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Corrosion Testing of Refractory inContact with Molten Glasses Designed for Waste Vitrification - VSL Touchpoint Matrix Glasses

It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests. Refractory corrosion is generally reported as physical material loss, measured in units of distance (e.g., inch) or as physical material loss rate, measured in units of distance per time (e.g., inch/day). In post-operational melters, the refractory corrosion is measured directly, sometimes reported as corrosion depth. Crucible tests are used in the laboratory to accelerate the refractory corrosion to facilitate a meaningful measurement in a commensurate amount of time. Crucible tests are particularly useful in understanding refractory corrosion across a large glass composition space, where operational testing would be prohibitive. Some of the critical parameters that are known to influence refractory corrosion by molten glass in a crucible test are temperature, system redox, molten salt phases, glass chemistry, and test duration. The majority of data collected for Monofrax® K-3 (hereafter referred to as K-3) corrosion is from crucible tests, but a small amount comes directly from scaled and production melters. Crucible test data has been collected under varying conditions, whereas data collected from operational melters is relatively fewer and represents conditions specific to the melter campaign. The result is that the published data can be grouped and analyzed in multiple ways, not all of which are readily comparable. The Standard Test Method for Isothermal Corrosion Resistance of Refractories to Molten Glass (ASTM C621) outlines the general guidelines used across industry. That method describes a sealed, static test in which the surface area of the refractory coupon and the volume of glass are fixed. A significant portion of the crucible data pertaining to nuclear waste glasses has been collected in a modified configuration; the most notable differences being the surface area of the refractory coupon to volume of the glass and use of a method for bubbling the melt. To our knowledge, the influence of those parameters on the refractory corrosion has not been quantified. In this work, it was determined that static tests and bubbled tests would be performed. Savannah River National Laboratory (SRNL) was tasked with setting up and performing static testing while PNNL was tasked with setting up and performing bubbled testing. Initial activities were performed to establish laboratory methods that reproduce data comparable to existing data sets of K-3 refractory corrosion by low activity waste (LAW) and high-level waste (HLW) glass compositions. Later activities were focused on refining the test parameters to establish a standard test practice to be used between Laboratories and collecting additional data to be used in the enhanced waste glass model development. This document serves primarily to convey the refractory loss measurement results from corrosion testing of K-3 refractory with waste glass compositions developed for use in the WTP melters. The data will be used in the enhanced property/composition models being developed for waste glass vitrification and melter operations.

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Corrosion Testing of Refractory in Contact with Molten Glasses Designed for Waste Vitrification - HAL24 M1 Matrix Glasses

It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests.

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Reassessment of Dose Contributions from the M-Area Glass Special Waste Form Buried in the E-Area Low-Level Waste Facility

During a recent revision to the groundwater (GW) and inadvertent human intruder (IHI) screening analysis report (Aleman and Hamm, 2023), weaknesses within the screening logic were observed resulting in U-235 being brought back into the list of radionuclides requiring inventory limits within the M-Area Glass SWF. In addition, while reviewing the earlier vadose zone (VZ) transport analysis efforts, an input deck error was observed in the U-234G VZ transport simulation.

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Electrochemical Denitration and Caustic Generation (EDCGe) System: Year One Project Report

An advanced electrochemical denitration and caustic generation (EDCGe) system is being developed to process legacy waste through the direct feed high-level waste (DFHLW) flowsheet at Hanford. This system aims to destroy nitrates and organics in DFHLW and potentially DFHLAW feeds, significantly reducing off-gas concerns from both process safety and process flowsheet perspectives. Supported by a multidisciplinary team, this effort includes creating a tandem denitration electrolyzer/off-gas system as part of a broader mission to accelerate waste treatment through fundamental and applied research and development initiatives. The progress for the first year of the three-year program to develop technology for the EDCGe system is described within this document.

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FY25 Progress Report: SRNL Analysis of ICCWR LCM and WAMS data for Corrosion and Cracking

Algorithms for Machine Learning (ML) and image analysis for the 3013 Surveillance Program have been developed in an ongoing collaborative effort by the Savannah River National Laboratory (SRNL) and the University of South Carolina (USC). The objective of the algorithms is to automate the identification of corrosion and cracks in the Inner Container Closure Weld Region (ICCWR) of the canister system used to store Pu-bearing material. Data for corrosion and cracking is collected from large binary files generated by a Laser Confocal Microscope (LCM), the Wide Area 3D Measurement System (WAMS), or, in a recent proposal, by a Scanning Electron Microscope (SEM). The ML software uses the physical attributes in the data files (e.g., one or more of: height, color, and 16-bit grayscale values as functions of position in a plane projection) to detect signs of surface corrosion and cracking after being trained on similar data with the features to be detected. Although the initial scope included screening for broader indicators of corrosion, e.g., pitting, the identification of potential cracks was prioritized for the past several years at the request of program leadership.

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Vitrification of Hanford Tank 241-AW-105 Waste and Equivalent Simulant

Hanford Site nuclear waste is to be vitrified at the Waste Treatment and Immobilization Plant (WTP), which is a part of the safe and efficient retrieval, treatment, and disposal mission of the U.S. Department of Energy - Hanford Field Office. A portion of Hanford tank 241-AW-105 (referred to herein as AW-105) waste was retrieved by Hanford Tank Waste Operations and Closure (H2C) and transferred to Pacific Northwest National Laboratory (PNNL). Compared to previously received and vitrified wastes (AP-107, AP-101, AN-107 and AP-105), the concentration of potassium in AW-105 was greater by an order of magnitude.

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Enhanced Hanford High-Aluminum Waste Glass Property Data Development

This study investigated the effects of aluminum concentration on simulated high level waste glass properties to eventually establish an aluminum limit (as single-component or multiple-component constraints) for glass formulations for high-aluminum Hanford wastes. A test matrix of 25 high-aluminum glasses (20 = Al 2 O 3 = 28.57 wt%) was generated, and the chemical compositions were measured. The following properties were measured: crystal formation after centerline canister cooling, crystallinity as a function of temperature, density, viscosity, electrical conductivity, toxic leaching characteristics using the Toxicity Characteristic Leaching Procedure, product consistency using the Product Consistency Test, and SO 3 solubility. These results are reported here.

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Ion Exchange Processing of AW-105 Hanford Tank Waste through Crystalline Silicotitanate in a Staged 2- then 3-Column System

The Hanford Site stores an estimated 56 million gallons of mixed radioactive and chemically hazardous waste in large underground tanks. In support of the Direct Feed Low-Activity Waste (DFLAW) Program for expediting Hanford tank waste supernate treatment, laboratory-scale ion exchange processing using prototypic unit operations was conducted on AW-105 tank waste at the Pacific Northwest National Laboratory Radiochemical Processing Laboratory. This report describes the small-scale ion exchange testing with 9.2 L of diluted and filtered supernate from Tank 241-AW-105 (hereafter referred to as AW-105) at 16 °C (62 °F). One of the waste acceptance criteria (WAC) for the Waste Treatment Plant (WTP) Low-Activity Waste Facility is that the waste must contain less than 3.18×10 -5 Ci 137 Cs per mole of Na. For the AW-105 tank waste to meet this criterion, only 0.225% of the influent 137 Cs concentration may be delivered to the WTP; this requires a Cs decontamination factor of 445. Testing with AW-105 matched current Tank Side Cesium Removal (TSCR) facility prototypic operations where a lead-lag configuration was used until the lag column reached the WAC limit, then a polish column was brought online for continued processing in a lead-lag-polish column configuration. Feed was processed at 1.9 bed volumes (BVs) per hour; the flowrate, in terms of contact time with the crystalline silicotitanate (CST) bed, matched the expected flowrate at TSCR. The Cs-decontaminated product was retained for vitrification testing (to be reported separately). The lead column reached 83% Cs breakthrough after processing ~1500 BVs of feed; the 50% Cs breakthrough was interpolated from the breakthrough data and occurred at 1041 BVs. Despite the AW-105 having a significantly higher K concentration (0.55 M compared to 0.10 M), testing compared to previous AP-107 ion exchange column testing at 16 °C showed no difference in BVs processed to reach the WAC on the lead column and only an approximate ~20 BV decrease in volume processed to reach the WAC limit on the lag column. The negligible differences in capacity despite the 5x concentration differences in K was determined to be due to the significantly lower NO3 concentration in the AW-105 supernate compared to the AP-107 tank waste matrix. A comparison in breakthrough curves for the two tests also indicated slightly faster kinetic behavior in the AW-105, with the variations in feed matrices (lower NO3 concentration) likely responsible for the deviation. The Cs effluent from the lag column reached the WAC limit after processing 772 BVs. Anticipating this breakthrough point, the polish column was preemptively installed around 675 BVs. Cs breakthrough from the lag column began at 300 BVs, reaching 1.10×10 1 µCi/mL, or 14.13 % Cs breakthrough, after processing all 1500 BVs of feed. The polish column processed nominally 830 BVs and reached 2.10×10 -1 µCi/mL, or 0.27 % Cs breakthrough at the conclusion of the test. Table S.1 and Figure S.1 summarize the observed column performance and relevant Cs loading characteristics.

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Assessment and Simulation of Particulate Transport for Delivery of Solid Amendments into the Subsurface: FY25 Status Report

For particulate-based amendments to be viable for field-scale remediation at the Hanford Site (e.g., the 200 DV-1 Operable Unit), amendment particles need to be delivered a reasonable distance away from an injection well to provide cost effective in situ treatment. Field-scale particle transport models can estimate spatial deposition of amendment particles in the subsurface, which is critical for developing an overall remediation strategy. However, field-scale particle simulations are currently limited due to insufficient simulation capability and a lack of experimental data to validate and parameterize particle transport models. During this fiscal year, the following progress has been made toward a field-scale particle transport modeling evaluation: (1) in addition to the two particle transport models implemented last FY, four additional particle transport models have been implemented within PFLOTRAN; (2) a Python-based pre-screening tool was finalized, enabling users to quickly estimate the particle radius of influence (ROI) for any given particle-amendment system; and (3) an initial compatibility assessment was completed using both particle transport simulations deployed through the pre-screening tool, in conjunction with general guidelines to (a) identify the most suitable amendment particle sizes for various Hanford sediments and (b) evaluate amendment-delivery fluid compatibility. The preliminary compatibility assessment revealed that for amendment delivery success to the various Hanford target formations, amendment particle sizes will likely need to be smaller than the amendment sizes tested in the DV-1 treatability study. It is recommended that amendment particles be decreased in size, or alternative smaller size amendments be obtained from the manufacture, prior to any further experimental testing. Also, preliminary testing suggests that xanthan gum may be the most broadly compatible delivery fluid. Planned laboratory experiments will be instrumental in validating and refining the PFLOTRAN particulate transport model formulations, ultimately enabling predictive capabilities to facilitate the design of field-scale amendment delivery systems. This work consists of acquiring new theoretical or experimental knowledge. The information associated with this report should not be used as design input or operating parameters without additional qualification.

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Effects of Borate and Organics on U(VI) Solubility in WIPP Brine

This report provides an update to a previously issued report on the solubility of uranium (VI) at different borate concentrations and in the presence of organics. The solubility of uranium (VI) in the Waste Isolation Pilot Plant (WIPP)-relevant brine was determined to support ongoing WIPP recertification activities (CRA-2026). This research was performed by the Los Alamos National Laboratory-Carlsbad Operations (LANL-CO) Actinide Chemistry and Repository Science Program (ACRSP).

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Microbial Influence on Radionuclide Transport through the Culebra

The potential release of radionuclides into the Culebra dolomite formation is modeled extensively in the Waste Isolation Pilot Plant’s Performance Assessment (WIPP PA) calculations. Uranium is of chief concern in these modeled scenarios, as it shows the greatest release. Because of this, a series of experiments was undertaken to determine if microbial activity in the Culebra formation could transform uranium, either directly or indirectly, to a state that could be immobilized.

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Tank 48H Phase 1 Initial Testing Using Sodium Permanganate to Decompose Tetraphenylborate: Simulant Studies with Shaker Oven and 2-L Vessel

Tank 48H currently holds legacy material including organic tetraphenylborate (TPB) compounds from the operation of the In-Tank Precipitation process. The large quantity of TPB is not compatible with the waste treatment facilities at SRS and must be removed or undergo treatment to oxidize the organic compounds before the tank can be returned to routine Tank Farm service. Tank 48H currently holds approximately 270,000 gallons of legacy material comprised of decontaminated salt solution, approximately 20,000 kilograms of TPB solids, 3,400 kilograms of sludge solids, and 1,800 kilograms of monosodium titanate (MST).

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Neptunium (V) Solubility in WIPP Brine: Presence and Absence of WIPP-Relevant Organic and Inorganic Ligands

The oxidation state and solubility of neptunium (Np) in 5 M NaCl and high ionic strength synthetic WIPP (Waste Isolation Pilot Plant) brines were systematically investigated as a function of pCH+ (7-11) in the presence and absence of WIPP-relevant organic ligands, including EDTA (Ethylenediaminetetraacetic acid), oxalate, citrate, and acetate, as well as inorganic ligands such as borate and carbonate at a temperature of 23 ± 2°C. This study was conducted through long-term batch solubility experiments spanning approximately 950 days, using an undersaturation approach. A comprehensive set of experimental and spectroscopic techniques, including UV-VIS-NIR spectroscopy and Np L III -edge X-ray Absorption Spectroscopy (XAS), was employed to identify the solubility-controlling Np solid phases and the predominant aqueous Np species present in the samples.

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Effects of Salt Concentration, Ionic Strength, and Water Activity on the Growth of a WIPP Archaeal Isolate, Halobacterium sp.

An extremely halophilic archaeon ( Halobacterium sp., WIPP strain), isolated from WIPP halite, was tested for its ability to grow in media containing various combinations of sodium and magnesium chloride that influenced overall ionic strength and water activity. Halobacterium sp. grew well in most tested salt combinations, and its growth appeared to depend more upon the relative contribution of sodium to overall ionic strength than on other parameters. Growth rates were highest when media consisted of at least 2 M NaCl and lowest when NaCl dropped below 20% of the ionic strength (usually less than 0.5 M). High magnesium concentrations ( 1 and 1.5 M MgCh 2 ) did not prevent Halobacterium sp. growth, as long as the sodium contribution was sufficient. Water activity was not a definitive factor in determining growth, because this value did not reach an extreme lower limit in the experimental media.

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Effect of Citrate on the Solubility of Uranium (VI) in WIPP Brine

The Waste Isolation Pilot Plant (WIPP) is the only active deep geological repository in the United States for the disposal of defense-related transuranic (TRU) waste, located in the northern part of the Delaware Basin in southeastern New Mexico, approximately 26 miles east of Carlsbad. The repository is situated 2,150 feet (about 610 meters) underground within the Salado Formation, a thick layer of stable salt deposits. This unique geological formation provides a secure and long-term environment for isolating TRU waste, ensuring its safe containment for thousands of years.

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Biologically Influenced Transport of the +3 Actinide Oxidation State from the WIPP Environment, Using Neodymium as an Analog

This report provides an update to a previously issued report on the bioassociation of the +3 actinide analog, neodymium, with Waste Isolation Pilot Plant (WIPP) microbial isolates (LCO ACP-32, Biologically Influenced Transport of the +3 Actinide Oxidation State from the WIPP Environment, Using Neodymium as an Analog ). Results contribute to updates for the biocolloid parameters for the 2026 Compliance Recertification Application (CRA-2026).

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Real Time, In-line Monitoring of Hanford Tank Wastes - Year 1 Report

The team comprised of students, postdocs, early, mid and senior career scientists from Los Alamos National Laboratory, Savanah River National Laboratory, Georgia Tech and Florida International University, with the guidance of H2C, is developing a suite of in-line instruments for the Hanford high level waste (HLW) and low active waste (LAW) processes to provide near-real-time analysis of waste form physical properties and composition. The work builds on results from the recent DOE-ORP, EM Technology Development and other projects that demonstrated promise for the use of real-time in-line monitoring (RTIM) to measure chemical compositions of slurries of up to 20 weight % solids. The goal is for this instrument suite is to substantially reduce the need for sampling for process control. Sample waste, exposure associated with sample analysis, and the demand for an external laboratory facility would be greatly reduced. The throughput of waste treatment systems would be improved by elimination of the downtime caused by waiting for sample results. This translates into reduced process storage as process knowledge will be continuously updated in near-real-time. These breakthrough technologies would significantly reduce the life cycle cost and accelerate the schedule for the Hanford tank waste mission.

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Updates to the Hanford Soil Inventory Model (SIM Version 2) for FY 2025

Update SIM to newest version (SIMv2.3). SIM is being updated to reflect the updates to the tank leak inventories performed in ECF-HANFORD-24-0061. This update is also being done to publish the site inventories in both 2001 decayed and back-decayed formats. This is particularly needed for modeling that requires inventory data from before 2001 that includes decay information for radionuclides.

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