time; this assumption resulted from a worst-case, weighted (by relative layer thickness), arithmetic average of intact and backfill material hydraulic conductivities representing flow parallel to a layered system. This research indicates that the effective saturated hydraulic conductivity of the degraded SDU vault concrete should be based on the relative thickness-weighted geometric mean of the intact and degraded layers hydraulic conductivities. This alternative, which is supported extensively in the relevant literature and evaluated in this paper, leads to a more realistic and defensible estimate of the effective saturated hydraulic conductivity in degraded vault concrete while remaining conservative. The impact of using the more realistic estimate of the effective saturated hydraulic conductivity for the degraded concrete decreases the effective saturated hydraulic conductivity by up to several orders of magnitude for early times (i.e., when the SDU vault concrete is assumed degraded via sulfate attack and carbonation). This revised estimate of the effective saturated hydraulic conductivity has been implemented in the recently revised SDF PA. (authors)

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FY25 Organic Evaporation Testing in Support of Hanford Sample-and-Send

The Hanford Waste Treatment and Immobilization Plant (WTP) is being built to treat and immobilize the approximately 56 million gallons of radioactive mixed waste stored in 156 underground storage tanks. The baseline method for immobilization of Low-Activity Waste (LAW) is vitrification, but additional immobilization capacity is needed to supplement the initial LAW melters. Additionally, efforts are being undertaken to accelerate the disposition of Pre-Treated Waste (PTW) in Hanford’s West Area. An alternative cementitious waste form is being investigated as an alternative immobilization method. However, one impediment to a cementitious waste form is the presence of Land Disposal Restricted (LDR) organic chemicals in tank waste, which are regulated on a concentration-based standard in the final waste form. Hence, if the quantity of organics in PTW and LAW is high enough, treatment may be needed to destroy or remove said organics to make a waste form compatible with disposal in a mixed low level waste landfill. This work evaluates evaporation as a potential avenue for treatment of LDR organics to eliminate the impediment and permit possible use of a cementitious waste form.

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Proton nuclear magnetic resonance (1H NMR) of flammable organic chemicals in radioactive high–level supernatant waste at the Savannah River Site (SRS)

The Savannah River Site stores approximately 36 million gallons of radioactive and hazardous waste that contains approximately 245 million curies. The waste is sent through various chemical processes to reduce its volume and to separate various components. The facility plans to replace formic acid (a chemical used to reduce soluble mercury) with glycolic acid. Recycle solution with glycolate may flow back to the tank farm, where the glycolate can generate hydrogen gas by thermal and radiolytic mechanisms. The current analytical method for detecting glycolate (ion chromatography) in supernatant requires a large dilution to reduce interference from the nitrate anions. Hydrogen nuclear magnetic resonance is an analytical method that requires less sample dilution. It takes advantage of the CH 2 group in glycolate. Liquid samples were spiked with four different levels of glycolate to build a calibration line, as it is recommended in the standard addition method. The detection and quantitation limits determined were 1 and 5 ppm, respectively, for 32 scans, which is well below the process limit of 10 ppm. In one test, 800 scans of a supernatant spiked with 1 ppm glycolate resulted in a -CH 2 peak with a signal-to-noise ratio of 36.

1H↗

Melt-Spun PAN Precursor for Cost-Effective Carbon Fibers in High Pressure Compressed Gas Tankage

The objective of this program was to synthesize melt-spinnable polyacrylonitrile (PAN) precursor that will lead to carbon fiber 25% less expensive than carbon fiber produced from conventional PAN precursor when produced in large volumes. The carbon fiber produced from this precursor needs to achieve ≥ 700 ksi tensile strength with this cost reduction to replace the incumbent fiber. In this program, the technology for producing precursor and then converted carbon fiber (CF) capable of meeting the 700 ksi target was to be demonstrated at a small scale in tows, containing ≥ 100 filaments. If this program moved on to a “Phase 2”, the processes would be scaled up to produce and test Type IV compressed gas storage tanks capable of meeting the 700-bar ultimate targeted FOA performance level. Precursor fiber production typically contributes a large fraction (~50%) to finished CF manufactured cost. Presently, all high strength CFs are manufactured from solution spun PAN precursor, accomplished at low temperatures using large amounts of environmentally unfriendly solvents that impart major impact to line speed and costs involved with handling and reclaiming the solvents and associated “waste streams” required in spinning and extracting those solvents. PAN melt spinning was demonstrated by the company BASF in CF precursor production and used in production of some other acrylic fibers, but significant production challenges remain for meeting the established CF metrics. Melt spinning requires use of plasticizers to suppress the melt temperature of the predominantly PAN formulation to a point sufficiently below the temperature of significant cross-linking. Fortunately, BASF and this team’s earlier work had demonstrated acrylic formulations melt spun with combinations of plasticizing solvents at much lower solvent levels. This project team made significant progress in understanding technical issues and identifying formulation pathways in earlier work in this area where >250ksi strength was achieved. The goal of this program was to pursue a more comprehensive approach with a larger, more diverse team having greater equipment design and overall production capabilities to push rapidly beyond the science to resolve remaining “engineering” issues associated with establishing stable, continuous processes for precursor fiber leading to enhanced, cost-effective CF and composite tank production.

36 MATERIALS SCIENCE↗

Demonstration Test Report: Vacuum Thermal Desorption (VTD) Testing to Support West Area Waste Feed Test 2

Approximately 54 million gallons of radioactive and hazardous waste are stored in underground storage tanks at the U.S. Department of Energy’s (DOE’s) Hanford Site in southeastern Washington State. The Hanford Waste Treatment and Immobilization Plant (WTP) is being constructed to immobilize the waste in glass waste forms. The baseline configuration of the WTP includes a Pretreatment Facility to separate the wastes into a small volume of high-level waste (HLW) containing most of the radioactivity and a larger volume of low-activity waste (LAW) containing most of the non-radioactive chemicals. The HLW will be converted to glass in the HLW vitrification facility for ultimate disposal at a federal repository.

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Identification and Quantification of Technetium Species in Hanford Waste Tank AN-102

Technetium-99 (Tc) generated from the fission of 235U and 239Pu in high yields is one of the most difficult contaminants to be addressed at the U.S. Department of Energy Hanford Site. In strongly alkaline solutions typifying Hanford tank waste, Tc exists as pertechnetate (TcO4-) (oxidation state VII) as well as in reduced forms (oxidation state < VII) collectively known as non-pertechnetate species. Designing strategies for effective Tc management, including separation and immobilization, necessitates understanding the molecular structure of the non- pertechnetate species and their identification in the actual tank waste samples, which would facilitate development of new treatment technologies effective for dissimilar Tc species. Toward this objective, a spectroscopic library of the Tc(I) [fac-Tc(CO)3]+ and Tc(IV, VII) compounds was generated using a range of techniques and applied to the characterization of the actual tank waste supernatant collected from the tank 241-AN-102 at Hanford, WA. A sample of the 241-AN-102 tank waste supernatant was processed to adjust Na concentration to about 5.6 M and remove 137Cs by spherical resorcinol-formaldehyde (sRF) ion exchange resin. Cesium-loaded sRF column was eluted with 0.5 M HNO3. As received AN-102, Cs-depleted AN-102 effluent, and sRF eluate fractions were comprehensively characterized for chemical composition and speciation of Tc using 99Tc nuclear magnetic resonance spectroscopy and X-ray absorption spectroscopy. It was demonstrated for the first time that non-pertechnetate Tc present in the 241-AN-102 tank waste is composed of several low-valent Tc species, including the Tc(I) [fac-Tc(CO)3]+ and Tc(IV) compounds. This is the second experimental observation of the [fac-Tc(CO)3]+ species in the Hanford tank waste and the first demonstration of multiple forms of non-pertechnetate species existing simultaneously in the waste, cumulatively highlighting their importance for the waste processing.

Low Activity Waste (LAW), High Level Waste, nuclea↗

Initial Testing of Alkaline Earth Metal Ion Absorption on Crystalline Silicotitanate - 20440

The Tank Closure Cesium Removal process at the Savannah River Site (SRS) has processed aqueous tank waste using the inorganic ion exchange media IONSIV{sup TM} R9120-Ba (which is also known as Crystalline Silicotitanate (CST)). Salt-cake in Tank 10H at SRS was dissolved and processed through filters and ion exchange columns. The primary purpose of the process is to remove Cs-137 from the aqueous waste so that it can be disposed as low level waste. It is known that this inorganic media also absorbs strontium from solution, and that strontium competes with cesium ions for absorption sites. The strontium ion is actually more strongly absorbed than the cesium ion from typical tank waste. However, strontium is typically present in low concentrations so does not normally cause a significant impact. Strontium is present as both non-radioactive isotopes and the radioactive Sr-90 isotope; with the non-radioactive isotopes being much more abundant. Although the total strontium solubility is usually much lower than cesium, some tank waste compositions can have a high enough soluble strontium concentration to decrease the cesium absorption. Relatedly, some testing at SRS suggested that another alkaline earth metal, calcium, may also absorb onto CST and may decrease cesium absorption. Barium is also an important species in treatment of tank waste, but is also usually present at low concentrations. However, after the Cs-137 is absorbed onto CST, it emits a beta particle and converts to Ba-137m, which then decays to non-radioactive Ba-137 by emission of a gamma ray. If the Ba-137m were to desorb quickly, it could impact the dose rate in down-stream equipment. In order to understand the impact of these alkaline earth metals on CST, SRNL performed testing using simulants of SRS tank waste that contain soluble barium, strontium, and calcium. Testing examined both removal of the alkaline earth metals and their impact on removal of cesium. Testing involved first developing realistic waste simulant formulations and dissolving the alkaline earth metals to high enough concentrations to potentially impact the Cs absorption. Once the formulations were developed and prepared, computer modeling was used to calculate the expected Cs absorption behavior to determine if the alkaline earth metals impact the performance. Measurements of the alkaline earth metals absorption by the media is also important for disposition of spent media because of the added radionuclide inventory from the Sr-90. These initial tests are examining the general impact and will be used to determine if further testing or measurements are needed. (authors)

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Antifoam Development for Eliminating Flammability Hazards and Decreasing Cycle Time in the Defense Waste Processing Facility

Foam, due to the high gas generation rates of boiling and chemical reaction offgasing, requires control measures to prevent the foam from contaminating the condensate and to facilitate efficient plant operation. Antifoam was utilized to minimize foam production during chemical processing in the DWPF and during High-Level Waste (HLW) evaporation at SRS and Hanford. However, the current antifoam used in the SRS DWPF increases flammability risk during chemical processing (generates three flammable degradation products) and while feeding the melter (can decompose to CO/hydrogen). It is also the likely source of methyl functional groups for the organo-mercury present in the tank farm and excessive mercury in Saltstone. Additionally, the planned startup of Salt Waste Processing Facility (SWPF), with much higher throughput, will challenge DWPF to process at higher gas generation rates. DWPF employs Antifoam 747, a superspreader produced by Momentive Performance Materials, as an antifoaming agent during waste processing. During DWPF chemical processing, antifoam must be effective up to boiling (i.e., up to 103°C) and between a pH of 3-13. Antifoam 747 is most effective at a pH range of 6-8 and degrades as pH deviates. In addition, SRNL identified three flammable antifoam degradation products using mass spectrometer (MS) and fourier transform infrared (FTIR) offgas analyzers during simulations. A new antifoam or a new method to control foam is needed to minimize DWPF processing time and reduce the risk of contamination. In addition, testing should be completed to ensure that other antifoams used in HLW processing do not have similar flammability hazards or cause unintended impacts in downstream processing.

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Compositing and Characterization of SE Quadrant Waste Exemplars

This report outlines the experimental investigation and characterization of transport properties in Hanford SE quadrant High-Level Waste (HLW). The goal of the study was to establish baseline behaviors of bulk composite rheology and settling characteristics to facilitate waste treatment process design for the Waste Treatment and Immobilization Plant (WTP) and avoid waste conditions and properties favorable to bubble cascade gas release events. The study focused on two major objectives: 1) identifying, obtaining, and preparing relevant Hanford tank waste samples for evaluation and 2) quantifying the “as-received” rheology and transport properties of the samples. Twenty-three centrifuged core segments originating from tanks AN-101, AN-106, and AW-105 were selected based on compositional relevance to SE quadrant PUREX cladding waste. These materials were composited into five waste composites enriched with target analytes: aluminum (Al), iron (Fe), phosphate (PO 4 ), uranium (U), and zirconium (Zr). Physical property and transport testing examined particle size distributions, bulk densities, settling behaviors, rheological properties, shear strengths, and just-suspended mixing speeds (NJS). Testing revealed two distinct composite classifications based on rheological characteristics: non-Newtonian composites (Fe and PO 4 ) and Newtonian composites (Al, U, and Zr). The Fe and PO 4 composites exhibited slow settling rates and reduced mobilization proclivity, attributable to strong particle-particle interactions and the formation of yield structures within non-Newtonian slurries. In contrast, the Al, U, and Zr composites displayed rapid settling and dense compaction behaviors, indicative of minimal structuring and interactions. Shear strengths for all composites were generally low relative to prior studies of SE quadrant waste, with only the U composite showing elevated strength approaching values reported in previous literature. Repeat shear strength measurements revealed contributions from dense granular material in the U composite and stronger cohesive properties in the Al composite. Settling data highlighted hindered settling behavior, with rates falling more than one order of magnitude below estimates based on Stokes’ law and rate decreasing as composite UDS content increased. NJS testing demonstrated different mobilization behaviors between cohesive and granular composites. The Fe composite required the highest mixing rate for resuspension, while the Al composite was the easiest to resuspend. Comparison of measured NJS against predictions made using the Zwietering correlation suggests non-Newtonian behavior alters resuspension mechanics, rendering non-Newtonian systems more stable against resuspension lift forces relative to their granular counterparts.

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Analysis of Ionic Mercury Species in SRR Samples Measured by SRNL and Eurofins FGS

Savannah River Remediation (SRR) requested the development of mercury speciation capabilities at the Savannah River National Laboratory (SRNL) to support the Liquid Waste Operations at SRS. As part of that method development, SRR requested that SRNL Analytical Development (AD) compare their results with those obtained from their outside contract laboratory, Eurofins Frontier Global Sciences (FGS). This document reports on this method development work performed at SRNL as well as the comparative analyses conducted between the two laboratories. Development, optimization, and validation were undertaken at SRNL to produce a method for the species-specific analysis of ionic mercury. This method was developed as a secondary step to an existing method, L16.1-ADS-1579 Purgeable Mercury Cold Vapor Atomic Fluorescence Spectrophotometry. As such, much of the development and validation were performed in service of development of L16.1-ADS-1579. Six samples, representing two consecutive quarterly Tank 50 batches, were tested for ionic mercury by SRNL-AD and Eurofins FGS. The mean values reported by each lab for ionic mercury differed by less than one standard deviation, therefore the values reported by both labs were considered to be in agreement. SRNL-AD reported values for the six samples that differed by -5.56 mean percent, relative to Eurofins FGS. Together with comparable quality control data reported by each laboratory, these data represent a high level of agreement among both laboratories. With a viable method for ionic mercury that matches the data quality provided by outside commercial laboratories, SRNL-AD has demonstrated competency in measuring methylmercury, ethylmercury, total mercury, soluble & particulate mercury, purgeable mercury, and ionic mercury species in a variety of radioactive tank samples.

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Glycolate Analysis in Tank 22: Developing and Testing Analytical Methods for the Savannah River Site Liquid Waste System

Researchers developed and tested a range of techniques to support a low mg/L Limit of Quantitation (LOQ) of glycolate in radioactive Tank 22 waste solution by Ion Chromatography (IC) and by proton NMR. For the IC method, Dionex OnGuard II cartridges were tested as a means of removing alkali earth and transition metals that can interfere during ion chromatography applications especially when analyzing for low-concentration, chelating analytes. Additionally, concentrations of nitrate in the raw Tank 22 sample (5,000 to 10,000 mg/L) were managed by using reasonable levels of sample dilution. The resulting IC performance quality was enhanced by improving the baseline, increasing sensitivity [Limit of Quantitation (LOQ) of 12 mg/L and Limit of Detection (LOD) of 4.0 mg/L], and resolving analytes into well-defined Gaussian peaks when using the Dionex OnGuard II H⁺ cartridges to remove matrix interferences. High concentrations of nitrate limited the performance of the IC method. To achieve an acceptable baseline, samples with high nitrate content require more dilution, resulting in higher detection limits. Tests on samples with higher concentrations of nitrate (Tank 30 and 32 supernate with approximately 150000 mg/L nitrate) suggested that IC detection limits for glycolate in these samples would be > 500 mg/L. Thus, an LOQ of 12 mg/L is not feasible by this IC method on evaporator feed samples. An alternative method of glycolate analysis, using proton nuclear magnetic resonance (H NMR), was developed by the research team. In initial tests, the H NMR technique provided reasonable quantitation of glycolate in Tank 22 conditions by direct observation of the liquid. The H NMR method may provide improved detection limits for solutions with higher nitrate concentrations. We recommend further development of this analysis for high nitrate LWS samples such as evaporator feed and evaporator drop tank content. A method for pretreatment of samples using crystalline silicotitanate (CST) was developed and tested. The objective of the pretreatment was to facilitate analysis of samples with higher levels of radioactivity. The pretreatment did not influence the glycolate concentration in solution, and the pretreatment is projected to reduce Cs 137 activity in a sample by a factor of 16,200. The double strike CST pretreatment was demonstrated and would allow milliliters of higher activity samples to be transferred from the Shielded Cells and handled in a containment unit for glycolate analysis. The various studies validated IC and H NMR methods for glycolate analysis, defined the range of applicability, and demonstrated key supporting analytical protocols. Based on the results, high quality glycolate analysis of Tank 22 is feasible down to approximately 12 mg/L, with the potential for broader applicability of the methods to other conditions in the Savannah River Site Liquid Waste System (LWS).

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Determining the Solubility Behavior of Kogarkoite in Simulated Nuclear Waste

Kogarkoite (Na 3 FSO 4 ) is a sparingly soluble fluoride–sulfate double salt that has been identified in high level nuclear waste sludge at the Hanford Site and, more recently, in sludge batch compilation samples at the Savannah River Site (SRS). Due to its complex dissolution behavior, which exhibits an inverse dependence on sodium ion activity, the presence of this mineral poses significant challenges to waste retrieval and processing. Incomplete dissolution during sludge washing can lead to the retention of fluoride and sulfate in the high-level waste feed, potentially causing the formation of corrosive, immiscible molten salt layers, known as "glass gall,” in vitrification melters. Current efforts to optimize flowsheet parameters and wash-water volumes are hindered by the absence of a commercially available, certified reference material, which prevents the accurate calibration of analytical methods and the verification of dissolution kinetics. To address this critical gap, this research focuses on the laboratory synthesis of pure Kogarkoite to serve as a standard for comprehensive solubility and washing performance testing. A coupled synthesis and simulant campaign was executed using an evaporative crystallization protocol designed to replicate the dynamic concentration effects observed in tank farm operations. Thirteen simulant matrices were prepared by dissolving systematically varied ratios of sodium fluoride (NaF) and sodium sulfate (Na 2 SO 4 ) in deionized water under three distinct caustic regimes: 0.0 g (control), 4.0 g (~1 M), and 12.0 g (~3 M) sodium hydroxide (NaOH). While thermodynamic equilibrium models suggest that high-caustic environments should favor the stability of the double salt7, results from this evaporative study at 25 0 C revealed a distinct kinetic divergence. Simulants with high hydroxide loading predominantly yielded large, blocky crystals of sodium sulfate decahydrate (Na 2 SO 4 .10H 2 O). Successful synthesis of pure Kogarkoite was achieved exclusively in specific NaOH-free compositional windows, where the precipitate manifested as fine, opaque granular aggregates. Ion chromatography (IC) analysis confirmed phase purity through the simultaneous stoichiometric depletion of both fluoride and sulfate from the supernatant. This successful synthesis establishes a reproducible route to generate bulk Kogarkoite, enabling the subsequent phase of quantitative dissolution testing using inhibited water to optimize sludge-batch assembly.

Sarker, Md Sharif [Florida International Univ. (FI↗

INL Site ARG-US Implementation – FY22 Activities and FY23 Plans

The Packaging Certification and Life Cycle Management program at Argonne National Laboratory (ANL) developed a suite of monitoring systems collectively referred to here as ARG-US. ARG-US provides necessary data for nuclear facility and system operation and maintenance, and has been previously demonstrated in hot cells, radioactive material (RAM) storage areas, and RAM shipment trucks. It has also been installed directly on RAM storage and shipment containers. ARG-US offers some unique advantages over other commercially available systems by using wireless data connections, battery power supplies, and customizable monitoring methods. Idaho National Laboratory (INL) has been tasked with investigating applications for ARG-US at INL site facilities, which are operated by several different contractors. The initial investigation scope centered on CPP-603 Irradiated Fuel Storage Facility in relation to the upcoming Department of Energy (DOE) Spent Nuclear Fuel (SNF) Packaging Demonstration. The investigation has been led by the Used Fuel Management Department in INL’s Nuclear Science and Technology (NS&T) directorate. This investigation is expected to recommend INL site processes or facilities in which to implement ARG-US systems. INL has engaged local site technical and oversight representatives, security, nuclear safeguards, and program management personnel to identify good candidates for ARG-US test implementations. INL has identified the following high-level goals for any INL site implementation of ARG-US: provide unique testing environments, prompt development of new monitoring methods/techniques for the ARG-US suite, and acquire useful monitoring for the user facility. As a result, INL suggests three program areas for further investigation: CPP-603 Fuel Handling Cave (FHC), legacy mixed waste storage systems at Idaho Nuclear Technology & Engineering Center (INTEC) known as the “Tank Farm,” and periodic and emergency environmental monitoring. This progress report relates activities undertaken in this investigation, describes the preliminary areas of interest for limited scope ARG-US testing or implementation, and relays expected actions for completing the task scope. This report offers an opportunity to the program sponsor, technical leads at ANL, and INL site representatives to give feedback on the initial assessment and make recommendations on the forthcoming activities.

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Investigation of INL Site Implementation of ARG-US

The Packaging Certification and Life Cycle Management department at Argonne National Laboratory (ANL) developed a suite of monitoring systems collectively referred to here as ARG-US. ARG-US is used to provide necessary data for nuclear facility and system operation and maintenance. ARG-US has been previously demonstrated in hot cells, radioactive material (RAM) storage areas, and RAM shipment trucks. It has also been installed directly on RAM storage and shipment containers. ARG-US offers some unique advantages over other commercially available systems by using wireless data connections, battery power supplies, and customizable monitoring methods. Idaho National Laboratory (INL) has been tasked with investigating applications for ARG-US at INL site facilities, which are operated by several different contractors. The initial investigation scope centered on CPP-603 Wet & Dry Fuel Storage Facility in relation to the upcoming DOE Spent (SNF) Packaging Demonstration. The investigation has been led by the Used Fuel Management Department in the Nuclear Science and Technology Directorate. This investigation is expected to recommend processes or facilities at the INL site at which to implement ARG-US systems. INL has engaged local site technical and oversite representatives, security, nuclear safeguards, and program management to identify good candidates for ARG-US test implementations. INL has identified high-level goals for any INL site implementation of ARG-US: provide unique testing environments, prompt development of new monitoring methods/techniques for the ARG-US suite, and acquire useful monitoring for the user facility. To these ends, INL suggests 3 program areas for further investigation: CPP-603 Fuel Handling Cave (FHC), legacy mixed waste storage systems at Idaho Nuclear Technology & Engineering Center (INTEC) known as the “tank farm”, and periodic and emergency environmental monitoring. This progress report relates activities undertaken in this investigation, describes the preliminary areas of interest for limited scope ARG-US testing or implementation, and relays expected actions needed to complete the task scope. This report offers an opportunity to the program sponsor, technical leads at ANL, and INL site representatives to give feedback on the initial assessment and make recommendations on the forthcoming activities.

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Development of a Conditioned System-Level Groundwater Model to Evaluate Long-Term Groundwater Impacts within a Performance Assessment - 20115

A preliminary performance assessment (PA) of single-shell tank Waste Management Area (WMA) A-AX located at the U.S. Department of Energy (DOE)'s Hanford Site in southeastern Washington is being conducted to satisfy the requirements of DOE Order 435.1 [1] as it relates to closure of the single-shell radioactive waste tanks in the WMA A-AX tank farms. A PA assesses the fate, transport, and impacts of radionuclides within a low-level radioactive waste disposal facility in its assumed closure configuration and the subsequent potential doses to humans over a 1,000-year compliance period and a 10,000-year performance evaluation period. The WMA A-AX preliminary PA evaluation is structured around the complementary use of process-level and system-level models to calculate the facility performance against established DOE Order 435.1 [1] performance objectives. Process-level models are those that represent a detailed phenomenological representation of processes of concern in the PA. Process models typically only represent one or a few of the components of the PA, such as groundwater flow and transport, and must be integrated with other modeling elements to perform PA calculations. System-level models are those that are abstracted from the process models, retaining the essential features of the process model, while allowing integration of all aspects of the PA in a single modeling framework. System-level models are often characterized by coarser numerical discretization, lower dimensionality, or other similar simplifications compared to the process-level model. Traditionally, a three-dimensional (3-D) process-level model is utilized primarily to evaluate the long-term impact on groundwater and the potential doses to individuals who consume contaminated groundwater. System-level models are also utilized to evaluate the groundwater pathway in PAs. These models typically have reduced dimensionality (1-D) and are conditioned utilizing flow fields (Darcy fluxes) and moisture content distributions that are abstracted from the process level models. The abstraction approach assures that the flow field in both models is consistent for a specific set of input parameters for flow, differing only in the discretization and dimensionality of the two models. The preliminary WMA A-AX PA incorporates a detailed representation of the geological system and hydraulic properties within the 3-D model STOMP{sup C} numerical code so that the effects of relevant features and processes on water flow and radionuclide transport in the subsurface can be evaluated. The complementary system-level model is developed utilizing the GoldSim{sup C} code to implement a simplified, 1-D equivalent model to represent the groundwater pathway. Contaminant transport through the vadose zone and unconfined aquifer for Tc-99 and I-129 were evaluated in each of the models. Adjustments to the saturated portion of the GoldSim{sup C} 1-D model were required to mimic the dispersion effect captured with the 3-D STOMP{sup C} model. Once this conditioning was conducted, highly similar results for the transport of Tc-99 and I-129 were achieved at the point of calculation, located 100 m downgradient from the WMA A-AX fenceline. These radionuclides represent elements that are regarded as primary dose drivers in the PA groundwater pathway analysis. The high degree of conformance between the two models suggests that the use of the equivalent 1-D system model is suitable for evaluating the full suite of radionuclides that will be released from the tank sources within WMA A-AX over the 1,000-year compliance period and over the 10,000-year evaluation period. (authors)

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Technology Feasibility of High-Temperature Heat Pumps for Industrial Drying Process in the US

High-temperature heat pumps are a prospective technology for electrifying and decarbonizing industrial drying processes. This study investigates the technological potential of HTHPs in replacing fossil-fuel burners or steam boilers in industrial spray dryers. The performance of HTHPs with three configurations was investigated, including high high-temperature heat pump boosted with an electric air heater, a steam-generating high-temperature heat pump with multi-stage mechanical vapor compressions, and transcritical high-temperature heat pumps. R1336mzz(Z) is used as the refrigerant in both subcritical and transcritical high-temperature heat pumps, and R717 is used as the working fluid in the mechanical vapor recompression and the heat transfer fluids. Thermodynamic models are built to evaluate the energy efficiency of HTHPs. A case study was carried out on an industrial spray dryer integrated with a waste heat recuperator, where the HTHPs are used to recover precooled air with a dew point of 40℃ and supply heat for drying air at 200℃. For a high-temperature heat pump boosted with an electric air heater, a higher system-level COP is achieved with a high supply temperature from high-temperature heat pump. For a high-temperature heat pump with mechanical vapor recompressions, larger temperature drops in the flashing tank provide higher heat capacities but almost constant values of the coefficient of performance. For a transcritical high-temperature heat pump, an optimum discharge pressure exists for the temperature profiles within the gas cooler and the coefficient of performance. The transcritical high-temperature heat pump provides the best energy efficiency among the three configurations. The theoretical results prove the technical feasibility of high-temperature heat pumps in industrial air-drying applications. .

Wang, Pengtao↗

High Solids Performance Testing in a Scaled TSCR System

The Tank Side Cesium Removal (TSCR) project is a technology demonstration that will pretreat Hanford tank waste supernatant in support of the Direct Feed Low-Activity Waste (DFLAW) mission. The TSCR system employs two key separation technologies: dead-end filtration (DEF) and ion exchange (IX) using crystalline silicotitanate (CST) media. DEF will be used to remove undissolved solids from tank waste to protect the functionality of the IX columns and the IX system will remove Cs-137 from tank waste. The separation technologies (DEF and IX) used in TSCR are technically mature and have also been successfully deployed at the Savannah River site in a similar facility known as the Tank Closure Cesium Removal (TCCR) system. While testing with simulants and real waste has been successfully performed under conditions expected during the initial operation of TSCR, test data is absent for assessing off normal high solids loading that may be in the TSCR waste feed. Normal TSCR treatment operations are expected to handle wastes with solids content on the order of 200 ppm, and off normal solids loading could be much larger than the nominal level. The testing program described in this report was conducted to understand the consequence of operating the TSCR system at elevated solids loadings up to the high-solids limit of 15,000 ppm [i.e., 1.5-wt%] identified in the TSCR design basis. Although the system is not required to make throughput above the nominal solids loading, the testing was intended to provide important information related to potential off normal operations. At off normal levels near the high-solids limit, there are potential implications for TSCR performance in the areas of throughput, DEF pressure drop, filter backflush frequency, and IX column pressure drop. In addition, intrusion of solids into the IX column was postulated to impact the Cs-137 loading behavior by promoting channeling or flow maldistribution in the column; since the magnitude of the postulated effect was unknown, assessing it was also of interest. The testing was performed using representative waste simulants and a prototypic, integrated TSCR system designed and assembled specifically to conduct the high solids performance assessment. Overall, the scaled TSCR testing demonstrated that full-scale unit operations can succeed in fulfilling their processing objectives in the presence of solids up to 3,000 ppm, but there are potential performance challenges to filtration operations at solids loadings as low as ~500 ppm. The severity of the challenge is likely to be dependent on the type and size distribution of solids, of which the current testing only examined a single type and size distribution. To provide some flexibility for future full-scale operations, the results of the testing suggest two possible risk reduction strategies that can be implemented without any changes in TSCR design or configuration. One option would be to enact an administrative limit on the solids loading to protect TSCR from feeds that are likely to require a high DEF swap frequency. Another option is to permit operation of the DEFs at differential pressures greater than 2 psid before swapping filters. The selection of a higher differential pressure target is not anticipated to adversely impact DEF backflushing efficacy and would reduce both swap frequency and the amount of waste sent to AP-108.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Viscosity Measurements of the HLW APPS Glasses

The U.S. Department of Energy is responsible for building the Hanford Waste Treatment and Immobilization Plant (WTP) at the Hanford site in Washington to remediate 56 million gallons of radioactive waste historically stored in 177 underground tanks. The Office of River Protection has requested that the Savannah River National Laboratory (SRNL) contribute in areas of recognized capabilities and expertise for glass waste form development to support successful startup of the WTP. SRNL support of this work is defined in the Task Technical and Quality Assurance Plan.1 This report provides results from viscosity measurements on a series of simulated nuclear waste glasses designed and fabricated at Pacific Northwest National Laboratory (PNNL). The glasses were designated the high-level waste – Aspen Process Performance Simulation (HLW-APPS) study glasses. The data provided in this report is to be used in the development, validation, and implementation of enhanced property/composition models for nuclear waste glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗