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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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2015 Annual Summary Report for the Area 3 and Area 5 RWMs

This annual summary report presents results and conclusions of the Fiscal Year (FY) 2015 review to assess the adequacy of the performance assessments (PAs) and composite analyses (CAs) in support of the Disposal Authorization Statements for the Area 3 and Area 5 Radioactive Waste Management Sites at the Nevada National Security Site (NNSS). The report presents results and conclusions of the FY 2015 review and determines the adequacy of the PAs and CAs. Operational factors (e.g., waste forms and containers, facility design, and waste receipts), closure plans, monitoring results, and research and development (R&D) activities were reviewed to determine the adequacy of the PAs. Likewise, the environmental restoration activities at the NNSS relevant to the sources of residual radioactive material that are considered in the CAs, the land-use planning, and the results of the environmental monitoring and R&D activities were reviewed to determine the adequacy of the CAs.

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2016 Annual Summary Report for the Area 3 and Area 5 Radioactive Waste Management Sites at the Nevada National Security Site, Nye County, Nevada: Review of the Performance Assessments and Composite Analyses

The Maintenance Plan for the Performance Assessments and Composite Analyses for the Area 3 and Area 5 Radioactive Waste Management Sites at the Nevada Test Site (National Security Technologies, LLC 2007a) requires an annual review to assess the adequacy of the performance assessments (PAs) and composite analyses (CAs), with the results submitted to the U.S. Department of Energy (DOE) Office of Environmental Management. The Disposal Authorization Statements for the Area 3 and Area 5 Radioactive Waste Management Sites (RWMSs) also require that such reviews be made and that secondary or minor unresolved issues be tracked and addressed as part of the maintenance plan.The U.S. Department of Energy, National Nuclear Security Administration Nevada Field Office (NNSA/NFO) performed an annual review of the Area 3 and Area 5 RWMS PAs and CAs for federal fiscal year (FY) 2016. This annual summary report presents results and conclusions of the FY 2016 review, and determines the adequacy of the PAs and CAs. Operational factors (e.g., waste forms and containers, facility design, and waste receipts), closure plans, monitoring results, and research and development (R&D) activities were reviewed to determine the adequacy of the PAs. Likewise, the environmental restoration activities at the Nevada National Security Site (NNSS) relevant to the sources of residual radioactive material that are considered in the CAs, the land-use planning, and the results of the environmental monitoring and R&D activities were reviewed to determine the adequacy of the CAs. Important developments in FY 2016 include the following: Development of a new Area 5 RWMS closure inventory estimate based on disposals through FY 2016, Evaluation of new or revised waste streams by special analysis, and Development and acceptance of version 4.200 of the Area 5 RWMS GoldSim PA/CA model. The Area 3 RWMS has been in inactive status since July 1, 2006, with the last shipment received in April 2006. The FY 2016 review of operations, facility design, closure plans, monitoring results, and R&D results for the Area 3 RWMS indicates no changes that would impact PA validity. The conclusion of the annual review is that all performance objectives can be met and the Area 3 RWMS PA remains valid. There is no need to revise the Area 3 RWMS PA. Review of Area 5 RWMS operations, design, closure plans, monitoring results, and R&D activities indicates that no significant changes have occurred. The FY 2016 PA results, generated with the Area 5 RWMS v4.200 GoldSim PA model, indicate that there continues to be a reasonable expectation of meeting all performance objectives. All results remain less than 50% of their performance objectives. The results and conclusions of the Area 5 RWMS PA are judged valid, and there is no need to the revise the PA. A review of changes potentially impacting the CAs indicates that no significant changes occurred in FY 2016. A new Corrective Action Unit (CAU), CAU 576, with corrective action sites near the Area 3 RWMS and Area 5 RWMS was identified in FY 2016. The sites are currently under investigation and not expected to be important sources for the CA. The continuing adequacy of the CAs was evaluated with the new models, and no significant changes that would alter the CAs’ results or conclusions were found. The revision of the Area 3 RWMS CA, which will include the Yucca Flat Underground Test Area (CAU 97) source, is scheduled for FY 2024, following the completion of the Corrective Action Decision Document/Corrective Action Plan. Inclusion of the Frenchman Flat Underground Test Area (CAU 98) source in the Area 5 RWMS CA is planned pending the completion of the CAU 98 Closure Report in FY 2017. Near-term R&D efforts will focus on continuing development of the PA, CA, and inventory models for the Area 3 and Area 5 RWMSs.

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Ensuring Longevity: Ancient Glasses Help Predict Durability of Vitrified Nuclear Waste

How does glass alter with time? For the last hundred years this has been an important question to the fields of object conservation and archeology to ensure the preservation of glass artifacts. This same question is part of the development and assessment of durable glass waste forms for the immobilization of nuclear wastes. Researchers have developed experiments ranging from simple to highly sophisticated to answer this question, and, as a result, have gained significant insight into the mechanisms that drive glass alteration. However, the gathered data have been predominately applicable to only short-term alteration times, i.e. over the course of decades. What has remained elusive is the long-term mechanisms of glass alteration[1]. These mechanisms are of particular interest to the international nuclear waste glass community as they strive to ensure that vitrified products will be durable for thousands to tens of thousands of years. For the last thirty years this community has been working to fill this research gap by partnering with archeologists, museum curators, and geologists to identify hundred to million-year old glass analogues that have altered in environments representative of those expected at potential nuclear waste disposal sites. The process of identifying a waste glass relevant analogue is challenging as it requires scientists to relate data collected from short-term laboratory experiments to observations made from long-term analogues and extensive geochemical modeling.

Ancient Glass↗

Precipitation of Epsilon Particles in Metal Doped Ceria Irradiated with Energetic Ions

Metallic particles precipitated from fission products in oxide fuel matrix (e.g., UO{sub 2}) have a great impact on the thermal and mechanical properties of the fuel. A burn-up of 40 MWd/kg U results in the conversion of 4% of the uranium to approximately 3% fission products and 1% transuranium elements. Epsilon phase is the major metallic phase of the precipitates with a hexagonal-closed packed (HCP) crystal structure. It can exist in a variety of metallic forms in UO{sub 2}, but typically, it consists of five metals: Mo, Pd, Rh, Ru and Tc. Epsilon particles can form over a wide range of stoichiometries in the five metal system. Simulated compositions with Re as a surrogate for Tc have been investigated as a waste form for {sup 99}Tc, an isotope with a long half-life of 2.13 10{sup 5} years and a high solubility under oxidizing conditions in addition to Mo in the corrosion process. There is a pressing need to understand the factors influencing the formation and growth of the metallic phase in fuel. Efforts are currently underway to perform careful neutron irradiation of nuclear fuel under controlled conditions in a test reactor, recover metallic phases that may be present, and characterize the resulting structure and chemistry. Due to the long duration, high cost and radiological concerns associated with neutron irradiation and sample characterizations, ion irradiation studies of a surrogate material with a full control of the processing parameters can emulate different stages of the particle precipitation, which can add a tremendous value to reactor-based studies. This presentation reports our recent ion irradiation results on the metallic particle precipitation under various irradiation and thermal annealing conditions.

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Potential of hybrid functionalized meso-porous materials for the separation and immobilization of radionuclides

Functionalized meso-porous materials are a class of hybrid organic-inorganic material in which a meso-porous metal oxide framework is functionalized with multifunctional organic molecules. These molecules may contain one or more anchor groups that form strong bonds to the pore surfaces of the metal oxide framework and free functional groups that can impart and or modify the functionality of the material such as for binding metal ions in solution. Such materials have been extensively studied over the past decade and are of particular interest in absorption applications because of the tremendous versatility in choosing the composition and architecture of the metal oxide framework and the nature of the functional organic molecule as well as the efficient mass transfer that can occur through a well-designed hierarchically porous network. A sorbent for nuclear applications would have to be highly selective for particular radio nuclides, it would need to be hydrolytically and radiolytically stable, and it would have to possess reasonable capacity and fast kinetics. The sorbent would also have to be available in a form suitable for use in a column. Finally, it would also be desirable if once saturated with radio nuclides, the sorbent could be recycled or converted directly into a ceramic or glass waste form suitable for direct repository disposal or even converted directly into a material that could be used as a transmutation target. Such a cradle-to- grave strategy could have many benefits in so far as process efficiency and the generation of secondary wastes are concerned.This paper will provide an overview of work done on all of the above mentioned aspects of the development of functionalized meso-porous adsorbent materials for the selective separation of lanthanides and actinides and discuss the prospects for future implementation of a cradle-to-grave strategy with such materials. (author)

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Combined effects of radiation damage and He accumulation on bubble nucleation in Gd2Ti2O7

Pyrochlores have long been considered as host phases for long-term immobilization of radioactive waste nuclides that would undergo ..alpha..-decay for hundreds of thousands of years. This work utilizes ion-beam irradiations to examine the combined effects of radiation damage and He accumulation on bubble formation in Gd2Ti2O7 over relevant waste-form timescales. Helium bubbles are not observed in pre-damaged Gd2Ti2O7 implanted with 2 x 1016 He/cm2, even after post-implantation irradiations with 7 MeV Au3+ at 300, 500, and 700 K. However, He bubbles with average diameters of 1.5 nm and 2.1 nm are observed in pre-damaged (amorphous) Gd2Ti2O7 and pristine Gd2Ti2O7, respectively, after implantation of 2 x 1017 He/cm2. The critical He concentration for bubble nucleation in Gd2Ti2O7 is estimated to be 6 at.% He.

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Framework for The Analysis of US Permanent Geologic Disposal Options for Radioactive Waste

The U.S. study of permanent geologic disposal options of spent nuclear fuel (SNF) and high-level radioactive waste (HLW) provided a technical basis for informing policy decisions regarding strategies for the management and disposal of radioactive waste requiring geologic isolation through the evaluation of potential impacts of waste forms on the feasibility and performance of representative generic concepts for geologic disposal. The goal of the study was to help inform relevant policy questions including: Is a "one-size-fits-all" repository a good strategic option for disposal? Do different waste types and forms perform differently enough in different disposal concepts that they warrant different treatment? Do some disposal concepts perform significantly better with or without specific waste types or forms?

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Overview of Features, Events, and Processes Affecting the Postclosure Performance of a Deep Borehole Disposal Facility - 17168

The United States Department of Energy's Office of Nuclear Energy (DOE-NE) is evaluating the feasibility of disposing of smaller DOE-managed waste forms in 5-km deep boreholes drilled in crystalline rock. It is thought that both the depth and the geological conditions at that depth will serve to isolate the waste from the accessible environment after the disposal facility is closed. This paper discusses the features, events, and processes (FEPs) that could affect the postclosure performance of a deep borehole disposal (DBD) facility and identifies those that would likely need to be considered in the context of conducting a performance assessment analysis. (authors)

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The U.S. Nuclear Waste Technical Review Board Intern Program: Developing Next Generation Nuclear Waste Professionals - 16102

The U.S. Nuclear Waste Technical Review Board (Board) created an internship program in the fall of 2013 for undergraduate and graduate students interested in management and disposal of spent nuclear fuel and high-level radioactive waste. Interns must select a project topic in a technical area related to the Board's mission and prepare a well-supported briefing for the agency. The ability to review technical and scientific information in a critical and unbiased manner is essential for completion of the intern's project and this is a particular focus of the interaction between the mentor and the intern. The interns from 2014 and 2015 selected and reviewed topics related to the areas of commingling waste forms for disposal and deep borehole disposal. In addition to the technical project, interns acquire a broad perspective of the federal agencies involved in managing and disposing of radioactive waste while participating in inter-agency networking opportunities. In this review of the Board internship experience, two past interns discuss the personal impact of the program and how they believe the experience prepared them to face the challenges of a career in management and disposal of spent nuclear fuel and high-level radioactive waste. (authors)

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Tank Side Cesium Removal System Project and Technology Maturation Program - 19519

Washington River Protection Solutions (WRPS) is the Tank Operating Contractor (TOC) for the U.S. Department of Energy-Office of River Protection (DOE-ORP) on the Hanford Site. The Hanford Site stores an estimated 56 million gallons of mixed radioactive and chemically hazardous waste in large underground tanks. WRPS is in the process of designing the Tank Side Cesium Removal (TSCR) system to produce Low Activity Waste (LAW) from Hanford tank waste. The LAW will be transferred to the Waste Treatment and Immobilization Plant (WTP) LAW Vitrification Facility, where the hazardous constituents in the LAW will be immobilized in a durable glass waste form for disposal. The TSCR Project demonstrates a tank-side treatment system for providing feed to the WTP LAW Vitrification Facility. This system removes cesium from supernatant tank waste using non-elutable cesium ion exchange media to meet the applicable waste acceptance criteria for the WTP. In support of the project, a tailored Technology Maturation/Testing Plan (TMP) has been developed to identify principal Technology Elements (TEs) for the proposed process, designate Critical Technology Elements (CTEs), identify gaps in the existing knowledge base and identify the necessary activities to mature the technologies for successful deployment of TSCR. The project scope and technology maturation approach are presented. (authors)

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NRC Monitoring of Salt Waste Disposal at the Savannah River Site - 13147

As part of monitoring required under Section 3116 of the Ronald W. Reagan National Defense Authorization Act for Fiscal Year 2005 (NDAA), the NRC staff reviewed an updated DOE performance assessment (PA) for salt waste disposal at the Saltstone Disposal Facility (SDF). The NRC staff concluded that it has reasonable assurance that waste disposal at the SDF meets the 10 CFR 61 performance objectives for protection of individuals against intrusion (chap.61.42), protection of individuals during operations (chap.61.43), and site stability (chap.61.44). However, based on its evaluation of DOE's results and independent sensitivity analyses conducted with DOE's models, the NRC staff concluded that it did not have reasonable assurance that DOE's disposal activities at the SDF meet the performance objective for protection of the general population from releases of radioactivity (chap.61.41) evaluated at a dose limit of 0.25 mSv/yr (25 mrem/yr) total effective dose equivalent (TEDE). NRC staff also concluded that the potential dose to a member of the public is expected to be limited (i.e., is expected to be similar to or less than the public dose limit in chap.20.1301 of 1 mSv/yr [100 mrem/yr] TEDE) and is expected to occur many years after site closure. The NRC staff used risk insights gained from review of the SDF PA, its experience monitoring DOE disposal actions at the SDF over the last 5 years, as well as independent analysis and modeling to identify factors that are important to assessing whether DOE's disposal actions meet the performance objectives. Many of these factors are similar to factors identified in the NRC staff's 2005 review of salt waste disposal at the SDF. Key areas of interest continue to be waste form and disposal unit degradation, the effectiveness of infiltration and erosion controls, and estimation of the radiological inventory. Based on these factors, NRC is revising its plan for monitoring salt waste disposal at the SDF in coordination with South Carolina Department of Health and Environmental Control (SCDHEC). DOE has completed or begun additional work related to salt waste disposal to address these factors. NRC staff continues to evaluate information related to the performance of the SDF and has been working with DOE and SCDHEC to resolve NRC staff's technical concerns. (authors)

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A Decade of Innovative Approaches to Treating and Dispositioning Radioactive Waste at the Savannah River Site - 20620

This year marks the 70. anniversary of the U.S. Department of Energy's (DOE) Savannah River Site (SRS), located near Aiken, South Carolina. SRS is a key industrial complex responsible for environmental stewardship, environmental cleanup, waste management, and disposition of nuclear materials. SRS also continues to have a role in critical defense-related activities and the reprocessing of used reactor fuel. The SRS encompasses 803 square kilometers (310 square miles) in parts of Aiken, Barnwell, and Allendale counties. The Liquid Waste Mission starts with the safe receipt and storage of radioactive liquid waste in the waste tanks, which principally includes Cold War legacy waste, but also waste from support of National Aeronautics Space Administration missions, medical isotope production, and research activities. This 133,000 cubic meters (m{sup 3}) (35 million gallons [Mgal]) of high-level radioactive waste (HLW) is currently held in 43 large underground waste tanks. The capacity of each of these tanks range from 2,800 m{sup 3} to 5,000 m{sup 3} (0.75 to 1.33 Mgal) and were placed in operation between 1954 and 1986. In July 2009, the DOE awarded a stand-alone contract to execute the Liquid Waste Mission at SRS. The Liquid Waste Contractor selected was Savannah River Remediation LLC1 (SRR), which is responsible for receipt, storage, retrieval and treatment of all HLW, disposal of the decontaminated low-activity waste fraction, as well as operationally closing cleaned HLW tanks. Since July 2009, SRR has successfully grouted and operationally closed six large underground tanks, poured 1,476 canisters of vitrified HLW (a stable glass waste form), treated approximately 34,200 m{sup 3} (9.0 Mgal) of HLW, and dispositioned over 41,200 m{sup 3} (10.9 Mgal) of decontaminated salt solution as low-level waste (LLW) into the Saltstone Disposal Units (SDUs) being constructed by SRR on site. The innovative work performed by SRR in the LLW portion of its mission has earned it the Richard S. Hodes Award. The work conducted by SRR is the same work championed by the late Richard S. Hodes, a respected physician, statesmen, and Chairman of the Southeast Compact Commission for Low-Level Radioactive Waste Management. (authors)

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Tank Side Cesium Removal System Project and Technology Maturation Program - 20101

Washington River Protection Solutions (WRPS) is the Tank Operating Contractor (TOC) for the U.S. Department of Energy-Office of River Protection (DOE-ORP) on the Hanford Site. The Hanford Site stores an estimated 56 million gallons of mixed radioactive and chemically hazardous waste in large underground tanks. WRPS is in the process of designing the Tank Side Cesium Removal (TSCR) system to produce a Low Activity Waste (LAW) feed from existing mixed Hanford tank waste. The LAW will be transferred to the Waste Treatment and Immobilization Plant (WTP) LAW Vitrification Facility, where it will be immobilized in a durable glass waste form for disposal. The TSCR Project demonstrates a tank-side treatment system for providing feed to the WTP LAW Vitrification Facility. This system removes undissolved solids and cesium from tank waste supernatant using non-elutable ion exchange media to meet the applicable waste acceptance criteria for the WTP. In support of the project, technology testing has been performed to answer design questions and reduce risk. The project scope and technology testing approach are presented. (authors)

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Stability of Super Absorbent Polymers in Sodium Nitrate - 16222

The stability of two different chemical types of cross-linked super absorbent polymers has been explored using a surrogate waste of 3M Sodium Nitrate (NaNO{sub 3}) that had pH adjusted using concentrated Nitric Acid (HNO{sub 3}) to pH of 1, 2, 4 and 6. Tests showed both types of polymer gelled the surrogate waste liquids. On-going stability tests revealed that there was no breakdown of the waste form after 11 months and no release of free liquids. (authors)

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Demonstration of SuperLig{sup R} 605 and SuperLig{sup R} 644 in a Regeneration Flow Sheet to Remove Radioactive Strontium and Cesium from Seawater - 16236

Remediation techniques are needed for efficient removal of radioactive strontium and cesium from seawater. Molecular Recognition Technology, using selective SuperLig{sup R} resins, demonstrates a clean chemistry approach to solving this problem. Molecular Recognition Technology offers high levels of separation of chemically pure metal contaminants, whose subsequent disposal is compatible with simple waste forms (grout and glass). SuperLig{sup R} resins can be regenerated with common reagents and used many times, limited by a dose of 1 E+9 Rad, which assures low volumes of secondary solid waste. The metal selectivity of the SuperLig{sup R} resin ensures that the solid waste is of low residual activity. These properties of sustainability are illustrated in a project that demonstrated the ability of two SuperLig{sup R} resins to selectively remove Cs and Sr from a seawater mimic representative of the contaminated seawater in Fukushima, Dai'ichi, Japan harbor. Removal of radioactive Sr-90 and Cs-134/Cs-137 from seawater using conventional ion exchange or a complexing agent is complicated by the presence of large excesses of competing ions such as Na, K, Ca, and Mg, which can be co-extracted. These competing ions, if co-extracted, reduce the capacity of a single pass resin with the consequent increase in volume of spent resin or decrease in capacity of a regenerable resin. The successful demonstration reported in this study has shown the ability of two proprietary resins, SuperLig{sup R} 605 and SuperLig{sup R} 644, to remove Sr and Cs, respectively, with high selectivity from simulated solutions containing these metal ions together with major constituents of seawater at their normal concentrations. This effort was part of a demonstration project to investigate methods for removal of Sr-90 and Cs-134/Cs-137 from 160,000 cubic meters of seawater impounded at Fukushima, Dai'ichi, Japan harbor. SuperLig{sup R} resins can be regenerated by elution with small volumes of simple acid solutions. SuperLig{sup R} resins have a high tolerance to radiation, with their performance not being degraded by doses of 1.0 E+9 Rad. Estimates, based on the results obtained, are that Cs and Sr levels in the volume of seawater in the Fukushima, Dai'ichi, Japan harbor could be reduced to desired discharge limits in 200 days with some 30 cubic meters of the two SuperLig{sup R} resins and that decontamination factors of 10 or more could be achieved. Results of the demonstration, together with advantages of the Molecular Recognition Technology process over conventional procedures for these separations are presented and discussed. (authors)

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Decontamination and Melting of Reactor Upper Internals - 18536

In a BWR, the upper reactor internals, i.e. the steam separators and the steam dryer converts the hot water to a dry steam for the turbines. These components have due to the distance to the reactor core low to very low levels of neutron activation, if any. The contamination of these components is usually significant and consists of both loose contamination and contamination bound in oxide layers. The upper reactor internals on a BWR are quite voluminous in relation to their weight, has a complex geometry and are therefore time consuming to cut in pieces that allows high density packing in waste containers for ILW. The incentives for decontamination of the components down to levels that allow melting for volume reduction are therefore high. A performed full-scale treatment project on a steam dryer confirms the significant volume reduction. The steam dryer was decayed prior to segmentation and melting for volume reduction. Cyclife/EDF has, since significant volume reduction is within reach if the inventory of gamma emitting nuclides and by then the dose rate can be reduced, taken benefit of chemical decontamination studies and an analyze of potential treatment results. The analyze confirm that high decontamination factors can be achieved and that the acceptance criteria for melting can be met, with margin. Full scale decontamination results achieved by AREVA NP and others do align fairly well with the test results. Even without the option of clearance/recycling of the metals, due to high residual activity, a high or very high volume reduction factors can be achieved by melting as well as a potential reclassification of the metal in a disposal perspective. One key aspect for success is to keep the volume of the secondary waste from the decontamination down and to make sure that the waste form fulfils the requirements for disposal. (authors)

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