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Updated Liquid Secondary Waste Grout Formulation and Preliminary Waste Form Qualification

This report describes the results from liquid secondary waste grout (LSWG) formulation and cementitious waste form qualification tests performed by Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions, LLC (WRPS). New formulations for preparing a cementitious waste form from a high-sulfate liquid secondary waste stream simulant, developed for Effluent Management Facility (EMF) process condensates merged with low activity waste (LAW) caustic scrubber, and the release of key constituents (e.g. 99 Tc and 129 I) from these monoliths were evaluated. This work supports a technology development program to address the technology needs for Hanford Site Effluent Treatment Facility (ETF) liquid secondary waste (LSW) solidification and supports future Direct Feed Low-Activity Waste (DFLAW) operations. High-priority activities included simulant development, LSWG formulation, and waste form qualification. The work contained within this report relates to waste form development and testing and does not directly support the 2017 integrated disposal facility (IDF) performance assessment (PA). However, this work contains valuable information for use in PA maintenance past FY17, and for future waste form development efforts. The provided data should be used by (i) cementitious waste form scientists to further understanding of cementitious dissolution behavior, (ii) IDF PA modelers who use quantified constituent leachability, effective diffusivity, and partitioning coefficients to advance PA modeling efforts, and (iii) the U.S. Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program. The results obtained help fill existing data gaps, support final selection of a LSWG waste form, and improve the technical defensibility of long-term waste form performance estimates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Updated Liquid Secondary Waste Grout Formulation and Preliminary Waste Form Qualification

This report describes the results from liquid secondary waste grout (LSWG) formulation and cementitious waste form qualification tests performed by Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions, LLC (WRPS). New formulations for preparing a cementitious waste form from a high-sulfate liquid secondary waste stream simulant, developed for Effluent Management Facility (EMF) process condensates merged with low activity waste (LAW) caustic scrubber, and the release of key constituents (e.g. 99Tc and 129I) from these monoliths were evaluated. This work supports a technology development program to address the technology needs for Hanford Site Effluent Treatment Facility (ETF) liquid secondary waste (LSW) solidification and supports future Direct Feed Low-Activity Waste (DFLAW) operations. High-priority activities included simulant development, LSWG formulation, and waste form qualification. The work contained within this report relates to waste form development and testing and does not directly support the 2017 integrated disposal facility (IDF) performance assessment (PA). However, this work contains valuable information for use in PA maintenance past FY17, and for future waste form development efforts. The provided data should be used by (i) cementitious waste form scientists to further understanding of cementitious dissolution behavior, (ii) IDF PA modelers who use quantified constituent leachability, effective diffusivity, and partitioning coefficients to advance PA modeling efforts, and (iii) the U.S. Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program. The results obtained help fill existing data gaps, support final selection of a LSWG waste form, and improve the technical defensibility of long-term waste form performance estimates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Liquid Secondary Waste Grout Formulation and Waste Form Qualification

This report describes the results from liquid secondary waste (LSW) grout formulation and waste form qualification tests performed at Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions (WRPS) to evaluate new formulations for preparing a grout waste form with high-sulfate secondary waste simulants and the release of key constituents from these grout monoliths. Specific objectives of the LSW grout formulation and waste form qualification tests described in this report focused on five activities: 1.preparing new formulations for the LSW grout waste form with high-sulfate LSW simulants and solid characterization of the cured LSW grout waste form; 2.conducting the U.S. Environmental Protection Agency (EPA) Method 1313 leach test (EPA 2012) on the grout prepared with the new formulations, which solidify sulfate-rich Hanford Tank Waste Treatment and Immobilization Plant (WTP) off-gas condensate secondary waste simulant, using deionized water (DIW); 3.conducting the EPA Method 1315 leach tests (EPA 2013) on the grout monoliths made with the new dry blend formulations and three LSW simulants (242-A evaporator condensate, Environmental Restoration Disposal Facility (ERDF) leachate, and WTP off-gas condensate) using two leachants, DIW and simulated Hanford Integrated Disposal Facility (IDF) Site vadose zone pore water (VZPW); 4.estimating the 99 Tc desorption K d (distribution coefficient) values for 99 Tc transport in oxidizing conditions to support the IDF performance assessment (PA); 5.estimating the solubility of 99 Tc(IV)-bearing solid phases for 99 Tc transport in reducing conditions to support the IDF PA.

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Secondary Waste Cast Stone Waste Form Qualification Testing Plan (Rev.1)

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). Cast Stone – a cementitious waste form, has been selected for solidification of this secondary waste stream after treatment in the ETF. The secondary-waste Cast Stone waste form must be acceptable for disposal in the IDF. This secondary waste Cast Stone waste form qualification testing plan outlines the testing of the waste form and immobilization process to demonstrate that the Cast Stone waste form can comply with the disposal requirements. Specifications for the secondary-waste Cast Stone waste form have not been established. For this testing plan, Cast Stone specifications are derived from specifications for the immobilized LAW glass in the WTP contract, the waste acceptance criteria for the IDF, and the waste acceptance criteria in the IDF Permit issued by the State of Washington. This testing plan outlines the testing needed to demonstrate that the waste form can comply with these waste form specifications and acceptance criteria. The testing program must also demonstrate that the immobilization process can be controlled to consistently provide an acceptable waste form product. This testing plan also outlines the testing needed to provide the technical basis for understanding the long-term performance of the waste form in the disposal environment. These waste form performance data are needed to support performance assessment analyses of the long-term environmental impact of the secondary-waste Cast Stone waste form in the IDF

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Effluent Management Facility Evaporator Bottom-Waste Streams Formulation and Waste Form Qualification Testing

This report describes the results from grout formulation and cementitious waste form qualification testing performed by Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions, LLC (WRPS). These results are part of a screening test that investigates three grout formulations proposed for wide-range treatment of different waste stream compositions expected for the Hanford Effluent Management Facility (EMF) evaporator bottom waste. This work supports the technical development need for alternative disposition paths for the EMF evaporator bottom wastes and future direct feed low-activity waste (DFLAW) operations at the Hanford Site. High-priority activities included simulant production, grout formulation, and cementitious waste form qualification testing. The work contained within this report relates to waste form development and testing, and does not directly support the 2017 Integrated Disposal Facility (IDF) performance assessment (PA). However, this work contains valuable information for use in PA maintenance past FY 2017 and future waste form development efforts. The provided results and data should be used by (1) cementitious waste form scientists to further the understanding of cementitious leach behavior of contaminants of concern (COCs), (2) decision makers interested in off-site waste form disposal, and (3) the U.S. Department of Energy, their Hanford Site contractors and stakeholders as they assess the IDF PA program at the Hanford Site. The results reported help fill existing data gaps, support final selection of a cementitious waste form for the EMF evaporator bottom waste, and improve the technical defensibility of long-term waste form risk estimates.

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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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Effluent Management Facility Evaporator Bottoms: Waste Streams Formulation and Waste Form Qualification Testing

This report describes the results from grout formulation and cementitious waste form testing performed by Pacific Northwest National Laboratory for Washington River Protection Solutions, LLC (WRPS). These results are part of a screening test that investigates grout formulations proposed for encapsulating a wide range of compositions predicted to be present in evaporator bottoms wastes from the Hanford Effluent Management Facility (EMF). This work supports the technical development need for alternative treatment and disposition paths for the EMF evaporator bottoms waste and future direct-feed low-activity waste (DFLAW) operations at the Hanford Site. High-priority activities included simulant production, grout formulation, and cementitious waste form testing. The work contained within this report relates to waste form development and testing, but does not directly support the 2017 Integrated Disposal Facility (IDF) performance assessment (PA). However, this work contains information useful for future PA updates [beyond fiscal year (FY) 2017] and future waste form development efforts. These analytical results can be used by (i) cementitious waste form scientists to further the understanding of cementitious leach behavior of contaminants of concern (COCs), (ii) decision makers interested in off-site waste form disposal, and (iii) the U.S. Department of Energy, their Hanford Site contractors, and stakeholders as they continue to assess the IDF PA program at the Hanford Site. The reported results help fill existing data gaps, support final selection of a cementitious waste form for the EMF evaporator bottoms waste, and improve the technical defensibility of long-term waste form risk estimates.

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Effluent Management Facility Evaporator Bottoms: Waste Streams Formulation and Waste Form Qualification Testing

This report describes the results from grout formulation and cementitious waste form testing performed by Pacific Northwest National Laboratory for Washington River Protection Solutions, LLC (WRPS). These results are part of a screening test that investigates grout formulations proposed for encapsulating a wide range of compositions predicted to be present in evaporator bottoms wastes from the Hanford Effluent Management Facility (EMF). This work supports the technical development need for alternative treatment and disposition paths for the EMF evaporator bottoms waste and future direct-feed low-activity waste (DFLAW) operations at the Hanford Site. High-priority activities included simulant production, grout formulation, and cementitious waste form testing. The work contained within this report relates to waste form development and testing, but does not directly support the 2017 Integrated Disposal Facility (IDF) performance assessment (PA). However, this work contains information useful for future PA updates [beyond fiscal year (FY) 2017] and future waste form development efforts. These analytical results can be used by (i) cementitious waste form scientists to further the understanding of cementitious leach behavior of contaminants of concern (COCs), (ii) decision makers interested in off-site waste form disposal, and (iii) the U.S. Department of Energy, their Hanford Site contractors, and stakeholders as they continue to assess the IDF PA program at the Hanford Site. The reported results help fill existing data gaps, support final selection of a cementitious waste form for the EMF evaporator bottoms waste, and improve the technical defensibility of long-term waste form risk estimates.

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DEVELOPMENT QUALIFICATION AND DISPOSAL OF AN ALTERNATIVE IMMOBILIZED LOW-ACTIVITY WASTE FORM AT THE HANFORD SITE

Demonstrating that a waste form produced by a given immobilization process is chemically and physically durable as well as compliant with disposal facility acceptance criteria is critical to the success of a waste treatment program, and must be pursued in conjunction with the maturation of the waste processing technology. Testing of waste forms produced using differing scales of processing units and classes of feeds (simulants versus actual waste) is the crux of the waste form qualification process. Testing is typically focused on leachability of constituents of concern (COCs), as well as chemical and physical durability of the waste form. A principal challenge regarding testing immobilized low-activity waste (ILAW) forms is the absence of a standard test suite or set of mandatory parameters against which waste forms may be tested, compared, and qualified for acceptance in existing and proposed nuclear waste disposal sites at Hanford and across the Department of Energy (DOE) complex. A coherent and widely applicable compliance strategy to support characterization and disposal of new waste forms is essential to enhance and accelerate the remediation of DOE tank waste. This paper provides a background summary of important entities, regulations, and considerations for nuclear waste form qualification and disposal. Against this backdrop, this paper describes a strategy for meeting and demonstrating compliance with disposal requirements emphasizing the River Protection Project (RPP) Integrated Disposal Facility (IDF) at the Hanford Site and the fluidized bed steam reforming (FBSR) mineralized low-activity waste (LAW) product stream.

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CESIUM REMOVAL FROM TANKS 241-AN-103 & 241-SX-105 & 241-AZ-101 & 241AZ-102 COMPOSITE FOR TESTING IN BENCH SCALE STEAM REFORMER

This report documents the preparation of three actual Hanford tank waste samples for shipment to the Savannah River National Laboratory (SRNL). Two of the samples were dissolved saltcakes from tank 241-AN-103 (hereafter AN-103) and tank 241-SX-105 (hereafter SX-105); one sample was a supernate composite from tanks 241-AZ-101 and 241-AZ-102 (hereafter AZ-101/102). The preparation of the samples was executed following the test plans LAB-PLAN-10-00006, Test Plan for the Preparation of Samples from Hanford Tanks 241-SX-105, 241-AN-103, 241-AN-107, and LAB-PLN-l0-00014, Test Plan for the Preparation of a Composite Sample from Hanford Tanks 241-AZ-101 and 241-AZ-102 for Steam Reformer Testing at the Savannah River National Laboratory. All procedural steps were recorded in laboratory notebook HNF-N-274 3. Sample breakdown diagrams for AN-103 and SX-105 are presented in Appendix A. The tank samples were prepared in support of a series of treatability studies of the Fluidized Bed Steam Reforming (FBSR) process using a Bench-Scale Reformer (BSR) at SRNL. Tests with simulants have shown that the FBSR mineralized waste form is comparable to low-activity waste glass with respect to environmental durability (WSRC-STI-2008-00268, Mineralization of Radioactive Wastes by Fluidized Bed Steam Reforming (FBSR): Comparisons to Vitreous Waste Forms and Pertinent Durability Testing). However, a rigorous assessment requires long-term performance data from FBSR product formed from actual Hanford tank waste. Washington River Protection Solutions, LLC (WRPS) has initiated a Waste Form Qualification Program (WP-5.2.1-2010-001, Fluidized Bed Steam Reformer Low-level Waste Form Qualification) to gather the data required to demonstrate that an adequate FBSR mineralized waste form can be produced. The documentation of the selection process of the three tank samples has been separately reported in RPP-48824, Sample Selection Process for Bench-Scale Steam Reforming Treatability Studies Using Hanford Waste Samples.

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CESIUM REMOVAL FROM TANKS 241-AN-103 & 241-SX-105 & 241-AZ-101/102 COMPOSITE FOR TESTING IN BENCH SCALE STEAM REFORMER

This report documents the preparation of three actual Hanford tank waste samples for shipment to the Savannah River National Laboratory (SRNL). Two of the samples were dissolved saltcakes from tank 241-AN-103 (hereafter AN-103) and tank 241-SX-105 (hereafter SX-105); one sample was a supernate composite from tanks 241-AZ-101 and 241-AZ-102 (hereafter AZ-101/102). The preparation of the samples was executed following the test plans LAB-PLAN-10-00006, Test Plan for the Preparation of Samples from Hanford Tanks 241-SX-105, 241-AN-103, 241-AN-107, and LAB-PLN-10-00014, Test Plan for the Preparation of a Composite Sample from Hanford Tanks 241-AZ-101 and 241-AZ-102 for Steam Reformer Testing at the Savannah River National Laboratory. All procedural steps were recorded in laboratory notebook HNF-N-274 3. Sample breakdown diagrams for AN-103 and SX-105 are presented in Appendix A. The tank samples were prepared in support of a series of treatability studies of the Fluidized Bed Steam Reforming (FBSR) process using a Bench-Scale Reformer (BSR) at SRNL. Tests with simulants have shown that the FBSR mineralized waste form is comparable to low-activity waste glass with respect to environmental durability (WSRC-STI-2008-00268, Mineralization of Radioactive Wastes by Fluidized Bed Steam Reforming (FBSR): Comparisons to Vitreous Waste Forms and Pertinent Durability Testing). However, a rigorous assessment requires long-term performance data from FB SR product formed from actual Hanford tank waste. Washington River Protection Solutions, LLC (WRPS) has initiated a Waste Form Qualification Program (WP-S.2.1-20 1 0-00 1, Fluidized Bed Steam Reformer Low-level Waste Form Qualification) to gather the data required to demonstrate that an adequate FBSR mineralized waste form can be produced. The documentation of the selection process of the three tank samples has been separately reported in RPP-48824, 'Sample Selection Process for Bench-Scale Steam Reforming Treatability Studies Using Hanford Waste Samples.'

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Fluidized bed steam reformed mineral waste form performance testing to support Hanford Supplemental Low Activity Waste Immobilization Technology Selection

This report describes the benchscale testing with simulant and radioactive Hanford Tank Blends, mineral product characterization and testing, and monolith testing and characterization. These projects were funded by DOE EM-31 Technology Development & Deployment (TDD) Program Technical Task Plan WP-5.2.1-2010-001 and are entitled “Fluidized Bed Steam Reformer Low-Level Waste Form Qualification”, Inter-Entity Work Order (IEWO) M0SRV00054 with Washington River Protection Solutions (WRPS) entitled “Fluidized Bed Steam Reforming Treatability Studies Using Savannah River Site (SRS) Low Activity Waste and Hanford Low Activity Waste Tank Samples”, and IEWO M0SRV00080, “Fluidized Bed Steam Reforming Waste Form Qualification Testing Using SRS Low Activity Waste and Hanford Low Activity Waste Tank Samples”. This was a multi-organizational program that included Savannah River National Laboratory (SRNL), THOR® Treatment Technologies (TTT), Pacific Northwest National Laboratory (PNNL), Oak Ridge National Laboratory (ORNL), Office of River Protection (ORP), and Washington River Protection Solutions (WRPS). The SRNL testing of the non-radioactive pilot-scale Fluidized Bed Steam Reformer (FBSR) products made by TTT, subsequent SRNL monolith formulation and testing and studies of these products, and SRNL Waste Treatment Plant Secondary Waste (WTP-SW) radioactive campaign were funded by DOE Advanced Remediation Technologies (ART) Phase 2 Project in connection with a Work-For-Others (WFO) between SRNL and TTT.

Jantzen, C. M.↗

Glass Property Models, Constraints, and Formulation Approaches for Vitrification of High-Level Nuclear Wastes at the US Hanford Site

The legacy nuclear wastes stored in underground tanks at the US Department of Energy’s Hanford site is planned to be separated into high-level waste and low-activity waste fractions and vitrified separately. Formulating optimized glass compositions that maximize the waste loading in glass is critical for successful and economical treatment and immobilization of nuclear wastes. Glass property-composition models have been developed and applied to formulate glass compositions for various objectives for the past several decades. The property models with associated uncertainties and combined with composition and property constraints have been used to develop preliminary glass formulation algorithms designed for vitrification process control and waste form qualification at the planned waste vitrification plant. This paper provides an overview of current status of glass property-composition models, constraints applicable to Hanford waste vitrification, and glass formulation approaches that have been developed for vitrification of hazardous and highly radioactive wastes stored at the Hanford site.

composition constraint↗

Reporting the Radionuclide Inventory of the DWPF Product

In the Defense Waste Processing Facility (DWPF) at the Savannah River Site (SRS), the radionuclides contained in the liquid high-level waste currently stored at SRS are being converted into a durable borosilicate glass. This glass in its sealed stainless-steel canister, the DWPF product, eventually must be sent to a federal repository for final disposal. In order to ensure that the DWPF product is suitable for acceptance by the U. S. Department of Energy’s (DOE) Civilian Radioactive Waste Management System (CRWMS)*, the DOE Office of Environmental Management (DOE-EM) established the Waste Acceptance Product Specifications for Vitrified High-Level Waste Forms (WAPS). DOE-EM is tentatively performing surrogate CRWMS waste acceptance functions, as the office was eliminated in 2009, for review and concurrence of technical baseline documents and waste form non conformances. The specifications are divided into five sections, dealing with the waste form (borosilicate glass) itself, the canister, the canistered waste form, quality assurance, and documentation and other administrative requirements. The DWPF is required to document its compliance with the specifications in the Waste Form Compliance Plan (WCP), the Waste Form Qualification Report (WQR), the Production Records, and the Storage and Shipping Records. The WCP provides general information about the DWPF process and product, and a general description of the methods and programs by which the DWPF will demonstrate compliance with each specification in the WAPS. The WCP was vital to DWPF startup with respect to operations planning and also assurance to DOE that the canistered waste forms would be acceptable for disposal at any future High-Level Waste (HLW) geologic repository. The WQR is a compilation of the results of the testing and analysis programs identified in the WCP. The WQR details the method of compliance with each specification, and the testing performed to demonstrate the effectiveness of each method. The WQR is published in separate volumes which each correspond to one or more of the specifications. The WQR also contains a description of the DWPF’s Glass Product Control Program. Each volume contains Part and Item designators which indicate the corresponding item(s) in the WCP. The Production Records, and the Storage and Shipping Records document that each DWPF product has been produced and stored in compliance with the WAPS. This document, Volume 4 of the WQR, responds to WAPS Specifications 1.2.2, 1.6, and 3.14 which require that the DWPF report the radionuclide inventory of each canistered waste form, and of each waste type. This volume describes the systems the DWPF uses to determine and report the radionuclide inventory of the glass product, and provides evidence that these systems allow the DWPF to satisfy the WAPS specification. This volume of the WQR has been prepared to establish that methods are available to determine and report the radionuclide inventory, and that the DWPF is ready to collect the facility-specific data necessary to provide definitive estimates of the errors associated with the use of these methods.

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SUMMARY PLAN FOR BENCH-SCALE REFORMER AND PRODUCT TESTING TREATABILITY STUDIES USING HANFORD TANK WASTE

This paper describes the sample selection, sample preparation, environmental, and regulatory considerations for shipment of Hanford radioactive waste samples for treatability studies of the FBSR process at the Savannah River National Laboratory and the Pacific Northwest National Laboratory. The U.S. Department of Energy (DOE) Hanford tank farms contain approximately 57 million gallons of wastes, most of which originated during the reprocessing of spent nuclear fuel to produce plutonium for defense purposes. DOE intends to pre-treat the tank waste to separate the waste into a high level fraction, that will be vitrified and disposed of in a national repository as high-level waste (HLW), and a low-activity waste (LAW) fraction that will be immobilized for on-site disposal at Hanford. The Hanford Waste Treatment and Immobilization Plant (WTP) is the focal point for the treatment of Hanford tank waste. However, the WTP lacks the capacity to process all of the LAW within the regulatory required timeframe. Consequently, a supplemental LAW immobilization process will be required to immobilize the remainder of the LAW. One promising supplemental technology is Fluidized Bed Steam Reforming (FBSR) to produce a sodium-alumino-silicate (NAS) waste form. The NAS waste form is primarily composed of nepheline (NaAlSiO{sub 4}), sodalite (Nas[AlSiO{sub 4}]{sub 6}Cl{sub 2}), and nosean (Na{sub 8}[AlSiO{sub 4}]{sub 6}SO{sub 4}). Semivolatile anions such as pertechnetate (TcO{sub 4}{sup -}) and volatiles such as iodine as iodide (I{sup -}) are expected to be entrapped within the mineral structures, thereby immobilizing them (Janzen 2008). Results from preliminary performance tests using surrogates, suggests that the release of semivolatile radionuclides {sup 99}Tc and volatile {sup 129}I from granular NAS waste form is limited by Nosean solubility. The predicted release of {sup 99}Tc from the NAS waste form at a 100 meters down gradient well from the Integrated Disposal Facility (IDF) was found to be comparable to immobilized low-activity waste glass waste form in the initial supplemental LAW treatment technology risk assessment (Mann 2003). To confirm this hypothesis, DOE is funding a treatability study where three actual Hanford tank waste samples (containing both {sup 99}Tc and {sup 125}I) will be processed in Savannah River National Laboratory's (SRNL) Bench-Scale Reformer (BSR) to form the mineral product, similar to the granular NAS waste form, that will then be subject to a number of waste form qualification tests. In previous tests, SRNL have demonstrated that the BSR product is chemically and physically equivalent to the FBSR product (Janzen 2005). The objective of this paper is to describe the sample selection, sample preparation, and environmental and regulatory considerations for treatability studies of the FBSR process using Hanford tank waste samples at the SNRL. The SNRL will process samples in its BSR. These samples will be decontaminated in the 222-S Laboratory to remove undissolved solids and selected radioisotopes to comply with Department of Transportation (DOT) shipping regulations and to ensure worker safety by limiting radiation exposure to As Low As Reasonably Achievable (ALARA). These decontamination levels will also meet the Nuclear Regulatory Commission's (NRC's) definition of low activity waste (LAW). After the SNRL has processed the tank samples to a granular mineral form, SRNL and Pacific Northwest National Laboratory (PNNL) will conduct waste form testing on both the granular material and monoliths prepared from the granular material. The tests being performed are outlined in Appendix A.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

REPORTABLE RADIONUCLIDES IN DWPF SLUDGE BATCH 7A (MACROBATCH 8)

The Waste Acceptance Product Specifications (WAPS) 1.2 require that the waste producer 'shall report the curie inventory of radionuclides that have half-lives longer than 10 years and that are, or will be, present in concentrations greater than 0.05 percent of the total inventory for each waste type indexed to the years 2015 and 3115.' As part of the strategy to meet WAPS 1.2, the Defense Waste Processing Facility (DWPF) will report for each waste type all radionuclides that have half-lives longer than 10 years and contribute greater than 0.01 percent of the total curie inventory from the time of production through the 1100 year period from 2015 through 3115. The initial list of radionuclides to be reported is based on the design-basis glass identified in the Waste Form Compliance Plan (WCP) and Waste Form Qualification Report. However, it is required that the list be expanded if other radionuclides with half-lives greater than 10 years are identified that meet the 'greater than 0.01% of the curie inventory' criterion. Specification 1.6 of the WAPS, International Atomic Energy Agency Safeguards Reporting for High Level Waste (HLW), requires that the ratio by weights of the following uranium and plutonium isotopes be reported: U-233, U-234, U-235, U-236, and U-238; and Pu-238, Pu-239, Pu-240, Pu-241, and Pu-242. Therefore, the complete list of reportable radionuclides must also include these sets of U and Pu isotopes - and the U and Pu isotopic mass distributions must be identified. The DWPF receives HLW sludge slurry from Savannah River Site (SRS) Tank 40. For Sludge Batch 7a (SB7a), the waste in Tank 40 contained a blend of the heel from Sludge Batch 6 (SB6) and the Sludge Batch 7 (SB7) material transferred to Tank 40 from Tank 51. This sludge blend is also referred to as Macrobatch 8. Laboratory analyses of a Tank 40 sludge sample were performed to quantify the concentrations of pertinent radionuclides in the SB7a waste. Subsequently, radiological decay and in-growth were calculated over the time period from 2015 to 3115. This provided a basis for characterizing the radionuclide content of SB7a over time and for identifying the 'reportable radionuclides.' Details of the characterization methodology and the analytical results are the focus of this report. This work was performed at the request of the Waste Solidification Engineering Department of Savannah River Remediation, initiated via Technical Task Request (TTR) HLW-DWPF-TTR-2010-0031. A minor revision in the reporting requirements was requested via a subsequent email communication. The work was conducted in accordance with the protocols identified in Task Technical and Quality Assurance Plan SRNL-RP-2010-01218 and Analytical Study Plan SRNL-RP-2010-01219. All of the raw data related to this scope have been recorded in laboratory notebook SRNL-NB-2011-00061. The overall goal of this task was to characterize the radionuclide content of the SB7a waste sufficiently to meet the WAPS and DWPF reporting requirements. The specific objectives were: (1) Quantify the current concentrations of all radionuclides impacting (or potentially-impacting) the total curie content between calendar years 2011 and 3115. Also quantify the current concentrations of other radionuclides specifically requested in the TTR or required by the WAPS. (2) Calculate future concentrations of decayed and in-grown radionuclides impacting the total curie content between calendar years 2015 and 3115; (3) Identify as 'reportable' all radionuclides contributing {ge} 0.01% of the total curie content from 2015 to 3115 and having half-lives {ge} 10 years.

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DETERMINATION OF REPORTABLE RADIONUCLIDES FOR DWPF SLUDGE BATCH 6 (MACROBATCH 7)

The Waste Acceptance Product Specifications (WAPS) 1.2 require that 'The Producer shall report the inventory of radionuclides (in Curies) that have half-lives longer than 10 years and that are, or will be, present in concentrations greater than 0.05 percent of the total inventory for each waste type indexed to the years 2015 and 3115'. As part of the strategy to comply with WAPS 1.2, the Defense Waste Processing Facility (DWPF) will report for each waste type, all radionuclides (with half-lives greater than 10 years) that have concentrations greater than 0.01 percent of the total inventory from time of production through the 1100 year period from 2015 through 3115. The initial listing of radionuclides to be included is based on the design-basis glass as identified in the Waste Form Compliance Plan (WCP) and Waste Form Qualification Report (WQR). However, it is required that this list be expanded if other radionuclides with half-lives greater than 10 years are identified that may meet the greater than 0.01% criterion for Curie content. Specification 1.6 of the WAPS, International Atomic Energy Agency (IAEA) Safeguards Reporting for High Level Waste (HLW), requires that the ratio by weights of the following uranium and plutonium isotopes be reported: U-233, U-234, U-235, U-236, U-238, Pu-238, Pu-239, Pu-240, Pu-241, and Pu-242. Therefore, the complete set of reportable radionuclides must also include this set of U and Pu isotopes. The DWPF is receiving radioactive sludge slurry from HLW Tank 40. The radioactive sludge slurry in Tank 40 is a blend of the heel from Sludge Batch 5 (SB5) with H-Canyon Np transfers completed after the start of processing SB5, and Sludge Batch 6 (SB6) that was transferred to Tank 40 from Tank 51. The blend of sludge in Tank 40 is also referred to as Macrobatch 7 (MB7). This report develops the list of reportable radionuclides and associated activities as a function of time. The DWPF will use this list and the activities as one of the inputs for the development of the Production Records that relate to radionuclide inventory. This work was initiated through Technical Task Request (TTR) HLW-DWPF-TTR-2009-0014; Rev. 2 entitled Sludge Batch 6 SRNL Shielded Cells Testing. Specifically, this report details results from performing Subtask III, Item 2 of the TTR and, in part, meets Deliverable 7 of the TTR. The work was performed following the Task Technical and Quality Assurance Plan (TTQAP), SRNL-RP-2009-00473, Rev. 15 and Analytical Study Plan (ASP), SRNL-RP-2009-00474, Rev. 1. In order to determine the reportable radionuclides for SB6 (MB7), a list of radioisotopes that may meet the criteria as specified by the Department of Energy's (DOE) WAPS was developed. All radioactive U-235 fission products and all radioactive activation products that could be in the SRS HLW were considered. In addition, all U and Pu isotopes identified in WAPS 1.6 were included in the list. This list was then evaluated and some isotopes were excluded from the projection calculations. Based on measurements and analytical detection limits, 30 radionuclides have been identified as reportable for DWPF SB6 as specified by WAPS 1.2. The WCP and WQR require that all of the radionuclides present in the Design Basis glass be considered as the initial set of reportable radionuclides. For SB6, all of the radionuclides in the Design Basis glass are reportable except for three radionuclides: Pd-107, Cs-135, and Th-230. At no time during the 1100-year period between 2015 and 3115 did any of these three radionuclides contribute to more than 0.01% of the radioactivity on a Curie basis. Two additional uranium isotopes (U-235 and -236) must be added to the list of reportable radionuclides in order to meet WAPS 1.6. All of the Pu isotopes (Pu-238, -239, -240, -241, and -242) and other U isotopes (U-233, -234, and -238) identified in WAPS 1.6 were already determined to be reportable according to WAPS 1.2 This brings the total number of reportable radionuclides for SB6 to 32. The radionuclide measurements made for SB6 are the most extensive conducted to date. Some method development/refinement occurred during the conduct of these measurements, leading to lower detection limits and more accurate measurement of some isotopes than was previously possible. Improvement in the analytical measurements will likely continue, and this in turn should lead to improved detection limit values for some radionuclides and actual measurements for still others.

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Determination Of Reportable Radionuclides For DWPF Sludge Batch 7B (Macrobatch 9)

The Waste Acceptance Product Specifications (WAPS) 1.2 require that “The Producer shall report the inventory of radionuclides (in Curies) that have half-lives longer than 10 years and that are, or will be, present in concentrations greater than 0.05 percent of the total inventory for each waste type indexed to the years 2015 and 3115”. As part of the strategy to comply with WAPS 1.2, the Defense Waste Processing Facility (DWPF) will report for each waste type, all radionuclides (with half-lives greater than 10 years) that have concentrations greater than 0.01 percent of the total inventory from time of production through the 1100 year period from 2015 through 3115. The initial listing of radionuclides to be included is based on the design-basis glass as identified in the Waste Form Compliance Plan (WCP) and Waste Form Qualification Report (WQR). However, it is required that this list be expanded if other radionuclides with half-lives greater than 10 years are identified that may meet the greater than 0.01% criterion for Curie content. Specification 1.6 of the WAPS, International Atomic Energy Agency (IAEA) Safeguards Reporting for High Level Waste (HLW), requires that the ratio by weights of the following uranium and plutonium isotopes be reported: U-233, U-234, U-235, U-236, U-238, Pu-238, Pu-239, Pu-240, Pu-241, and Pu-242. Therefore, the complete set of reportable radionuclides must also include this set of U and Pu isotopes. The DWPF is receiving radioactive sludge slurry from HLW Tank 40. The radioactive sludge slurry in Tank 40 is a blend of the heel from Sludge Batch 7a (SB7a) and Sludge Batch 7b (SB7b) that was transferred to Tank 40 from Tank 51. The blend of sludge in Tank 40 is also referred to as Macrobatch 9 (MB9). This report develops the list of reportable radionuclides and associated activities as a function of time. The DWPF will use this list and the activities as one of the inputs for the development of the Production Records that relate to radionuclide inventory.

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