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HLW Processing for Complementary Disposition Strategy: Development and Testing of Glass and Feed Formulations

The objective of the work described herein was to develop and identify HLW glass compositions and glass forming additive blends for vitrification of selected HLW streams, which have undergone various degrees of washing but no other pretreatment, while maintaining high WLs, high processing rates, and acceptable glass properties. The glass formulations were actively designed and based on previous formulation experience and testing at VSL. The WTP baseline HLW property-composition models were used to select glass formulations for testing and to predict various glass properties. Crucible-scale fabrication of the HLW glasses that were formulated was performed and the product glasses were characterized with respect to select properties. A total of 10 HLW glasses were developed and tested for five fully washed waste batches and one singly washed waste batch.

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A Safety Case Approach for Deep Geologic Disposal of DOE HLW and DOE SNF in Bedded Salt - 13350

The primary objective of this study is to investigate the feasibility and utility of developing a defensible safety case for disposal of United States Department of Energy (U.S. DOE) high-level waste (HLW) and DOE spent nuclear fuel (SNF) in a conceptual deep geologic repository that is assumed to be located in a bedded salt formation of the Delaware Basin [1]. A safety case is a formal compilation of evidence, analyses, and arguments that substantiate and demonstrate the safety of a proposed or conceptual repository. We conclude that a strong initial safety case for potential licensing can be readily compiled by capitalizing on the extensive technical basis that exists from prior work on the Waste Isolation Pilot Plant (WIPP), other U.S. repository development programs, and the work published through international efforts in salt repository programs such as in Germany. The potential benefits of developing a safety case include leveraging previous investments in WIPP to reduce future new repository costs, enhancing the ability to effectively plan for a repository and its licensing, and possibly expediting a schedule for a repository. A safety case will provide the necessary structure for organizing and synthesizing existing salt repository science and identifying any issues and gaps pertaining to safe disposal of DOE HLW and DOE SNF in bedded salt. The safety case synthesis will help DOE to plan its future R and D activities for investigating salt disposal using a risk-informed approach that prioritizes test activities that include laboratory, field, and underground investigations. It should be emphasized that the DOE has not made any decisions regarding the disposition of DOE HLW and DOE SNF. Furthermore, the safety case discussed herein is not intended to either site a repository in the Delaware Basin or preclude siting in other media at other locations. Rather, this study simply presents an approach for accelerated development of a safety case for a potential DOE HLW and DOE SNF repository using the currently available technical basis for bedded salt. This approach includes a summary of the regulatory environment relevant to disposal of DOE HLW and DOE SNF in a deep geologic repository, the key elements of a safety case, the evolution of the safety case through the successive phases of repository development and licensing, and the existing technical basis that could be used to substantiate the safety of a geologic repository if it were to be sited in the Delaware Basin. We also discuss the potential role of an underground research laboratory (URL). (authors)

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Robust disposal concept, uniform regulations, and trust in the messenger; three fundamental building blocks for consent-based HLW-disposal solutions in the USA - 15104

Pending enabling legislation, the USA's HLW-disposal program had been held in political abeyance since 2009 at the crossroads to one or both of the Yucca Mountain candidate (since 1987) HLW-repository in Nevada and/or the consent-based siting of the new HLW-disposal and centralized HLW-storage facilities proposed in 2012; a road not previously travelled. The consent-based siting approach would require the following gap between the reality (A) and the requirement (B) for public trust, acceptance and sustained support (PASS) to be bridged: A. Less than 1% of the general public in any given country fully comprehends the scientific-underpinnings and the projected health risks imposed by a HLW repository. B. More than 50% of the general public in a given geographical area would have to accept to host it from start to end. The following PASS-building blocks, successfully used at the WIPP-site in New Mexico and abroad to get from A to B during the past 30+ years, are thus highly recommended: 1. Defining the consent footprint upon host-county/state boundaries and/or radiation/health-risks and/or to identify/designate the directly affected parties (DAPs). 2. Using databases and lessons-learned by other repository programs to advantage. 3. Presenting the information in terms and/or by examples more readily understood by laypeople, because both their acceptance and opposition/rejection are influenced by: a. The type, number, problems, and status of 'similar' disposal concepts; and b. The level of i. Radiation protection provided by applicable regulations; ii. Involvement and decision-making authority vested in the DAPs; and iii. Their trust in the 'spokesperson/messenger. (authors)

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Novel Foaming Solutions for High Level Waste (HLW) Processing - 20195

Foaming occurs during treatment of high level waste (HLW) at Savannah River Site's Defense Waste Processing Facility (DWPF) in the Chemical Process Cell (CPC) due to high gas generation from process steam and chemical offgas products [1]. The presence of amphiphilic particles in the waste slurry stabilizes the foam [2], [3]. Efficient processing of HLW requires foam control, as foam-overs lead to lower productivity and potential radioactive contamination of condensate streams. DWPF currently employs Siovation Antifoam 747, a surfactant produced by Momentive Performance Materials, as an antifoaming agent during waste treatment. Despite its ability to control foam generation, processing issues have arisen from its use [4]. During DWPF chemical processing, a chemical antifoam agent must be effective at temperatures up to 103 deg. C between pH 3-13. Antifoam 747 is effective at pH 7 but degrades as pH deviates [5]. Antifoam 747 is 90% by weight Momentive{sup TM} L77 and 10% by weight Momentive{sup TM} Y-17580. These ingredients are trisiloxane products, which are especially vulnerable to attack in acidic and caustic environments. Since Antifoam 747 readily degrades, periodic addition is required. Several processing concerns related to Antifoam 747 have affected DWPF operation. Its overuse warranted concern of potential flammable melter offgas under upset conditions due to the generation of carbon dioxide and hydrogen. As a result, a Potential Inadequacy in the Safety Analysis (PISA) was declared [6]. Antifoam contribution has been included in the melter offgas flammability strategy and the quantity of antifoam is monitored to ensure limits are not exceeded. Testing at Savannah River National Laboratory (SRNL) determined that propanal, tri-methylsilanol, and hexamethyldisiloxane are generated as Antifoam 747 degrades, leading to a second PISA [7]. The formation of these byproducts poses additional flammability risks. Furthermore, the methyl and ethyl groups of these compounds may be responsible for the formation of the methyl and ethyl mercury discovered in DWPF [8], [9]. The formation of organomercury has specifically been called out by DOE as a need for increased research. The effectiveness of non-chemical methods for foam control and the efficiency of alternative antifoam agents were evaluated as part of an effort to improve HLW treatment operations at DWPF and to reduce, or eliminate, the flammability hazards associated with Antifoam 747 currently in use. Foaming of high-level waste (HLW) slurries is an issue at the Defense Waste Processing Facility (DWPF) Chemical Process Cell (CPC) which is currently mitigated with a chemical antifoam agent. The effectiveness of non-chemical methods for foam control and the efficiency of alternative antifoams were examined to improve HLW treatment at DWPF and to eliminate the flammability hazards associated with Siovation Antifoam 747 currently in use. Non-chemical foam control methods were deemed unviable for chemical processing at DWPF, as the spray/mist technique requires too much water and space limitations make installation and implementation of headspace agitators unfeasible. The use of ultrasonic energy thickened and further stabilized the foam. Two suitable alternative defoaming agents, Momentive{sup TM} Y- 17112 and Evonik Surfynol{sup R} MD-20, were identified. Both defoamers control foam over a pH range of 4- 13 at boiling, with no flammable degradation products, and only minimal quantities (100-200 mg/kg) are required under glycolic acid conditions. In order to validate the effectiveness of these defoaming agents, SRNL recommends irradiation testing and laboratory scale SRAT/SME experiments with actual radioactive waste. (authors)

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Redox Control For Hanford HLW Feeds

The principal objectives of this work were to investigate the effects of processing simulated Hanford HLW at the estimated maximum concentrations of nitrates and oxalates and to identify strategies to mitigate any processing issues resulting from high concentrations of nitrates and oxalates. This report provides results for a series of tests that were performed on the DM10 melter system with simulated C-106/AY-102 HLW. The tests employed simulated HLW feeds containing variable amounts of nitrates and waste organic compounds corresponding to maximum concentrations projected for Hanford HLW streams in order to determine their effects on glass production rate, processing characteristics, glass redox conditions, melt pool foaming, and the tendency to form secondary phases. Such melter tests provide information on key process factors such as feed processing behavior, dynamic effects during processing, processing rates, off-gas amounts and compositions, foaming control, etc., that cannot be reliably obtained from crucible melts.

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Effects of High Spinel and Chromium Oxide Crystal Contents on Simulated HLW Vitrification in DM100 Melter Tests (Final Report)

The principal objective of the work was to evaluate the effects of spinel and chromium oxide particles on WTP HLW melter operations and potential impacts on melter life. This was accomplished through a combination of crucible-scale tests, settling and rheological tests, and tests on the DM100 melter system. Crucible testing was designed to develop and identify HLW glass compositions with high waste loadings that exhibit formation of crystalline spinel and/or chromium oxide phases up to relatively high crystal contents (i.e., > 1 vol%). Characterization of crystal settling and the effects on melt rheology was performed on the HLW glass formulations. Appropriate candidate HLW glass formulations were selected, based on characterization results, to support subsequent melter tests. In the present work, crucible melts were formulated that exhibit up to about 4.4 vol% crystallization.

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Regional Geologic Evaluations for Disposal of HLW and SNF: Alluvial Basins of the Basin and Range Province

The DOE Spent Fuel and Waste Technology (SFWT) R&D Campaign supports research on crystalline rock, shale (argillite) and salt as potential host rocks for disposal of HLW and SNF in a mined geologic repository. Modeling involving these host rocks for the generic GDSA reference cases has assumed saturated conditions at repository depths. In order to test two-phase flow capabilities of the GDSA flow and transport models, the SFWT Campaign is developing an unsaturated zone reference case. Alluvial basin-fill deposits within the Basin and Range province have unsaturated zones that can be as thick as 600 meters, although the thickness is typically much less. Basin-fill alluvium has been considered as a potential medium for HLW disposal in the US since the 1950s (NAS,1957; Smyth et al., 1979; Winograd, 1981). Attributes considered favorable for HLW disposal in alluvium in the Basin and Range province include an arid environment, low water flux , high sorption capacity (from clay s and zeolites), and ease of construction and stability of repository openings (Hardin et al., 2012). Hardin et al. (2012) also address the thermal issues inherent in the design of a HLW repository in alluvium with low thermal conductivity, which are not discussed in this report.

58 GEOSCIENCES↗

Support for HLW Direct Feed

This report describes work performed to develop and test new glass and feed formulations originating from a potential flow-sheet for the direct vitrification of High Level Waste (HLW) with minimal or no pretreatment. In the HLW direct feed option that is under consideration for early WTP operations, the pretreatment facility would be bypassed in order to support an earlier start-up of the vitrification facility. For HLW, this would mean that the ultrafiltration and caustic leaching operations that would otherwise have been performed in the pretreatment facility would either not be performed or would be replaced by an interim pretreatment function (in-tank leaching and settling, for example). These changes would likely affect glass formulations and waste loadings and have impacts on the downstream vitrification operations. Modification of the pretreatment process may result in: (i) Higher aluminum contents if caustic leaching is not performed; (ii) Higher chromium contents if oxidative leaching is not performed; (iii) A higher fraction of supernate in the HLW feed resulting from the lower efficiency of in-tank washing; and (iv) A higher water content due to the likely lower effectiveness of in-tank settling compared to ultrafiltration. The initial efforts reported here focused on the impacts of increased supernate and water content on wastes from one of the candidate source tanks for the direct feed option.

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Sludge Processing Options for early HLW Treatment at Hanford

The U.S. Department of Energy’s (DOE) Hanford Site has 177 underground storage tanks that contain wastes from past nuclear fuel reprocessing and waste-management operations. Over 20% of this waste is in the form of an insoluble sludge that will require solids concentration and washing prior to vitrification for long-term disposal. An assessment of potential flowsheet operations to support feed preparation activities prior to high level waste (HLW) vitrification has been conducted to better evaluate pretreatment processing options. Settling studies assessing the baseline approach of a settle-decant method were explored as well as a crossflow filtration system to be used alternatively for concentrating and washing HLW sludge. Significant variations in behavior of settling rates and sludge characteristics give reason to evaluate alternative pretreatment options for the HLW. Non-radioactive sludge containing iron oxide, boehmite, and gibbsite were evaluated via gravity settling and crossflow filtration to determine the behavior of these compounds in various tank waste matrices. Understanding the predictive capabilities of HLW solids settling as well as sludge concentration via crossflow filtration can help provide technical guidance during flowsheet planning.

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Enhanced HLW Glass Property-Composition Models – Phase 1 (Final Report)

In the present work, the previously compiled glass property-composition database for WTP HLW glasses has been updated with newly available data. The earlier evaluation of the baseline WTP models against the larger data sets, in terms of range of validity and prediction performance, has been used together with a review of the HLW glass data to identify gaps in the composition regions that need to be filled to support the development of expanded models. Subsequently, statistically-designed compositional matrices were developed to begin to fill these composition gaps. Crucible melts have been prepared for the matrix glasses and glass properties have been collected. Finally, preliminary models have been developed that are applicable to the expanded dataset. Additionally, the performance of the preliminary models have been reviewed to assess the relative advantages of developing one set of models for the entire HLW glass composition space or to developing separate models for discrete composition spaces. The longer-term objective of this multi-year task is to develop new glass property-composition models for PCT release, spinel crystallization (T 1% ), nepheline formation on CCC, TCLP Cd response, viscosity, and electrical conductivity to control glass compositions for HLW vitrification at Hanford.

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Enhanced HLW Glass Property-Composition Models – Phase 2

As a continuation of the Phase 1 HLW model development work as part of a phased approach to enhance and expand HLW glass property-composition models, additional data were collected for the HLW glass dataset and used to revise the models developed during Phase 1. These data are for glasses that are collectively referred to as ORP-2014 glasses. The sources of additional data for the Phase 2 work included: (i) actively designed glasses formulated to support various glass studies at VSL since the completion of Phase 1; and (ii) glasses from two statistically designed matrices to supplement the existing HLW compositional space. The Phase 2 matrix design was intended to augment and improve the coverage in the high aluminum region.

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Enhancement of HLW glass property-composition models

Since the WTP compositional space of HLW glasses is extremely large, development of HLW property-composition models is a multi-year task consisting of multiple phases. The primary focus of this work was to enhance the WTP HLW models of interest including PCT releases, spinel crystallization (T1%), viscosity, electrical conductivity, and TCLP-Cd response. Model development to predict nepheline formation upon CCC is the subject of a separate task. In particular, the earlier work has produced property-composition models for glass melt viscosity and glass melt electrical conductivity that showed good performance, while models for PCT releases and spinel crystallization (T1%) required improvement. Therefore, more efforts were directed in the present work to collect data and improve model performance for HLW glass PCT releases and spinel crystallization than for other properties. The present work is a continuation of earlier development phases and is responsive to the applicable Test Plan.

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The production of advanced glass ceramic HLW forms using cold crucible induction melter

Cold Crucible Induction Melters (CCIM) will favorably change how High-Level radioactive Waste (from nuclear fuel recovery) is treated in a near future. Unlike the existing Joule-Heated Melters (JHM) currently in operation for the glass-based immobilization of High-Level Waste (HLW), CCIM offers unique material features that will increase melt temperatures, increase throughput, increase mixing, increase loading in the waste form, lower melter foot prints, eliminate melter corrosion and lower costs. These features not only enhance the technology for producing HLW forms, but also provide advantageous attributes to the waste form by allowing more durable alternatives to glass. It is concluded that glass ceramic waste forms that are tailored to immobilize fission products of HLW can be can be made from the HLW processed with the CCIM. The advantageous higher temperatures reached with the CCIM and unachievable with JHM allows the lanthanides, alkali, alkaline earths, and molybdenum to dissolve into a molten glass. Upon controlled cooling they go into targeted crystalline phases to form a glass ceramic waste form with higher waste loadings than achievable with borosilicate glass waste forms. Natural cooling proves to be too fast for the formation of all targeted crystalline phases.

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A Bottom's-Up Model for Siting and Developing Consent-Based Disposal Solutions for SNF and HLW in the USA - 17332

At the end of 2016, the licensing and continued development of the USA's only candidate HLW-repository since 1987 at the Yucca Mountain (YM) site in Nevada had been on hold since 2010 pending the enactment of enabling legislation for one or more of the following paths forward: 1. Re-start of the YM HLW repository. 2. Consent-based siting and development (S and D) of new HLW-repositories for commingled disposal of commercially- (CHLW) and defense-generated (DHLW) HLW. 3. Consent-based S and D of a repository and/or deep boreholes for DHLW only. Public trust in the implementing and regulating entities and a definitive say in an apolitical S and D process by the directly affected parties (DAPs) are historical imperatives for gaining public acceptance and maintaining sustained support of any or all of them. However, due to the widespread negative legacy currently attributed to past politically-controlled S and D organizations, an even more politically controlled organizational structure and an amorphous, 'consent-based', S and D model like that introduced twice in proposed Senate bills since June 2013 will exacerbate, rather than mitigate, the main root causes to past contentions, lawsuits, delays, and cost-increases. We therefore recommend: 1) Assigning the responsibility for safe disposal of CHLW to an independent, chartered public corporation with requisite subject-matter expertise and adequate financial resources. 2) Enacting a related law that: a. Defines 'consent-based' in measurable terms; b. Assigns irrevocable veto rights to facility host state(s) based upon the majority opinion of its legal residents at pre-determined S and D milestones. c. Requires Congressional approval before the facility can open and close. (authors)

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Progress in demonstrating the performance of Engineered Barriers for the disposal of HLW and SNF: lab studies and demonstration experiments - 20293

Disposal of high-level radioactive waste (HLW) and spent nuclear fuels (SNF) in a geological disposal facility requires a fundamental understanding of the degradation processes of materials used in its engineered barrier system (EBS) over very long timescales. Beyond the wasteform itself (i.e. the borosilicate glass for HLW or the fuel matrix and cladding for SNF), materials often employed in a disposal concept include metallic containers (typically copper and/or carbon steel) and clay-based buffer materials (typically bentonite). In this paper we explore key developments on the long-term evolution of materials employed for the immobilisation, isolation and containment of HLW and SNF in a geological disposal facility, including nuclear glasses, candidate container materials and clay buffers. Our discussion is based on the latest findings from both experimental studies and in-situ demonstration experiments. We present relevant findings from the long-term evolution of HLW glasses (UK composition), metallic materials for the containment system (envisaged in Switzerland, Sweden, Canada and other countries), and bentonite clays (envisaged in many national disposal programmes). (authors)

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Effects of He Ion Irradiation in Simple Borosilicate Glasses for HLW Immobilisation - 20324

High-level radioactive waste (HLW) consists of fission products and minor actinides. Borosilicate glass is the host material of choice in most countries to safely immobilize HLW, followed by eventual geological disposal. HLW glasses will experience both self-heating and self-irradiation effects due to the decay of fission products and minor actinides present therein. During the first 500 years of geological disposal, beta-gamma decay will be the main source of radiation due to short half-lives of fission products, as compared to very long-lived actinides which will be responsible for irradiation over much longer timescales. High-energy alpha particles and alpha recoil nuclei can potentially have significant impact (stored energy, volume change, accumulated dose, chemical durability) on the performance of the wasteform over longer timescales. Thus, to ensure safe and economic disposal over geological periods (10{sup 4} - 10{sup 6} years), the assessment of performance and properties in terms of radiation effects becomes indispensable. This work aims to simulate the effects of alpha decay in radioactive waste glasses. Two international glasses, namely UK 'MW' lithium-sodium borosilicate and Indian sodium-barium borosilicate, which are being used as HLW immobilization matrices by the UK and India respectively, were prepared by a melt-quench method and annealed below their glass transition temperatures. Both glasses were irradiated with 650 KeV He{sup 2+} ions with doses ranging from 10{sup 15} to 10{sup 17} ions/cm{sup 2}. Structural analysis was carried out using electron paramagnetic resonance (EPR) and Raman spectroscopies. First derivative continuous wave EPR spectra were recorded for all pristine and irradiated glass monoliths at room temperature using an X-band (frequency 9.6 GHz) EPR Bruker spectrometer. Results from EPR analyses showed the formation of irradiation induced paramagnetic centers at g ∼ 2.00 in all irradiated glasses. Raman spectra of pristine and irradiated samples were acquired, and showed notable changes in glass structure post-irradiation, with the emergence of a broad Raman band at 1560 cm{sup -1} upon irradiation with high fluences. (authors)

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The Effects of Mixing Multi-Component HLW Glasses on Spinel Crystal Size

The Hanford Waste Treatment and Immobilization Plant will vitrify radioactive waste into borosilicate glass. The high-level waste (HLW) glass formulations are constrained by processing and property requirements, including restrictions aimed at avoiding detrimental impacts of spinel crystallization in the melter. To understand the impact of glass chemistry on crystallization, two HLW glasses precipitating small (?5 µm) spinel crystals were individually mixed with a glass that precipitated large (?45 µm) spinel crystals in ratios of 25, 50, and 75 wt%. The size of spinel crystals in the mixed glasses varied from 5 to 20 µm. Small crystal size was attributed to: (1) high concentrations of nuclei due to the presence of ruthenium oxide and (2) chromium oxide aiding high rates of nucleation. Results indicate that the spinel crystal size can be controlled using chromium oxide and/or noble metal concentrations in the melt, even in complex mixtures like HLW glasses. Small crystals tend to settle slowly, so they are acceptable in the melter without a risk of failure. Allowing higher concentrations of spinel-forming waste components in the waste glass enables glass compositions with higher waste loading, thus increasing plant operational flexibility. An additional benefit to the presence of chromium oxide in the glass composition is the potential for the oxide to protect melter walls against corrosion.

Lonergan, Charmayne E.↗

HLW Melter Control Strategy Without Visual Feedback

Plans for the treatment of high level waste (HL W) at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) are based upon the inventory of the tank wastes, the anticipated performance of the pretreatment processes, and current understanding of the capability of the borosilicate glass waste form. The WTP HLW melter design, unlike earlier DOE melter designs, incorporates an active glass bubbler system. The bubblers create active glass pool convection and thereby improve heat and mass transfer and increase glass melting rates. The WTP HLW melter has a glass surface area of 3.75 m 2 and depth of ~ 1.1 m. The two melters in the HLW facility together are designed to produce up to 7.5 MT of glass per day at 100% availability. Further increases in HL W waste processing rates can potentially be achieved by increasing the melter operating temperature above 1150°C and by increasing the waste loading in the glass product. Increasing the waste loading also has the added benefit of decreasing the number of canisters for storage.

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