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Enhanced HLW glass formulations for the waste treatment and immobilization plant

Current estimates and glass formulation efforts are conservative vis-a-vis achievable waste loadings. These formulations have been specified to ensure that glasses are homogenous, contain essentially no crystalline phases, are processable in joule-heated, ceramic-lined melters and meet WTP Contract terms. The WTP's overall mission will require the immobilization of tank waste compositions that are dominated by mixtures of aluminum, chromium, bismuth, iron, phosphorous, zirconium, and sulfur compounds as waste-limiting components. Glass compositions for these waste mixtures have been developed based upon previous experience and current glass property models. DOE has a testing program to develop and characterize HLW glasses with higher waste loadings. This work has demonstrated the feasibility of increases in waste loading from 25 wt% to 33-50 wt% (based on oxide loading) in the glass depending on the waste stream. It is expected these higher waste loading glasses will reduce the HLW canister production requirement by 25% or more. (authors)

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Durability testing of actual Hanford waste glasses and their non-radioactive simulant glasses

The low-activity waste (LAW) fraction of Hanford tank waste will be converted to glass at the Waste Treatment and Immobilization Plant (WTP) and disposed on the Hanford site. The chemical durability of LAW glasses has been researched for decades to satisfy contract requirements. Most LAW glass durability data has been generated on non-radioactive simulant glasses fabricated via crucible melts. These non-radioactive glasses were chosen due to safety and cost reasons with confidence that radioactive waste glasses would exhibit similar behavior. To reduce the risk of significant differences in laboratory test response data between WTP melter waste glass and simulant glass, Product Consistency Tests (PCT, i.e., ASTM C1285-21) and Environmental Protection Agency (EPA) 1313 durability tests were performed on actual and simulant LAW glasses fabricated using laboratory-scaled melters. Actual and simulant glass durability test results are presented and statistically compared. Finally, differences in test responses were found to be within experimental uncertainty.

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Fire Safety Tests for Spherical Resorcinol Formaldehyde Resin: Data Summary Report

A draft safety evaluation of the scenario for spherical resorcinol-formaldehyde (SRF) resin fire inside the ion exchange column was performed by the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Fire Safety organization. The result of this draft evaluation suggested a potential change of the fire safety classification for the Cesium Ion Exchange Process System (CXP) emergency elution vessels, equipment, and piping, which may be overly bounding based on the fire performance data from the manufacturer of the ion exchange resin selected for use at the WTP. To resolve this question, the fire properties of the SRF resin were measured by Southwest Research Institute (SwRI), following the American Society for Testing and Materials (ASTM) standard procedures, through a subcontract managed by Pacific Northwest National Laboratory (PNNL). For some tests, the ASTM standard procedures were not entirely appropriate or practical for the SRF resin material, so the procedures were modified and deviations from the ASTM standard procedures were noted. This report summarizes the results of fire safety tests performed and reported by SwRI. The efforts by PNNL were limited to summarizing the test results provided by SwRI into one consolidated data report. All as-received SwRI reports are attached to this report in the Appendix. Where applicable, the precision and bias of each test method, as given by each ASTM standard procedure, are included and compared with the SwRI test results of the SRF resin.

cesium ion exchange↗

Simulant Development for Hanford Double-Shell Tank Mixing and Waste Feed Delivery Testing

The U.S. Department of Energy Office of River Projection manages the River Protection Project, which has the mission to retrieve and treat the Hanford tank waste for disposal and close the tank farms (Certa et al. 2011). Washington River Protection Solutions, LLC (WRPS) is responsible for a primary objective of this mission which is to retrieve and transfer tank waste to the Hanford Waste Treatment and Immobilization Plant (WTP). A mixing and sampling program with four separate demonstrations is currently being conducted to support this objective and also to support activities in a plan for addressing safety concerns identified by the Defense Nuclear Facilities Safety Board related to the ability of the WTP to mix, sample, and transfer fast settling particles. Previous studies have documented the objectives, criteria, and selection of non-radioactive simulants for these four demonstrations. The identified simulants include Newtonian suspending liquids with densities and viscosities that span the range expected in waste feed tanks. The identified simulants also include non-Newtonian slurries with Bingham yield stress values that span a range that is expected to bound the Bingham yield stress in the feed delivery tanks. The previous studies identified candidate materials for the Newtonian and non-Newtonian suspending fluids, but did not provide specific recipes for obtaining the target properties and information was not available to evaluate the compatibility of the fluids and particles or the potential for salt precipitation at lower temperatures. The purpose of this study is to prepare small batches of simulants in advance of the demonstrations to determine specific simulant recipes, to evaluate the compatibility of the liquids and particles, and to determine if the simulants are stable for the potential range of test temperatures. The objective of the testing, which is focused primarily on the Newtonian and non-Newtonian fluids, is to determine the composition of simulant materials that give the desired density and viscosity or rheological parameters.

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Enhanced Sulfate Management in HLW Glass Formulations

The present report describes a series of small-scale crucible tests to determine sulfate solubility in HLW glasses, tests to assess the effect of compositional changes on sulfate solubility, and small-scale meIter tests to determine maximum acceptable sulfate loadings in HLW feeds to the meIter. The work was performed in accordance with the Test Plan for this work and the ORP contract. Glasses produced in previous melter tests using WTP and ORP waste and glass compositions were tested in the present work to determine sulfur solubility. In parallel, a glass formulation was developed for a previously untested HLW composition with one of the highest projected sulfate concentrations; that formulation was subsequently processed on the DM10 melter system at successively higher waste loadings to determine the maximum waste loading. Tests were also conducted on the DM10 on several HLW formulations which had been previously subjected to crucible-scale sulfur solubility testing; these formulations were selected based on sulfur solubility information for HLW glasses that was compiled in a previous report to WTP; similar information for LAW glasses was compiled in a report to ORP.

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Development Of High Waste-Loading HLW Glasses For High Bismuth Phosphate Wastes

This report presents results from tests with new glass formulations that have been developed for several high Bi-P HLW compositions that are expected to be processed at the WTP that have not been tested previously. WTP HLW feed compositions were reviewed to select waste batches that are high in Bi-P and that are reasonably distinct from the Bi-limited waste that has been tested previously. Three such high Bi-P HLW compositions were selected for this work. The focus of the present work was to determine whether the same type of issues as seen in previous work with high-Bi HLW will be seen in HLW with different concentrations of Bi, P and Cr and also whether similar glass formulation development approaches would be successful in mitigating these issues. New glass compositions were developed for each of the three representative Bi-P HLW wastes and characterized with respect to key processing and product quality properties and, in particular, those relating to crystallization and foaming tendency.

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Large-Scale Spray Releases: Initial Aerosol Test Results

One of the events postulated in the hazard analysis at the Waste Treatment and Immobilization Plant (WTP) and other U.S. Department of Energy (DOE) nuclear facilities is a breach in process piping that produces aerosols with droplet sizes in the respirable range. The current approach for predicting the size and concentration of aerosols produced in a spray leak involves extrapolating from correlations reported in the literature. These correlations are based on results obtained from small engineered spray nozzles using pure liquids with Newtonian fluid behavior. The narrow ranges of physical properties on which the correlations are based do not cover the wide range of slurries and viscous materials that will be processed in the WTP and across processing facilities in the DOE complex. Two key technical areas were identified where testing results were needed to improve the technical basis by reducing the uncertainty due to extrapolating existing literature results. The first technical need was to quantify the role of slurry particles in small breaches where the slurry particles may plug and result in substantially reduced, or even negligible, respirable fraction formed by high-pressure sprays. The second technical need was to determine the aerosol droplet size distribution and volume from prototypic breaches and fluids, specifically including sprays from larger breaches with slurries where data from the literature are scarce.

Schonewill, Philip P.↗

Fire Safety Tests for Cesium-Loaded Spherical Resorcinol Formaldehyde Resin: Data Summary Report

A draft safety evaluation of the scenario for spherical resorcinol formaldehyde (SRF) resin fire inside the ion exchange column was performed by the Hanford Tank Waste Treatment and Immobilization Plant (WTP) Fire Safety organization. The result of this draft evaluation suggested a potential change of the fire safety classification for the Cesium Ion Exchange Process System (CXP) emergency elution vessels, equipment, and piping. To resolve this question, the fire properties of the SRF resin were measured by Southwest Research Institute (SwRI) through a subcontract managed by Pacific Northwest National Laboratory (PNNL). The results of initial fire safety tests on the SRF resin were documented in a previous report (WTP-RPT-218). The present report summarizes the results of additional tests performed by SwRI on the cesium-loaded SRF resin. The efforts by PNNL were limited to summarizing the test results provided by SwRI into one consolidated data report. The as-received SwRI report is attached to this report in the Appendix A. Where applicable, the precision and bias of each test method, as given by each American Society for Testing and Materials (ASTM) standard procedure, are included and compared with the SwRI test results of the cesium-loaded SRF resin.

Fire Safety↗

Ion Exchange Testing with SRF Resin FY2012

Ion exchange using spherical resorcinol-formaldehyde (SRF) resin has been selected by the U.S. Department of Energy’s Office of River Protection (DOE-ORP) for use in the Pretreatment Facility (PTF) of the Hanford Tank Waste Treatment and Immobilization Plant (WTP) and for potential application in at-tank deployment. Numerous studies have shown SRF resin to be effective for removing 137Cs from a wide variety of actual and simulated tank waste supernatants (Adamson et al. 2006; Blanchard et al. 2008; Burgeson et al. 2004; Duignan and Nash 2009; Fiskum et al. 2006a; Fiskum et al. 2006b; Fiskum et al. 2006c; Fiskum et al. 2007; Hassan and Adu-Wusu 2003; King et al. 2004; Nash et al. 2006). Prior work at the Pacific Northwest National Laboratory (PNNL) has focused primarily on the loading behavior for 4 to 6 M Na solutions at 25 to 45°C. Recent proposed changes to the WTP ion exchange process baseline indicate that loading may include a broader range of sodium molarities (0.1 to 8 M) and higher temperatures (50°C) to alleviate post-filtration precipitation issues. This report discusses ion exchange loading kinetics testing activities performed in accordance with Test Plan TP-WTPSP-002, Rev. 3.0, which was prepared and approved in response to the Test Specification 24590 PTF-TSP-RT-09-002, Rev. 0 (Lehrman 2010) and Test Exception 24590 PTF TEF RT-11-00003, Rev. 0 (Meehan 2011). This testing focused on column tests evaluating the impact of elevated temperature on resin degradation over an extended period of time and batch contacts evaluating the impact on Cs loading over a broad range of sodium concentrations (0.1 to 5 M). These changes may be required to alleviate post-filtration precipitation issues and broaden the data range of SRF resin loading under the conditions expected with the new equipment and process changes.

Hanford Tank Waste Treatment and Immobilization Pl↗

Potential Application Of Radionuclide Scaling Factors To High Level Waste Characterization

Production sources, radiological properties, relative solubilities in waste, and laboratory analysis techniques for the forty-five radionuclides identified in Hanford's Waste Treatment and Immobilization Plant (WTP) Feed Acceptance Data Quality Objectives (DQO) document are addressed in this report. Based on Savannah River Site (SRS) experience and waste characteristics, thirteen of the radionuclides are judged to be candidates for potential scaling in High Level Waste (HLW) based on the concentrations of other radionuclides as determined through laboratory measurements. The thirteen radionuclides conducive to potential scaling are: Ni-59, Zr-93, Nb-93m, Cd-113m, Sn-121m, Sn-126, Cs-135, Sm-151, Ra-226, Ra-228, Ac-227, Pa-231, and Th-229. The ability to scale radionuclides is useful from two primary perspectives: 1) it provides a means of checking the radionuclide concentrations that have been determined by laboratory analysis; and 2) it provides a means of estimating radionuclide concentrations in the absence of a laboratory analysis technique or when a complex laboratory analysis technique fails. Along with the rationale for identifying and applying the potential scaling factors, this report also provides examples of using the scaling factors to estimate concentrations of radionuclides in current SRS waste and into the future. Also included in the report are examples of independent laboratory analysis techniques that can be used to check results of key radionuclide analyses. Effective utilization of radionuclide scaling factors requires understanding of the applicable production sources and the chemistry of the waste. As such, the potential scaling approaches identified in this report should be assessed from the perspective of the Hanford waste before reaching a decision regarding WTP applicability.

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Letter Report: LAW Simulant Development for Cast Stone Screening Test

More than 56 million gallons of radioactive and hazardous waste are stored in 177 underground storage tanks at the U.S. Department of Energy’s (DOE’s) Hanford Site in southeastern Washington State. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is being constructed to treat the wastes and immobilize them in a glass waste form. 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 nonradioactive chemicals. The HLW will be converted to glass in the HLW vitrification facility for ultimate disposal at an offsite federal repository. At least a portion (~35%) of the LAW will be converted to glass in the LAW vitrification facility and will be disposed of onsite at the Integrated Disposal Facility (IDF). The pretreatment and HLW vitrification facilities will have the capacity to treat and immobilize the wastes destined for each facility. However, a second facility will be needed for the expected volume of additional LAW requiring immobilization. A cementitious waste form known as Cast Stone is being considered to provide the required additional LAW immobilization capacity. The Cast Stone waste form must be acceptable for disposal in the IDF. The Cast Stone waste form and immobilization process must be tested to demonstrate that the final Cast Stone waste form can comply with waste acceptance criteria for the IDF disposal facility and that the immobilization processes can be controlled to consistently provide an acceptable waste form product. Further, the waste form must be tested to provide the technical basis for understanding the long term performance of the waste form in the IDF disposal environment. These waste form performance data are needed to support risk assessment and performance assessment (PA) analyses of the long-term environmental impact of the waste disposal in the IDF. A testing program was developed in fiscal year (FY) 2012 describing in some detail the work needed to develop and qualify Cast Stone as a waste form for the solidification of Hanford LAW (Westsik et al. 2012). Included within Westsik et al. (2012) is a section on the near-term needs to address Tri-Party Agreement Milestone M-062-40ZZ. The objectives of the testing program to be conducted in FY 2013 and FY 2014 are to: • Determine an acceptable formulation for the LAW Cast Stone waste form. • Evaluate sources of dry materials for preparing the LAW Cast Stone. • Demonstrate the robustness of the Cast Stone waste form for a range of LAW compositions. • Demonstrate the robustness of the formulation for variability in the Cast Stone process. • Provide Cast Stone contaminant release data for PA and risk assessment evaluations. The first step in determining an acceptable formulation for the LAW Cast Stone waste form is to conduct screening tests to examine expected ranges in pretreated LAW composition, waste stream concentrations, dry-materials sources, and mix ratios of waste feed to dry blend. A statistically designed test matrix will be used to evaluate the effects of these key parameters on the properties of the Cast Stone as it is initially prepared and after curing. The second phase of testing will focus on selection of a baseline Cast Stone formulation for LAW and demonstrating that Cast Stone can meet expected waste form requirements for disposal in the IDF. It is expected that this testing will use the results of the screening tests to define a smaller suite of tests to refine the composition of the baseline Cast Stone formulation (e.g. waste concentration, water to dry mix ratio, waste loading).

Russell, Renee L.↗

Preliminary ILAW Formulation Algorithm Description (Rev. 1)

The U.S. Department of Energy (DOE), Office of River Protection (ORP), has contracted with Bechtel National, Inc. (BNI) to design, construct, and commission the Hanford Tank Waste Treatment and Immobilization Plant (WTP) at the Hanford Site (DOE 2000). This plant is designed to operate for 40 years and treat roughly 50 million gallons of mixed hazardous high-level waste (HLW) stored in 177 underground tanks at the Hanford Site. The process involves separating the high-level and low-activity waste (LAW) fractions through filtration, leaching, Cs ion exchange, and precipitation. Each fraction will be separately vitrified into borosilicate waste glass. This report documents the initial algorithm for use by Hanford WTP in batching LAW and glass-forming chemicals (GFCs) in the LAW melter feed preparation vessel (MFPV). Algorithm inputs include the chemical analyses of the pretreated LAW in the concentrate receipt vessel (CRV), the volume of the MFPV heel, and the compositions of individual GFCs. In addition to these inputs, uncertainties in the LAW composition and processing parameters are included in the algorithm.

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Supplemental Immobilization Cast Stone Technology Development and Waste Form Qualification Testing Plan

The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is being constructed to treat the 56 million gallons of radioactive waste stored in 177 underground tanks at the Hanford Site. The WTP includes a pretreatment facility to separate the wastes into high-level waste (HLW) and low-activity waste (LAW) fractions for vitrification and disposal. The LAW will be converted to glass for final disposal at the Integrated Disposal Facility (IDF). The pretreatment facility will have the capacity to separate all of the tank wastes into the HLW and LAW fractions, and the HLW Vitrification Facility will have the capacity to vitrify all of the HLW. However, a second immobilization facility will be needed for the expected volume of LAW requiring immobilization. A number of alternatives, including Cast Stone—a cementitious waste form—are being considered to provide the additional LAW immobilization capacity.

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Ion Exchange Distribution Coefficient Tests and Computer Modeling at High Ionic Strength Supporting Technetium Removal Resin Maturation

The primary treatment of the tank waste at the DOE Hanford site will be done in the Waste Treatment and Immobilization Plant (WTP) that is currently under construction. The baseline plan for this facility is to treat the waste, splitting it into High Level Waste (HLW) and Low Activity Waste (LAW). Both waste streams are then separately vitrified as glass and poured into canisters for disposition. The LAW glass will be disposed onsite in the Integrated Disposal Facility (IDF). There are currently no plans to treat the waste to remove technetium, so its disposition path is the LAW glass. Due to the water solubility properties of pertechnetate and long half-life of 99 Tc, effective management of 99 Tc is important to the overall success of the Hanford River Protection Project mission. To achieve the full target WTP throughput, additional LAW immobilization capacity is needed, and options are being explored to immobilize the supplemental LAW portion of the tank waste. Removal of 99 Tc, followed by off-site disposal, would eliminate a key risk contributor for the IDF Performance Assessment (PA) for supplemental waste forms, and has potential to reduce treatment and disposal costs. Washington River Protection Solutions (WRPS) is developing some conceptual flow sheets for supplemental LAW treatment and disposal that could benefit from technetium removal. One of these flowsheets will specifically examine removing 99 Tc from the LAW feed stream to supplemental immobilization. To enable an informed decision regarding the viability of technetium removal, further maturation of available technologies is being performed. This report contains results of experimental ion exchange distribution coefficient testing and computer modeling using the resin SuperLig ® 639 a to selectively remove perrhenate from high ionic strength simulated LAW. It is advantageous to operate at higher concentration in order to treat the waste stream without dilution and to minimize the volume of the final wasteform. This work examined the impact of high ionic strength, high density, and high viscosity if higher concentration LAW feed solution is used. Perrhenate (ReO 4 - ) has been shown to be a good nonradioactive surrogate for pertechnetate in laboratory testing for this ion exchange resin, and the performance bias is well established. Equilibrium contact testing with 7.8 M [Na + ] average simulant concentrations indicated that the SuperLig ® 639 resin average perrhenate distribution coefficient was 368 mL/g at a 100:1 phase ratio. Although this indicates good performance at high ionic strength, an equilibrium test cannot examine the impact of liquid viscosity, which impacts the diffusivity of ions and therefore the loading kinetics. To get an understanding of the effect of diffusivity, modeling was performed, which will be followed up with column tests in the future.

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Literature Review: Assessment of DWPF Melter and Melter Off-gas System Lifetime

Testing to date for the MOC for the Hanford Waste Treatment and Immobilization Plant (WTP) melters is being reviewed with the lessons learned from DWPF in mind and with consideration to the changes in the flowsheet/feed compositions that have occurred since the original testing was performed. This information will be presented in a separate technical report that identifies any potential gaps for WTP processing.

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Evaluation of Technetium Getters to Improve the Performance of Cast Stone

Cast Stone has been selected as the preferred waste form for solidification of aqueous secondary liquid effluents from the Hanford Tank Waste Treatment and Immobilization Plant (WTP) process condensates and low-activity waste (LAW) melter off-gas caustic scrubber effluents. Cast Stone is also being evaluated as a supplemental immobilization technology to provide the necessary LAW treatment capacity to complete the Hanford tank waste cleanup mission in a timely and cost effective manner. One of the major radionuclides that Cast Stone has the potential to immobilize is technetium (Tc). The mechanism for immobilization is through the reduction of the highly mobile Tc(VII) species to the less mobile Tc(IV) species by the blast furnace slag (BFS) used in the Cast Stone formulation. Technetium immobilization through this method would be beneficial because Tc is one of the most difficult contaminants to address at the U.S. Department of Energy (DOE) Hanford Site due to its complex chemical behavior in tank waste, limited incorporation in mid- to high-temperature immobilization processes (vitrification, steam reformation, etc.), and high mobility in subsurface environments. In fact, the Tank Closure and Waste Management Environmental Impact Statement for the Hanford Site, Richland, Washington (TC&WM EIS) identifies technetium-99 ( 99 Tc) as one of the radioactive tank waste components contributing the most to the environmental impact associated with the cleanup of the Hanford Site. The TC&WM EIS, along with an earlier supplemental waste-form risk assessment, used a diffusion-limited release model to estimate the release of different contaminants from the WTP process waste forms. In both of these predictive modeling exercises, where effective diffusivities based on grout performance data available at the time, groundwater at the 100-m down-gradient well exceeded the allowable maximum permissible concentrations for 99 Tc. (900 pCi/L). Recent relatively short-term (63 day) leach tests conducted on both LAW and secondary waste Cast Stone monoliths indicated that 99 Tc diffusivities were at or near diffusivities where the groundwater at the 100-m down-gradient well would exceed the allowable maximum permissible 99 Tc concentrations. There is, therefore, a need and an opportunity to improve the retention of Tc in the Cast Stone waste form. One method to improve the performance of the Cast Stone waste form is through the addition of “getters” that selectively sequester Tc inside Cast Stone.

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Chemical analysis of simulated high level waste glasses to support stage III sulfate solubility modeling

The U.S. Department of Energy (DOE), Office of Environmental Management (EM) is sponsoring an international, collaborative project to develop a fundamental model for sulfate solubility in nuclear waste glass. The solubility of sulfate has a significant impact on the achievable waste loading for nuclear waste forms within the DOE complex. These wastes can contain relatively high concentrations of sulfate, which has low solubility in borosilicate glass. This is a significant issue for low-activity waste (LAW) glass and is projected to have a major impact on the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Sulfate solubility has also been a limiting factor for recent high level waste (HLW) sludge processed at the Savannah River Site (SRS) Defense Waste Processing Facility (DWPF). The low solubility of sulfate in glass, along with melter and off-gas corrosion constraints, dictate that the waste be blended with lower sulfate concentration waste sources or washed to remove sulfate prior to vitrification. The development of enhanced borosilicate glass compositions with improved sulfate solubility will allow for higher waste loadings and accelerate mission completion.The objective of the current scope being pursued by SHU is to mature the sulfate solubility model to the point where it can be used to guide glass composition development for DWPF and WTP, allowing for enhanced waste loadings and waste throughput at these facilities. A series of targeted glass compositions was selected to resolve data gaps in the model and is identified as Stage III. SHU fabricated these glasses and sent samples to SRNL for chemical composition analysis. SHU will use the resulting data to enhance the sulfate solubility model and resolve any deficiencies. In this report, SRNL provides chemical analyses for the Stage III, simulated HLW glasses fabricated by SHU in support of the sulfate solubility model development.

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Liquid secondary waste. Waste form formulation and qualification

The Hanford Site Effluent Treatment Facility (ETF) currently treats aqueous waste streams generated during Site cleanup activities. When the Hanford Tank Waste Treatment and Immobilization Plant (WTP) begins operations, a liquid secondary waste (LSW) stream from the WTP will need to be treated. The volume of effluent for treatment at the ETF will increase significantly. Washington River Protection Solutions is implementing a Secondary Liquid Waste Immobilization Technology Development Plan to address the technology needs for a waste form and solidification process to treat the increased volume of waste planned for disposal at the Integrated Disposal Facility IDF). Waste form testing to support this plan is composed of work in the near term to demonstrate the waste form will provide data as input to a performance assessment (PA) for Hanford’s IDF.

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