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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

GeoMelt{sup R} In-Container Vitrification (ICV){sup TM} for Fukushima Daiichi Water Treatment Secondary Wastes - 20212

The Japanese government is supporting development work implemented jointly by Veolia subsidiaries Kurion Japan, K.K., Veolia Nuclear Solutions (VNS), Inc., and Veolia Nuclear Solutions Federal Services, LLC for treating radioactive waste generated from Fukushima Daiichi Nuclear Power Station (NPS) water treatment using the GeoMelt{sup TM} In-Container Vitrification (ICV){sup TM} technology. The initial work consisted of glass formulation and engineering-scale testing which was completed in 2018, in the frame of an IRID (International Research Institute for Nuclear Decommissioning) program as part of a project subsidized by Japan's Ministry of Economy, Trade and Industry (METI). The Fukushima Daiichi NPS Mid- and Long-Term Road-map requires investigation of methods to stabilize solid wastes (and to immobilize radioisotopes in the wastes) generated as a result of emergency response and decommissioning activities. Cooling water treatment has resulted in a significant amount of solid and slurry secondary wastes (mostly adsorbents and ion-exchange materials) which will require processing at some point. GeoMelt{sup R} ICV{sup TM} is a joule-heated melter technology which uses a refractory-lined single-use container combining the melter and disposal container. There is no pouring required nor concerns with refractory corrosion which allows the process to accommodate a wide range of waste chemistries and high waste loadings. The testing described here consisted of three engineering-scale melts, each processing between 212 kg and 240 kg of waste simulants, glass formers, and non-radioactive cesium (Cs) and strontium (Sr) tracers. Continuous isokinetic stack sampling of off-gas emissions was performed for each test in order to calculate Cs and Sr retention in the glass wasteform. Single-pass retention of Cs in the final glass wasteform ranged from 91.46 to 99.30%, and single-pass retention of Sr ranged from 99.76 to 100%. Planned particulate recycle will increase these retention levels. Melt 1 processed a mixture of KUR-EH (a zeolite-based ion-exchange material), simulated Advanced Liquid Processing System (ALPS) Carbonate and Iron Slurries, and glass additives. Melt 2 processed a mixture of KUR-EH, KUR-TSG (a titanate-based adsorbent), and glass additives. Melt 3 processed a mixture of KUR-EH, simulated barium sulfate/iron ferrocyanide sludge (AREVA sludge), and glass additives. Waste loadings for these melts ranged from 70 weight percent (wt%) to 82 wt%. Vitrification produces a waste form much denser than the stored water treatment secondary waste wastes, resulting in significant volume reduction. Volume reductions for the three tests ranged from 74 to 79 vol%. Vitrification produces a chemically durable wasteform. Pacific Northwest National Laboratory (PNNL) tested three glass samples from each engineering-scale melt) by the Materials Characterization Center 1 (MCC-1) test, an international standard leach test of the chemical durability of nuclear waste glasses. PNNL also obtained one U.S. reference glass (EA Glass) and two Japan reference glasses P0798) and tested these under the same MCC-1 conditions (90 deg. C, 10 m-1, DIW, and 7, 14, 28-day) as the GeoMelt{sup R} ICV{sup TM} glasses. The GeoMelt{sup R} ICV{sup TM} glasses exhibited lower total normalized releases and 14- to 28-day normalized release rates than the three reference glasses. These results suggest that the GeoMelt{sup R} ICV{sup TM} glasses have durabilities on par with high-level waste glasses under standard test conditions. Post-melt process sampling and analysis indicated no Cs migration into the melter refractory materials and very little deposition of Cs or Sr onto the melter hood or off-gas piping internals. The results of the testing indicated good Cs retention in the glass, high volume reduction and waste loadings, and excellent chemical durability. These factors are important to minimize treatment costs and to protect workers and the environment. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Alloying of Pu-Al with Stainless Steel for Material Disposition

The Savannah River National Laboratory (SRNL) has evaluated several options for the disposition of stainless-steel clad plutonium metal alloy. One of the technologies under consideration is alloying of the material with stainless steel (SS). The resulting SS-Pu alloy would be a non-proliferable waste form consisting of a secondary Pu composition region microencapsulated in the refractory stainless steel. Two 8-kg ingots were made at SS-1.8Zr-0.4Pu alloys (wt %); 8 kg was determined in a previous study to be the maximum mass of SS ingot at the maximum target Pu loading of 350-g that would result in a SS-4.4Pu alloy (wt %). Two smaller 500-g ingots were also produced at SS-1.6Zr-1.4Pu and SS-1.4Pu (wt %). The 500-g ingots evaluated alloying at a higher Pu concentration than in the 8 kg ingots, and they evaluated the necessity of adding Zr metal to incorporate the Pu and control Pu oxidation. Zr addition was found to be unnecessary to incorporate the Pu and control Pu oxidation. Drill turnings were collected from the large and small ingots and metallographic samples were directly cut from the small ingots. Both were analyzed to validate the structure and composition region formation. Chemical analyses of turnings proved that the Pu was dispersed within the SS ingots.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Corrosion Behavior and Microstructure Influence of Glass-Ceramic Nuclear Waste Forms

Glass ceramic waste forms present a potentially viable technology for the long term immobilization and disposal of liquid nuclear wastes. Through control of chemistry during fabrication, such waste forms can have designed secondary crystalline phases within a borosilicate glass matrix. In this work, a glass ceramic containing powellite and oxyapatite secondary phases was tested for its corrosion properties in dilute conditions using single pass flow through testing (SPFT). Three glass ceramic samples were prepared using different cooling rates to produce samples with varying microstructure sizes. In testing at 90 °C in buffered pH 7 and pH 9 solutions, it was found that increasing pH and decreasing microstructure size (resulting from rapid cooling during fabrication) both led to a reduction in overall corrosion rate. The phases of the glass ceramic were found, using a combination of solutions analysis, SEM and AFM, to corrode preferably in the order of powellite > bulk glass matrix > oxyapatite.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2020

Drying Spent Magnox Fuel for Interim Dry Storage

Spent Magnox fuel is usually stored under water for shielding and cooling following use in-reactor, but the storage water can react with Magnox clad fuel and cause corrosion and forms a sludge which generates a secondary waste product. One option to prevent unwanted corrosion and avoid expensive waste management is to dry the wet fuel. This project aims to test a drying process which will convert wet and corroded Magnox fuel to a stable form to demonstrate viability for conversion from wet to dry storage. Samples of corroded Magnox supplied by National Nuclear Laboratory. Corrosion product retrieved by various methods including dry scraping, ultrasonic treatment to form sludge and sludge drying to isolate suspension. TGA undertaken on Sample 1 and Sample 2, with brucite and hydromagnesite for comparison. Both samples showed ∼10% mass loss up to 250 deg. C attributable to water held in sample. Mass loss from dehydroxylation which liberates further water in both samples. TGA data plotted alongside chemically pure brucite and hydromagnesite shows expected similarities/differences between Sample 1(mostly brucite) and Sample 2 (brucite/hydromagnesite mixture). Following treatment, dried samples observed to slowly gain mass in ambient conditions. Presumed to be hygroscopic absorption of air water vapour as effect is reversible, with similar effect observed for hydromagnesite and brucite. Etched Magnox vacuum dried for 3.5 h at 90 deg. C to test for reaction with residual water - some discoloration but no noticeable corrosion observed. Drying etched Magnox metal to observe surface effects/corrosion during drying process.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2014

SRNL CRP progress report [Development of Melt Processed Ceramics for Nuclear Waste Immobilization]

A multi-phase ceramic waste form is being developed at the Savannah River National Laboratory (SRNL) for treatment of secondary waste streams generated by reprocessing commercial spent nuclear. The envisioned waste stream contains a mixture of transition, alkali, alkaline earth, and lanthanide metals. Ceramic waste forms are tailored (engineered) to incorporate waste components as part of their crystal structure based on knowledge from naturally found minerals containing radioactive and non-radioactive species similar to the radionuclides of concern in wastes from fuel reprocessing. The ability to tailor ceramics to mimic naturally occurring crystals substantiates the long term stability of such crystals (ceramics) over geologic timescales of interest for nuclear waste immobilization [1]. A durable multiphase ceramic waste form tailored to incorporate all the waste components has the potential to broaden the available disposal options and thus minimize the storage and disposal costs associated with aqueous reprocessing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles: CRP T21027 1813: Processing technologies for high level waste, formulation of matrices and characterization of waste forms, Task 17208 (Final Report)

A multi-phase ceramic waste form is being developed at the Savannah River National Laboratory (SRNL) for treatment of secondary waste streams generated by reprocessing commercial spent nuclear. The envisioned waste stream contains a mixture of transition, alkali, alkaline earth, and lanthanide metals. Ceramic waste forms are tailored (engineered) to incorporate waste components as part of their crystal structure based on knowledge from naturally found minerals containing radioactive and non-radioactive species similar to the radionuclides of concern in wastes from fuel reprocessing. The ability to tailor ceramics to mimic naturally occurring crystals substantiates the long term stability of such crystals (ceramics) over geologic timescales of interest for nuclear waste immobilization [1]. A durable multi-phase ceramic waste form tailored to incorporate all the waste components has the potential to broaden the available disposal options and thus minimize the storage and disposal costs associated with aqueous reprocessing. This report summarizes results from three years of work on the IAEA Coordinated Research Project on “Processing technologies for high level waste, formulation of matrices and characterization of waste forms” (T21027), and specific task “Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles” (17208).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles CRP T21027 1813: Processing technologies for high level waste, formulation of matrices and characterization of waste forms, Task 17208 (Final Report)

A multi-phase ceramic waste form is being developed at the Savannah River National Laboratory (SRNL) for treatment of secondary waste streams generated by reprocessing commercial spent nuclear. The envisioned waste stream contains a mixture of transition, alkali, alkaline earth, and lanthanide metals. Ceramic waste forms are tailored (engineered) to incorporate waste components as part of their crystal structure based on knowledge from naturally found minerals containing radioactive and non-radioactive species similar to the radionuclides of concern in wastes from fuel reprocessing. The ability to tailor ceramics to mimic naturally occurring crystals substantiates the long term stability of such crystals (ceramics) over geologic timescales of interest for nuclear waste immobilization. A durable multi-phase ceramic waste form tailored to incorporate all the waste components has the potential to broaden the available disposal options and thus minimize the storage and disposal costs associated with aqueous reprocessing. This report summarizes results from three years of work on the IAEA Coordinated Research Project on “Processing technologies for high level waste, formulation of matrices and characterization of waste forms” (T21027), and specific task “Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles” (17208).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Candidate Low-Temperature Glass Waste Forms for Technetium-99 Recovered from Hanford Effluent Management Facility Evaporator Concentrate

Alternative treatment and disposition options may exist for technetium-99 (99Tc) in secondary liquid waste from the Hanford Direct-Feed Low-Activity Waste (DFLAW) process. One approach includes development of an alternate glass waste form that is suitable for on-site disposition of technetium, including salts and other species recovered by ion exchange or precipitation from the EMF evaporator concentrate. By recovering the Tc content from the stream, and not recycling the treated concentrate, the DFLAW process can potentially be operated in a more efficient manner that lowers the cost to the Department of Energy. This report provides a survey of candidate glass formulations and glass-making processes that can potentially incorporate technetium at temperatures <700 °C to avoid volatilization. Three candidate technetium feed streams are considered: (1) dilute sodium pertechnetate loaded on a non-elutable ion exchange resin; (2) dilute sodium-bearing aqueous eluent from ion exchange recovery of pertechnetate, or (3) technetium(IV) oxide precipitate containing Sn and Cr solids in an aqueous slurry. From the technical literature, promising candidate glasses are identified based on their processing temperatures and chemical durability data. The suitability and technical risk of three low-temperature glass processing routes (vitrification, encapsulation by sintering into a glass composite material, and sol-gel chemical condensation) for the three waste streams was assessed, based on available low-temperature glass data. For a subset of candidate glasses, their long-term thermodynamic behavior with exposure to water and oxygen was modeled using Geochemist’s Workbench, with and without addition of reducing stannous ion. For further evaluation and development, encapsulation of precipitated TcO2/Sn/Cr in a glass composite material based on lead-free sealing glasses is recommended as a high priority. Vitrification of pertechnetate in aqueous anion exchange eluent solution using a high lead content borate glass, or other low melting glass is also recommended for further evaluation and development. Additional laboratory studies of phase behavior and chemical durability of low-temperature glasses is also recommended to provide risk mitigation if one of the primary development paths proves infeasible. This report is a deliverable for the task “Candidate Low-T Glass Waste Forms for EMF Bottoms On-Site Disposition Alternative Option.”

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Screening of Additional Candidate Low-Temperature Glasses for Technetium Recovered from Hanford Effluent Management Facility Evaporator Bottoms

In this annex to a previously reported study, a series of laboratory screening tests was conducted to identify low-temperature glasses that have significant potential for use in disposition of technetium from a Hanford Tank Waste Treatment & Immobilization Plant (WTP) secondary liquid waste stream. Specifically, a glass waste form is sought that would be suitable for on-site disposition of technetium, salts, and other species in a Tc-rich stream recovered by ion exchange from the future Effluent Management Facility (EMF) evaporator concentrate. In the current study, several additional candidate glasses were identified, and testing of previous candidates was extended to include the Toxicity Characteristic Leaching Procedure (TCLP). In non-radioactive testing with rhenium surrogate, new formulations incorporated a simulated ion exchange eluate at temperatures below 750 °C to produce an amorphous, or mixed crystalline-amorphous, product. Incorporation of technetium (NaTcO 4 )-containing simulated eluate was evaluated for two of these glasses. Technetium was not retained well in these glasses, confounding the previous conclusion that Tc volatilization during vitrification can be reduced by appropriate selection of low-temperature glasses. Preliminary data for additional low-temperature glass compositions and recommendations for future work are provided. This report is a deliverable associated with requisition 55068-004-03 NFE-17-0020 "Candidate Low-T Glass Waste Forms for EMF Bottoms On-Site Disposition Alternative."

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

The Effect of Ettringite on Cementitious Waste Form Development for Low- Activity Waste - 17170

The current Cast Stone formulation, with 8% ordinary Portland cement (OPC), 45% fly ash (FA), and 47% blast furnace slag (BFS), proposed for cementitious waste forms (CWFs) at the Hanford site has been shown to be inadequate for secondary liquid wastes sent to the Effluent Treatment Facility (ETF). This is due to the high sulfate concentrations and non-alkaline conditions present in the ETF waste stream that lead to the late formation of ettringite, [Ca{sub 6}Al{sub 2}(SO{sub 4}){sub 3}(OH){sub 12}.26(H{sub 2}O)], which can consequently cause undesirable swelling and cracks in the CWF that facilitate {sup 99}Tc release. To overcome this challenge, hydrated lime (HL), Ca(OH){sub 2}, can be used instead of FA to provide the Ca necessary to sequester sulfate early in the cast stone curing process through early formation of ettringite. Early ettringite formation minimizes the risk of localized disruptive action or harmful stress that lead to undesirable swelling and cracking of the CWF. Furthermore, early formation reduces the permeability of the CWF, further reducing the risk of {sup 99}Tc release and increasing structural stability. Two liquid waste simulants, 1) WTP off-gas condensate (WTP) and 2) Effluent Management Facility (EMF) process condensate combined with low activity waste (LAW) caustic scrubber (labeled EMF/CS), were prepared and tested for ettringite formation effects on HL-containing CWF development and {sup 99}Tc leachability. After curing for 28 days, X-ray diffraction analysis revealed that ettringite was formed in the early stages of curing for the CWFs prepared using both simulants. However, because of the higher sulfate concentration in the EMF/CS simulant and limited Ca and Al sources, some sulfate did not form ettringite during the early stages of curing, resulting in significant monolith swelling and cracking during subsequent leaching tests. Despite observable cracking in monoliths prepared with the EMF/CS simulant, low {sup 99}Tc release from HL-based waste forms was measured in later leaching periods tested by the EPA Method 1315 in both simulants. Ettringite-{sup 99}Tc co-precipitation batch experiments support a possible chemical sequestration mechanism that is hypothesized to contribute to the observed low {sup 99}Tc leach rates, which are likely the result of an additional chemical reaction that sequesters {sup 99}Tc rather than simply physical factors such as reduced porosity and permeability (or tortuosity). Overall these findings quantitatively support the use of HL to overcome the deleterious effects of sulfate-rich conditions on CWFs through early formation of ettringite and provide evidence for {sup 99}Tc release rates that fall within low risk levels reported by the United States Department of Energy (US DOE). (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Hot Isostatic Pressing of Engineered Forms of I-AgZ

Hot isostatic pressing (HIP) is being considered for direct conversion of 129 I-bearing materials to a radiological waste form. The removal of volatile radioactive 129 I from the off-gas of a nuclear fuel reprocessing facility will be necessary to comply with regulatory requirements regarding reprocessing facilities sited within the United States, and any iodine-containing media or solid sorbents generated by offgas abatement will require disposal. Zeolite minerals such as silver-exchanged mordenite (AgZ) have been studied as potential iodine sorbents and will contain 129 I as chemisorbed AgI. Oak Ridge National Laboratory (ORNL) has conducted several recent studies on the HIP of both iodine-loaded AgZ (I-AgZ) and other iodine-bearing zeolite minerals. The goal of these research efforts is to achieve a stable, highly leach resistant material that is reduced in volume as compared to bulk iodine-loaded I-AgZ. Through the use of HIP, it may be possible to achieve this with the addition of little or no additional materials (waste formers). Other goals for the process include that the waste form will be tolerant to high temperatures and pressures, not chemically hazardous, and that the process will result in minimal secondary waste generation. This document describes the preparation of 27 samples that are distinct from previous efforts in that they are prepared exclusively with an engineered form of AgZ that is manufactured using a binder. Iodine was incorporated solely by chemisorption. This base material is expected to be more representative of an operational system than were samples prepared previously with pure minerals.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Predicting zeolites’ stability during the corrosion of nuclear waste immobilization glasses: Comparison with glass corrosion experiments

During the long-term corrosion of nuclear waste glasses under nuclear waste disposal conditions, the precipitation of zeolitic phases has been linked to a delayed acceleration in glass corrosion (known as “Stage III”). Hence, predicting the thermodynamic propensity for zeolites to form upon the dissolution of nuclear waste glasses is key to ensure their long-term performance. Here, we compile a unified, internally-consistent thermodynamic database “clay20” to estimate the stability of clay and feldspar phases relevant to nuclear waste immobilization glasses, including beidellite(Mg, Ca, Na, K), kaolinite, montmorillonite(Mg, Ca, Na, K), nontronite(Mg, Ca, Na, K), saponite(Ca, Na, K), and albite. Based on this, we report a geochemical modeling method allowing us to predict the stability of secondary phases (including zeolites, calcium–silicate–hydrate gels, and clays) upon the dissolution of nuclear waste immobilization glasses. We show that this approach offers a realistic description of the stability of the secondary phases forming during the dissolution of two archetypical model nuclear glasses (namely, the International Simple Glass, ISG, and WVUTh-203) under conditions relevant to nuclear waste disposal (T = 90°C, p = 1 bar) as a function of pH. We find that the formation of silica and clay secondary phases is thermodynamically favored at low pH (pH < 10), whereas, in contrast, zeolite (analcime) and calcium–silicate–hydrate phases are favored at high pH (pH > 10.5). This suggests that thermodynamics (i.e., not solely kinetics) plays a key role in determining the range of solution pH wherein stage III corrosion may occur, i.e., when zeolite formation is favored.

Zhen-Wu, Bi Yun↗
DOE OSTI2012

Iron oxide waste form for stabilizing 99 Tc

Crystals of goethite were synthesized with reduced technetium [{sup 99}Tc(IV)] incorporated within the solid lattice. The presence of {sup 99}Tc(IV) as a substituting cation in the matrix and 'armoring' by an additional layer of precipitated goethite isolated the reduced {sup 99}Tc(IV) from oxidizing agents. These products were used to make monolithic pellets to quantify an effective diffusion coefficient for {sup 99}Tc from goethite waste form contacted with a synthetic Hanford IDF (integrated disposal facility) pore water solution (pH = 7.2, I = 0.05 M) at room temperature for up to 120 days in static reactors. XANES analysis of the goethite solids recovered post-run demonstrated that the {sup 99}Tc in the goethite crystals remains in the reduced {sup 99}Tc(IV) state. The slow release of pertechnetate concentration with time in the static experiments with the monolith followed a square root of time dependence, consistent with diffusion control for {sup 99}Tc release. An apparent diffusion coefficient of 6.15 x 10{sup -11} cm{sup 2}/s was calculated for the {sup 99}Tc-goethite pellet sample and the corresponding leaching index (LI) was 10.2. The results of this study indicate that technetium can be immobilized in a stable, low-cost Fe oxide matrix that is easy to fabricate and these findings can be useful in designing long-term solutions for nuclear waste disposal.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2012

Conditioning of Boron-Containing Low and Intermediate Level Liquid Radioactive Waste - 12041

Improved cementation of low and intermediate level radioactive waste (ILW and LLW) aided by vortex electromagnetic treatment as well as silica addition was investigated. Positive effects including accelerated curing of boron-containing cement waste forms, improve end product quality, decreased product volume and reduced secondary LRW volume from equipment decontamination were established. These results established the possibility of boron-containing LRW cementation without the use of neutralizing alkaline additives that greatly increase the volume of the final product intended for long-term storage (burial). Physical (electromagnetic) treatment in a vortex mixer can change the state of LRW versus chemical treatment. By treating the liquid phase of cement solution only, instead of the whole solution, and using fine powder and nano-particles of ferric oxides instead of separable ferromagnetic cores for the activating agents the positive effect are obtained. VET for 1 to 3 minutes yields boron-containing LRW cemented products of satisfactory quality. Silica addition at 10 % by weight will accelerate curing and solidification and to decrease radionuclide leaching rates from boron-containing cement products. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Measurement of Iodine, Iodide, and Iodate in Hanford Tank Waste: Technology Transfer from PNNL to Hanford 222-S Laboratory

This report summarizes the measurement of the inorganic chemical forms of iodine in Hanford tank waste. The Hanford tank wastes have roughly a part per million iodine. Part of the iodine is the long-lived beta emitter 129I, and the rest is stable 127I. Because tank waste iodine is radioactive and radiotoxic, its chemical form must be known so that its behavior in the vitrification process can be reliably known and anticipated in various waste streams (glass, secondary liquid and solid waste, and offgas emissions) at Hanford. Iodine in tank wastes exists in the inorganic chemical forms iodide and iodate (and possibly also periodate) and also as organic forms such as alkyl iodides. The measurement of organic iodides is very different from the measurement of inorganic forms and is outside the scope of this report. The inorganic chemical forms are chemically separated, in sequence, from the raw tank waste using solvent extractions and several redox reactions, then measured by ICP-MS. The inorganic chemical forms of iodine are chemically reactive, and so is the tank waste. The chemistry must be carefully designed to avoid unintended reactions that could convert one form of iodine to another during the analysis, which would skew the data and report iodine in the wrong chemical form. This iodine analysis, developed at PNNL, is being transferred to the DOE 222-S Laboratory on the Hanford Site, in Washington State, for implementation during waste processing operations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Supplemental Immobilization of Hanford Low-Activity Waste: Cast Stone Screening Tests

More than 56 million gallons of radioactive and hazardous waste are stored in 177 underground storage tanks at the U.S. Department of Energy’s (DOE’s) Hanford Site in southeastern Washington State. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is being constructed to treat the wastes and immobilize them in a glass waste form. The WTP includes a pretreatment facility to separate the wastes into a small volume of high-level waste (HLW) containing most of the radioactivity and a larger volume of low-activity waste (LAW) containing most of the nonradioactive chemicals. The HLW will be converted to glass in the HLW vitrification facility for ultimate disposal at an offsite federal repository. At least a portion (~35%) of the LAW will be converted to glass in the LAW vitrification facility and will be disposed of onsite at the Integrated Disposal Facility (IDF). The pretreatment and HLW vitrification facilities will have the capacity to treat and immobilize the wastes destined for each facility. However, a second LAW immobilization facility will be needed for the expected volume of LAW requiring immobilization. A cementitious waste form known as Cast Stone is being considered to provide the required additional LAW immobilization capacity. The Cast Stone waste form must be acceptable for disposal in the IDF. The Cast Stone waste form and immobilization process must be tested to demonstrate that the final Cast Stone waste form can comply with the waste acceptance criteria for the disposal facility and that the immobilization processes can be controlled to consistently provide an acceptable waste form product. Further, the waste form must be tested to provide the technical basis for understanding the long-term performance of the waste form in the disposal environment. These waste form performance data are needed to support risk assessment and performance assessment (PA) analyses of the long-term environmental impact of the waste disposal in the IDF. The PA is needed to satisfy both Washington State IDF Permit and DOE Order requirements. Cast Stone has been selected for solidification of radioactive wastes including WTP aqueous secondary wastes treated at the Effluent Treatment Facility (ETF) at Hanford. A similar waste form called Saltstone is used at the Savannah River Site (SRS) to solidify its LAW tank wastes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

Report for Treating Hanford LAW and WTP SW Simulants: Pilot Plant Mineralizing Flowsheet

The US Department of Energy is responsible for managing the disposal of radioactive liquid waste in underground storage tanks at the Hanford site in Washington State. The Hanford waste treatment and immobilization plant (WPT) will separate the waste into a small volume of high level waste (HLW), containing most of the radioactive constituents, and a larger volume of low activity waste (LAW), containing most of the non-radioactive chemical and hazardous constituents. The HLW and LAW will be converted into immobilized waste forms for disposal. Currently there is inadequate LAW vitrification capacity planned at the WTP to complete the mission within the required timeframe. Therefore additional LAW capacity is required. One candidate supplemental treatment technology is the fluidized bed steam reformer process (FBSR). This report describes the demonstration testing of the FBSR process using a mineralizing flowsheet for treating simulated Hanford LAW and secondary waste from the WTP (WTP SW). The FBSR testing project produced leach-resistant solid products and environmentally compliant gaseous effluents. The solid products incorporated normally soluble ions into an alkali alumino-silicate (NaS) mineral matrix. Gaseous emissions were found to be within regulatory limits. Cesium and rhenium were captured in the mineralized products with system removal efficiencies of 99.999% and 99.998 respectively. The durability and leach performance of the FBSR granular solid were superior to the low activity reference material (LMR) glass standards. Normalized product consistency test (PCT) release rates for constituents of concern were approximately 2 orders of magnitude less than that of sodium in the Hanford glass [standard].

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

The surface structure of α-uranophane and its interaction with Eu(III) – An integrated computational and fluorescence spectroscopy study

Uranophane is a rare U(VI) secondary silicate mineral formed in nature by the oxidation of the primary mineral uraninite. It is also relevant to the long-term geochemistry of nuclear waste repositories, where it can be formed under oxidizing conditions and has the potential to act as a secondary barrier to the migration of radionuclides through mineral sorption reactions. A combination of classical molecular dynamics and ab-initio density functional theory (DFT) has been employed to investigate the uranophane|water interface as well as the interfacial reactivity of the U(VI) silicate toward acidic conditions and radionuclide ion sorption. The sorption simulations have been complemented by experimental sorption studies and laser induced fluorescence spectroscopy to help identify the molecular structure of the surface sorbed species. Experimental distances and essential coordination numbers are properly captured by the simulation results within bulk uranophane, while interfacial water is found to orient primarily with the hydrogen-atoms directed towards the negatively charged surface. Sorption sites for water are observed to belong to 3 different groups: (1) those involving uranyl oxygen, (2) involving uranyl and silica hydroxyl oxygen atoms, and (3) involving hydroxyl hydrogen. The pKa of the surface -OH groups have been calculated using a variety of models, including a bond valence approach and utilization of the energetics of deprotonation within DFT. Under basic conditions, deprotonation of the Si-OH groups is likely responsible for uranophane dissolution. Finally, the stability and structure of surface sorbed Eu3+ has been examined, with a stable inner-sphere species being observed.

Environmental Molecular Sciences Laboratory↗