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Leach testing of Tank C-104 residual waste was completed using batch and column experiments. Tank C-104 residual waste contains exceptionally high concentrations of uranium (i.e., as high as 115 mg/g or 11.5 wt.%). This study was conducted to provide data to develop contaminant release models for Tank C-104 residual waste and Tank C-104 residual waste that has been treated with lime to transform uranium in the waste to a highly insoluble calcium uranate (CaUO4) or similar phase. Three column leaching cases were investigated. In the first case, C-104 residual waste was leached with deionized water. In the second case, crushed grout was added to the column so that deionized water contacted the grout prior to contacting the waste. In the third case, lime was mixed in with the grout. Results of the column experiments demonstrate that addition of lime dramatically reduces the leachability of uranium from Tank C-104 residual waste. Initial indications suggest that CaUO4 or a similar highly insoluble calcium rich uranium phase forms as a result of the lime addition. Additional work is needed to definitively identify the uranium phases that occur in the as received waste and the waste after the lime treatment.

The Office of Material Management and Minimization (M3) Reactor Conversion Fuel Thermo-Physical Characterization Project at Pacific Northwest National Laboratory (PNNL) was tasked with using PNNL facilities and processes to receive irradiated low enriched uranium–molybdenum (LEU-Mo) fuel plate samples and perform analysis in support of the M3 Reactor Conversion Program. This work is in support of the M3 Reactor Conversion Fuel Development Pillar that is managed by Idaho National Laboratory. The primary research scope was to determine the thermo-physical properties as a function of temperature and burnup. Work conducted in Fiscal Year (FY) 2014 complemented measurements performed in FY 2013 on four additional irradiated LEU-Mo fuel plate samples. Specifically, the work in FY 2014 investigated the influence of different processing methods on thermal property behavior, the absence of aluminum alloy cladding on thermal property behavior for additional model validation, and the influence of higher operating surface heat flux / more aggressive irradiation conditions on thermal property behavior. The model developed in FY 2013 and refined in FY 2014 to extract thermal properties of the U-Mo alloy from the measurements conducted on an integral fuel plate sample (i.e., U-Mo alloy with a thin Zr coating and clad in AA6061) continues to performmore » very well. Measurements conducted in FY 2014 on samples irradiated under similar conditions compare well to measurements performed in FY 2013. In general, there is no gross influence of fabrication method on thermal property behavior, although the difference in LEU-Mo foil microstructure does have a noticeable influence on recrystallization of grains during irradiation. Samples irradiated under more aggressive irradiation conditions, e.g., higher surface heat flux, revealed lower thermal conductivity when compared to samples irradiated at moderate surface heat fluxes, with the exception of one sample. This report documents thermal property measurements conducted in FY 2014 and compares results to values obtained from literature and measurements performed in FY 2013, where applicable, along with appropriate discussion.« less

The U.S. Department of Energy Office of Nuclear Energy (DOE-NE), Office of Fuel Cycle Technology has established the Used Fuel Disposition Campaign (UFDC) to conduct the research and development activities related to storage, transportation, and disposal of used nuclear fuel (UNF) and high-level radioactive waste. Within the UFDC, the components for a general system model of the degradation and subsequent transport of UNF is being developed to analyze the performance of disposal options [Sassani et al., 2012]. Two model components of the near-field part of the problem are the ANL Mixed Potential Model and the PNNL Radiolysis Model. This report is in response to the desire to integrate the two models as outlined in [Buck, E.C, J.L. Jerden, W.L. Ebert, R.S. Wittman, (2013) “Coupling the Mixed Potential and Radiolysis Models for Used Fuel Degradation,” FCRD-UFD-2013-000290, M3FT-PN0806058]

The primary purpose of this report is to describe the strategy for coupling three process level models to produce an integrated Used Fuel Degradation Model (FDM). The FDM, which is based on fundamental chemical and physical principals, provides direct calculation of radionuclide source terms for use in repository performance assessments. The G-value for H2O2 production (Gcond) to be used in the Mixed Potential Model (MPM) (H2O2 is the only radiolytic product presently included but others will be added as appropriate) needs to account for intermediate spur reactions. The effects of these intermediate reactions on [H2O2] are accounted for in the Radiolysis Model (RM). This report details methods for applying RM calculations that encompass the effects of these fast interactions on [H2O2] as the solution composition evolves during successive MPM iterations and then represent the steady-state [H2O2] in terms of an “effective instantaneous or conditional” generation value (Gcond). It is anticipated that the value of Gcond will change slowly as the reaction progresses through several iterations of the MPM as changes in the nature of fuel surface occur. The Gcond values will be calculated with the RM either after several iterations or when concentrations of key reactants reach threshold values determined from previous sensitivity runs. Sensitivity runs with RM indicate significant changes in G-value can occur over narrow composition ranges. The objective of the mixed potential model (MPM) is to calculate the used fuel degradation rates for a wide range of disposal environments to provide the source term radionuclide release rates for generic repository concepts. The fuel degradation rate is calculated for chemical and oxidative dissolution mechanisms using mixed potential theory to account for all relevant redox reactions at the fuel surface, including those involving oxidants produced by solution radiolysis and provided by the radiolysis model (RM). The RM calculates the concentration of species generated at any specific time and location from the surface of the fuel. Several options being considered for coupling the RM and MPM are described in the report. Different options have advantages and disadvantages based on the extent of coding that would be required and the ease of use of the final product.

Assessing the performance of Spent (or Used) Nuclear Fuel (UNF) in geological repository requires quantification of time-dependent phenomena that may influence its behavior on a time-scale up to millions of years. A high-level waste repository environment will be a dynamic redox system because of the time-dependent generation of radiolytic oxidants and reductants and the corrosion of Fe-bearing canister materials. One major difference between used fuel and natural analogues, including unirradiated UO2, is the intense radiolytic field. The radiation emitted by used fuel can produce radiolysis products in the presence of water vapor or a thin-film of water that may increase the waste form degradation rate and change radionuclide behavior. To study UNF, we have been working on producing synthetic UO2 ceramics, or SimFuels that can be used in testing and which will contain specific radionuclides or non-radioactive analogs so that we can test the impact of radiolysis on fuel corrosion without using actual spent fuel. Although, testing actual UNF would be ideal for understanding the long term behavior of UNF, it requires the use of hot cells and is extremely expensive. In this report, we discuss, factors influencing the preparation of SimFuels and the requirements for dopants to mimic themore » behavior of UNF. We have developed a reliable procedure for producing large grain UO2 at moderate temperatures. This process will be applied to a series of different formulations.« less

Assessing the performance of spent (used) nuclear fuel in geological repository requires quantification of time-dependent phenomena that may influence its behavior on a time-scale up to millions of years. A high-level waste repository environment will be a dynamic redox system because of the time-dependent generation of radiolytic oxidants and reductants and the corrosion of Fe-bearing canister materials. One major difference between used fuel and natural analogues, including unirradiated UO2, is the intense radiolytic field. The radiation emitted by used fuel can produce radiolysis products in the presence of water vapor or a thin-film of water (including OH• and H• radicals, O2-, eaq, H2O2, H2, and O2) that may increase the waste form degradation rate and change radionuclide behavior. H2O2 is the dominant oxidant for spent nuclear fuel in an O2 depleted water environment, the most sensitive parameters have been identified with respect to predictions of a radiolysis model under typical conditions. As compared with the full model with about 100 reactions it was found that only 30-40 of the reactions are required to determine [H2O2] to one part in 10–5 and to preserve most of the predictions for major species. This allows a systematic approach for model simplification and offersmore » guidance in designing experiments for validation.« less

The objective of this paper is to investigate the transport of uranium oxide particles that may be present in carbon dioxide (CO2) gas coolant, into the graphite blocks of gas-cooled, graphite moderated reactors. The transport of uranium oxide in the coolant system, and subsequent deposition of this material in the graphite, of such reactors is of interest because it has the potential to influence the application of the Graphite Isotope Ratio Method (GIRM). The GIRM is a technology that has been developed to validate the declared operation of graphite moderated reactors. GIRM exploits isotopic ratio changes that occur in the impurity elements present in the graphite to infer cumulative exposure and hence the reactor’s lifetime cumulative plutonium production. Reference Gesh, et. al., for a more complete discussion on the GIRM technology.

The Hanford Site in Washington State manages 177 underground storage tanks containing approximately 250,000 m3 of waste generated during past defense reprocessing and waste management operations. These tanks contain a mixture of sludge, saltcake and supernatant liquids. The insoluble sludge fraction of the waste consists of metal oxides and hydroxides and contains the bulk of many radionuclides such as the transuranic components and 90Sr. The saltcake, generated by extensive evaporation of aqueous solutions, consists primarily of dried sodium salts. The supernates consist of concentrated (5-15 M) aqueous solutions of sodium and potassium salts. The 177 storage tanks include 149 single-shell tanks (SSTs) and 28 double -hell tanks (DSTs). Ultimately the wastes need to be retrieved from the tanks for treatment and disposal. The SSTs contain minimal amounts of liquid wastes, and the Tank Operations Contractor is continuing a program of moving solid wastes from SSTs to interim storage in the DSTs. The Hanford DST system provides the staging location for waste feed delivery to the Department of Energy (DOE) Office of River Protection’s (ORP) Hanford Tank Waste Treatment and Immobilization Plant (WTP). The WTP is being designed and constructed to pretreat and then vitrify a large portion of the wastesmore » in Hanford’s 177 underground waste storage tanks.« less

Roman glasses that have been in the sea or underground for about 1800 years can serve as the independent “experiment” that is needed for validation of codes and models that are used in performance assessment. Two sets of Roman-era glasses have been obtained for this purpose. One set comes from the sunken vessel the Iulia Felix; the second from recently excavated glasses from a Roman villa in Aquileia, Italy. The specimens contain glass artifacts and attached sediment or soil. In the case of the Iulia Felix glasses quite a lot of analytical work has been completed at the University of Padova, but from an archaeological perspective. The glasses from Aquileia have not been so carefully analyzed, but they are similar to other Roman glasses. Both glass and sediment or soil need to be analyzed and are the subject of this analytical plan. The glasses need to be analyzed with the goal of validating the model used to describe glass dissolution. The sediment and soil need to be analyzed to determine the profile of elements released from the glass. This latter need represents a significant analytical challenge because of the trace quantities that need to be analyzed. Both pieces of informationmore » will yield important information useful in the validation of the glass dissolution model and the chemical transport code(s) used to determine the migration of elements once released from the glass. In this plan, we outline the analytical techniques that should be useful in obtaining the needed information and suggest a useful starting point for this analytical effort.« less

This report summarizes the methodology used to test the sequestration of technetium-99 present in both deionized water and simulated Hanford Tank Waste Treatment and Immobilization Plant waste solutions.

The DOE Fuel Cycle Research & Development (FCR&D) Program is developing aqueous and electrochemical approaches to the processing of used nuclear fuel that will generate technetium-bearing waste streams. This final report presents Pacific Northwest National Laboratory (PNNL) research in FY10 to evaluate an iron-based alloy waste form for Tc that provides high waste loading within waste form processing limitations, meets waste form performance requirements for durability and the long-term retention of radionuclides and can be produced with consistent physical, chemical, and radiological properties that meet regulatory acceptance requirements for disposal.

Epsilon metal (e-metal) is generated in nuclear fuel during irradiation. This metal consists of Pd, Ru, Rh, Mo, and some Te. These accumulate at the UO2 grain boundaries as small (ca 5 µm) particles. These metals have limited solubility in the acid used to dissolve fuel during reprocessing and in typical borosilicate glass. These must be treated separately to improve overall waste loading in glass. This low solubility and their survival in 2 Gy-old natural reactors led us to investigate them as a waste form for the immobilization of 99Tc and 107Pd, two very long-lived isotopes.

This report describes characterization of a sample obtained from the 3714 building in the 300 Area. Characterization of this unknown material was required for the demonolition activities in the 300 Area. The object of the study was to dertermine the nature of the material, composition, possible structure, evidence for hazards components. The green material is a sodium alumino-silicate glass. This conclusion is based on the composition provided by SEM-EDS, and the images that suggest a glass-like morphology. Further analysis with Ramin and/or infrared could be used to determine the presence of any organics.

According to Bechtel National Inc.’s (BNI’s) Test Specification 24590-PTF-TSP-RT-06-006, Rev 0, “Simulant Development to Support the Development and Demonstration of Leaching and Ultrafiltration Pretreatment Processes,” simulants for boehmite, gibbsite, and filtration are to be developed that can be used in subsequent bench and integrated testing of the leaching/filtration processes. These simulants will then be used to demonstrate the leaching process and to help refine processing conditions that may impact safety basis considerations (Smith 2006). This report documents the results of the boehmite simulant development.

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan (Barnes and Voke 2006). The test program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Hanford Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Under test plan TP RPP WTP 467 (Fiskum et al. 2007), eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. Under this test plan, a waste testing program was implemented that included: • Homogenizing the archive samples by group as defined in the test plan. • Characterizing the homogenized sample groups. • Performing parametric leaching testing on each group for compounds of interest. • Performing bench-top filtration/leaching tests in the hot cell for each group to simulate filtration and leaching activities if they occurred in the UFP2 vessel of the WTP Pretreatment Facility. This report focuses on a filtration/leaching test performed using two of the eight waste composite samples. The sample groups examined in this report were the plutonium-uranium extraction (PUREX) cladding waste sludge (Group 3, or CWP) and reduction-oxidation (REDOX) cladding waste sludge (Group 4, or CWR). Both the Group 3 and 4 waste composites were anticipated to be high in gibbsite, thus requiring caustic leaching. WTP RPT 167 (Snow et al. 2008) describes the homogenization, characterization, and parametric leaching activities before benchtop filtration/leaching testing of these two waste groups. Characterization and initial parametric data in that report were used to plan a single filtration/leaching test using a blend of both wastes. The test focused on filtration testing of the waste and caustic leaching for aluminum, in the form of gibbsite, and its impact on filtration. The initial sample was diluted with a liquid simulant to simulate the receiving concentration of retrieved tank waste into the UFP2 vessel (< 10 wt% undissolved solids). Filtration testing was performed on the dilute waste sample and dewatered to a higher solids concentration. Filtration testing was then performed on the concentrated slurry. Afterwards, the slurry was caustic leached to remove aluminum present in the undissolved solid present in the waste. The leach was planned to simulate leaching conditions in the UFP2 vessel. During the leach, slurry supernate samples were collected to measure the dissolution rate of aluminum in the waste. After the slurry cooled down from the elevated leach temperature, the leach liquor was dewatered from the solids. The remaining slurry was rinsed and dewatered with caustic solutions to remove a majority of the dissolved aluminum from the leached slurry. The concentration of sodium hydroxide in the rinse solutions was high enough to maintain the solubility of the aluminum in the dewatered rinse solutions after dilution of the slurry supernate. Filtration tests were performed on the final slurry to compare to filtration performance before and after caustic leaching.

This is the final report in a series of eight reports defining characterization, leach, and filtration testing of a wide variety of Hanford tank waste sludges. The information generated from this series is intended to supplement the Waste Treatment and Immobilization Plant (WTP) project understanding of actual waste behaviors associated with tank waste sludge processing through the pretreatment portion of the WTP. The work described in this report presents information on a high-iron waste form, specifically the ferrocyanide tank waste sludge. Iron hydroxide has been shown to pose technical challenges during filtration processing; the ferrocyanide tank waste sludge represented a good source of the high-iron matrix to test the filtration processing.

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan.( ) The test program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Under test plan TP-RPP-WTP-467, eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. Under this test plan, a waste-testing program was implemented that included: • Homogenizing the archive samples by group as defined in the test plan • Characterizing the homogenized sample groups • Performing parametric leaching testing on each group for compounds of interest • Performing bench-top filtration/leaching tests in the hot cell for each group to simulate filtration and leaching activities if they occurred in the UFP2 vessel of the WTP Pretreatment Facility. This report focuses on filtration/leaching tests performed on two of the eight waste composite samples and follow-on parametric tests to support aluminum leaching results from those tests.

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan.() The test program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. The actual waste-testing program included homogenizing the samples by group, characterizing the solids and aqueous phases, and performing parametric leaching tests. Two of the eight defined groups—bismuth phosphate sludge (Group 1) and bismuth phosphate saltcake (Group 2)—are the subjects of this report. The Group 1 waste was anticipated to be high in phosphorus and was implicitly assumed to be present as BiPO4 (however, results presented here indicate that the phosphate in Group 1 is actually present as amorphous iron(III) phosphate). The Group 2 waste was also anticipated to be high in phosphorus, but because of the relatively low bismuth content and higher aluminum content, it was anticipated that the Group 2 waste would contain a mixture of gibbsite, sodium phosphate, and aluminum phosphate. Thus, the focus of the Group 1 testing was on determining the behavior of P removal during caustic leaching, and the focus of the Group 2 testing was on the removal of both P and Al. The waste-type definition, archived sample conditions, homogenization activities, characterization (physical, chemical, radioisotope, and crystal habit), and caustic leaching behavior as functions of time, temperature, and hydroxide concentration are discussed in this report. Testing was conducted according to TP-RPP-WTP-467.

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan.(a) The testing program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. The actual wastetesting program included homogenizing the samples by group, characterizing the solids and aqueous phases, and performing parametric leaching tests. Two of the eight defined groups—plutonium-uranium extraction (PUREX) cladding waste sludge (Group 3, or CWP) and reduction-oxidation (REDOX) cladding waste sludge (Group 4, or CWR)—are the subjects of this report. Both the Group 3 and 4 waste composites were anticipated to be high in gibbsite, requiring caustic leaching. Characterization of the composite Group 3 and Group 4 waste samples confirmed them to be high in gibbsite. The focus of the Group 3 and 4 testing was on determining the behavior of gibbsite during caustic leaching. The waste-type definition, archived sample conditions, homogenization activities, characterization (physical, chemical, radioisotope, and crystal habit), and caustic leaching behavior as functions of time, temperature, and hydroxide concentration are discussed in this report. Testing was conducted according to TP-RPP-WTP-467.

Analytical electron microscopy using SEM and TEM has been used to analyze a ~5 g. ingot with composition 71.3 wt% 316SS-5.3 wt% Zr-13.2 wt% Mo-4.0 wt% Rh-6.2 wt% Re prepared at the Idaho National Laboratory. Four phase fields have been identified two of which are lamellar eutectics, with a fifth possibly present. A Zr rich phase was found distributed as fine precipitate, ~10µm in diameter, often coating large cavities. A Mo-Fe-Re-Cr lamellar eutectic phase field appears as blocky regions ~30µm in diameter, surrounded by a Fe-Mo-Cr lamellar eutectic phase field, and that in turn is surrounded by a Zr-Fe-Rh-Mo-Ni phase field. The eutectic phase separation reactions are different. The Mo-Fe-Re-Cr lamellar eutectic appears a result of austenitic steel forming at lower volume fraction within an Mo-Fe-Re intermetallic phase, whereas the Fe-Mo-Cr lamellar eutectic may be a result of the same intermetallic phase forming within a ferritic steel phase. Cavitation may have arisen either as a result of bubbles, or from loss of equiaxed particles during specimen preparation.

This report describes the bench-scale pretreatment processing of actual tank waste materials through the entire baseline WTP pretreatment flowsheet in an effort to demonstrate the efficacy of the defined leaching processes on actual Hanford tank waste sludge and the potential impacts on downstream pretreatment processing. The test material was a combination of reduction oxidation (REDOX) tank waste composited materials containing aluminum primarily in the form of boehmite and dissolved S saltcake containing Cr(III)-rich entrained solids. The pretreatment processing steps tested included • caustic leaching for Al removal • solids crossflow filtration through the cell unit filter (CUF) • stepwise solids washing using decreasing concentrations of sodium hydroxide with filtration through the CUF • oxidative leaching using sodium permanganate for removing Cr • solids filtration with the CUF • follow-on solids washing and filtration through the CUF • ion exchange processing for Cs removal • evaporation processing of waste stream recycle for volume reduction • combination of the evaporated product with dissolved saltcake. The effectiveness of each process step was evaluated by following the mass balance of key components (such as Al, B, Cd, Cr, Pu, Ni, Mn, and Fe), demonstrating component (Al, Cr, Cs) removal, demonstrating filterability by evaluating filtermore » flux rates under various processing conditions (transmembrane pressure, crossflow velocities, wt% undissolved solids, and PSD) and filter fouling, and identifying potential issues for WTP. The filterability was reported separately (Shimskey et al. 2008) and is not repeated herein.« less

This project had two primary objectives. The first was to understand the physical properties and behavior of select Hanford tank sludges under conditions that might exist during retrieval, treatment, packaging, and transportation for disposal at the Waste Isolation Pilot Plant (WIPP). The second objective was to develop a fundamental understanding of these sludge suspensions by correlating the macroscopic properties with particle interactions occurring at the colloidal scale. The specific tank wastes considered herein are contained in thirteen Hanford tanks including three double-shell tanks (DSTs) (AW-103, AW-105, and SY-102) and ten single-shell tanks (SSTs) (B-201 through B-204, T-201 through T-204, T-110, and T-111). At the outset of the project, these tanks were designated as potentially containing transuranic (TRU) process wastes that would be treated and disposed of in a manner different from the majority of the tank wastes.

We considered a sorption model containing the minimal dynamic features of the system to fit plutonium adsorption data similar to that developed by Painter et al. (2002). Global fits to recent data favored nonzero values of reversible sorption, allowing the definition of equilibrium distribution coefficients in all cases except the synthetic form of montmorillonite. In most cases, the two-site model was adequate to fit the data. The model represents a mathematic simplification of the time-dependent sorption process and takes no account for pH-dependent surface charge changes and actinide-mineral surface interfacial chemistry. However, this allows the model to be readily incorporated into existing performance assessment codes when applied to repository environment relevant data sets.

Spent fuel tests in support of Yucca Mountain have been performed for many years. Most of these tests have been either single-pass flowthrough (SPFT) or unsaturated drip tests that have been used to elucidate waste form degradation rates. In general, the tests have been considered accelerated tests per the definition found in ASTM Standard C1174 in that either the temperature or flow rate has been increased in order to increase the rate of alteration. However, as the design and models for the proposed repository have solidified, it is clear that much of what was originally considered an accelerated test is, in reality, either a service condition test or a test that determines bounding conditions that grossly overestimate radionuclide degradation and release rates under repository relevant conditions. This presentation will examine the factors that need to be considered for future waste form, including waste package internals, degradation tests.

There has been superb progress in understanding the neutrino sector of elementary particle physics in the past few years. It is now widely recognized that the possibility exists for a rich program of measuring CP violation and matter effects in future accelerator {nu} experiments, which has led to intense efforts to consider new programs at neutrino superbeams, off-axis detectors, neutrino factories and beta beams. However, the possibility of measuring CP violation can be fulfilled only if the value of the neutrino mixing parameter {theta}{sub 13} is such that sin{sup 2} (2{theta}{sub 13}) greater than or equal to on the order of 0.01. The authors of this white paper are an International Working Group of physicists who believe that a timely new experiment at a nuclear reactor sensitive to the neutrino mixing parameter {theta}{sub 13} in this range has a great opportunity for an exciting discovery, a non-zero value to {theta}{sub 13}. This would be a compelling next step of this program. We are studying possible new reactor experiments at a variety of sites around the world, and we have collaborated to prepare this document to advocate this idea and describe some of the issues that are involved.

Colloids have the potential to transport strongly sorbing radionuclide contaminants in soils and groundwater aquifers. Recent studies from the Nevada Test Site have indicated the enhanced mobility plutonium, albeit in minute quantities, associated with various silicate minerals (Kersting et al., 1999); however, significant colloidal transport of thorium (Th) and rare earths (RE) in nature, considered to be chemical analogs for plutonium, is rare. Yet, the current Yucca Mountain model for colloids would have predicted extensive Th- and RE migration, given these phases' association with clay minerals. Several studies have pointed to the effect of water flow rate on colloid and particulate migration. In this paper, we examine the benefit of relating water flow rate and the wasteform alteration structure to colloid release.

In this document, we summarize our study of the effects of radiation induced damage to the titanate ceramics that were to be the immobilization form for surplus weapons-grade Pu. In this study, we made five ceramic materials: pure-phase pyrochlore, pure-phase zirconolite, pyrochlore-rich baseline, zirconolite-rich baseline, and impurity baseline. Two-hundred specimens were made of which 130 contained approximately 10 mass% 238Pu and 70 contained 10 mass% 239Pu. The specimens containing 239Pu served as materials against which the behavior of the 238Pu-bearing specimens could be compared. In our studies, we measured the true density (density exclusive of surface connected porosity), bulk density, crystalline-phase composition with X-ray diffraction (XRD), and dissolution rates as radiation induced damage accumulated in the 238Pu-bearing specimens. We routinely took photographs of the specimens during each characterization period. From our studies, we determined that these materials swell less than 10% and generally less than 5%. As the material swells, some open porosity can be converted to closed porosity, often causing the true density to decrease more rapidly than the bulk density. In general, 3?1018 a/g of damage accumulation were required for the materials to become amorphous as determined with the XRD method. The order in which the phases becamemore » amorphous was brannerite, pyrochlore, and zirconolite with brannerite being the most susceptible to radiation induced damage. However, we also show that Pu is not evenly distributed amongst the phases when multiple phases are present. We were unsuccessful in making a pure brannerite to study. Therefore, the brannerite was always present with other phases. For a material containing about 10 mass% 239Pu, 3?1018 a/g represent about 500 years in the geologic repository. At no time in our studies was there evidence for microcracking in these materials, even upon close examination in a scanning-electron microscope . Upon careful comparison between the dissolution behavior of non-radioactive, 238Pu-bearing, and 239Pu-bearing titanate ceramic specimens of the same composition, we see no difference in the dissolution rates of the three materials. Our results reported earlier suggested that the concentrations were affected by the radiolysis of the water in the dissolution tests with the 238Pu-bearing specimens, which have an intense local radiation field that does not exist for the 239Pu-bearing ceramics. This means that there is no effect of radiation induced damage on the forward dissolution rate of these ceramics. The results from this study show that the titanate ceramic is a viable immobilization form for the disposition of surplus weapons-grade Pu in a geologic repository. As the material becomes amorphous over approximately 500 years, no change to its dissolution rate will take place nor will the surface area of the ceramic increase from extensive microcracking. Therefore, the safety case that was used for the initial assessment of the performance of the titanate ceramic in the Yucca Mountain repository is valid.« less

This study examines existing data on Np behavior from both spent fuel and borosilicate glass tests in effort to resolve issues concerning the selection of possible solubility limiting phases for neptunium and the methods for detecting neptunium at low levels in spent fuel. These issues were raised in a recent report by Finch and Fortner (2002) that argues that the Np analysis with Electron Energy-Loss Spectroscopy (EELS) reported by Buck et al., (1998) is incorrect and that based on a series of experiments with Np-doped U3O8, NpO2 should be adopted as the solubility controlling phase for Np, in the Yucca Mountain performance assessment model. In this report, we will refute the claim that EELS is unable to detect Np and will suggest that the use of NpO2 as the Np solubility controlling phase is not supported by available scientific data from both spent fuel and borosilicate glass.

Neptunium, because of its long half life, is an element of long-term interest to the Yucca Mountain repository. The fate of neptunium under repository settings is unknown. This report provides a review and new interpretation of past tests on commercial spent nuclear fuel and experimental evidence on the fate of neptunium. Tests on commercial spent nuclear fuel preformed previously at Pacific Northwest National Laboratory (PNNL) used a bathtub setup by immersing spent fuel in either deionized water or a groundwater typical of those at Yucca Mountain. The main goal of the tests was to determine the different concentrations of radionuclides in solution with different types of cladding defects. Neptunium was not the focus of these tests, nor were the tests designed to study neptunium. Drip tests performed at Argonne National Laboratory (ANL) are unsaturated tests that drip water at different rates on spent fuel. Relatively new tests at ANL examine the corrosion of Np-doped U3O8 in humid air at various temperatures. This review concludes that all tests reported here have analytical problems (i.e., relatively high detection limits for Np) and have been configured such that they limit the ability to interpret the available neptunium data. Past tests on spent nuclearmore » fuel do not unambiguously describe neptunium chemistry as there are multiple mechanisms that may explain the observed behavior in each test. One apparently major shortcoming of most tests is that the extent of fuel reaction was limited by the amount of oxygen present in the system. Further detailed studies under repository-relevant conditions, which include the assumption of a constant 20 percent oxygen atmosphere, are needed to provide the data necessary for the development and validation of models used to predict the long-term fate of neptunium and other radionuclides at Yucca Mountain.« less

We have conducted static dissolution tests to study the corrosion behavior of the Environmental Assessment (EA) glass, which is the benchmark glass for high-level waste glasses being produced at US Department of Energy facilities. These tests were conducted to evaluate the behavior of the EA glass under the same long-term and accelerated test conditions that are being used to evaluate the corrosion of waste glasses. Tests were conducted at 90 C in a tuff groundwater solution at glass surface area/solution volume (WV) ratios of about 2000 and 20,000 m{sup {minus}1}. The glass dissolved at three distinct dissolution rates in tests conducted at 2000 m{sup {minus}1}. Based on the release of boron, dissolution within the first seven days occurred at a rate of about 0.65 g/(m{sup 2} {center_dot} d). The rate between seven and 70 days decreased to 0.009 g/(m{sup 2} {center_dot} d). An increase in the dissolution rate occurred at longer times after the precipitation of zeolite phases analcime, gmelinite, and an aluminum silicate base. The dissolution rate after phase formation was about 0.18 g/(m{sup 2} {center_dot} d). The formation of the same zeolite alteration phases occurred after about 20 days in tests at 20,000 m{sup {minus}}. The average dissolutionmore » rate over the first 20 days was 0.5 g/(m{sup 2} {center_dot} d) and the rate after phase formation was about 0.20 g/(m{sup 2} {center_dot} d). An intermediate stage with a lower rate was not observed in tests at 20,000 m{sup {minus}1}. The corrosion behavior of EA glass is similar to that observed for other high-level waste glasses reacted under the same test conditions. The dissolution rate of EA glass is higher than that of other high-level waste glasses both in 7-day tests and after alteration phases form.« less

This document reports on the work done by the Nuclear Waste Management Section of the Chemical Technology Division of Argonne National Laboratory in the period of October 1996 through September 1997. Studies have been performed to evaluate the behavior of nuclear waste glass and spent fuel samples under the unsaturated conditions (low-volume water contact) that are likely to exist in the Yucca Mountain environment being considered as a potential site for a high-level waste repository. Tests with actinide-doped waste glasses, in progress for over 11 years, indicate that the transuranic element release is dominated by colloids that continuously form and span from the glass surface. The nature of the colloids that form in the glass and spent fuel testing programs is being investigated by dynamic light scattering to determine the size distribution, by autoradiography to determine the chemistry, and by zeta potential to measure the electrical properties of the colloids. Tests with UO{sub 2} have been ongoing for 12 years. They show that the oxidation of UO{sub 2} occurs rapidly, and the resulting paragenetic sequence of secondary phases forming on the sample surface is similar to that observed for uranium found in natural oxidizing environments. The reaction of spent fuel samples in conditions similar to those used with UO{sub 2} have been in progress for over six years, and the results suggest that spent fuel forms many of the same alteration products as UO{sub 2}. With spent fuel, the bulk of the reaction occurs via a through-grain reaction process, although grain boundary attack is sufficient to have reacted all of the grain boundary regions in the samples. New test methods are under development to evaluate the behavior of spent fuel samples with intact cladding: the rate at which alteration and radionuclide release occurs when water penetrates fuel sections and whether the reaction causes the cladding to split. Alteration phases have been formed on fine grains of UO{sub 2} in contact with small volumes of water within a several month period when the radiolysis product H{sub 2}O{sub 2} is added to the groundwater solution. The test setup has been mocked up for operation with spent fuel in the hot-cell.

Ionizing radiation may affect the performance of glass in an unsaturated repository site by interacting with air, water vapor, or liquid water to produce a variety of radiolytic products. Tests were conducted to examine the effects of radiolysis under high gas/liquid ratios. Results indicate that nitrate is the predominant radiolytic product produced following both gamma and alpha radiation exposure, with lesser amounts of nitrite and carboxylic acids. The formation of nitrogen acids during exposure to long-lived, alpha-particle-emitting transuranic elements indicates that these acids may play a role in influencing nuclear waste form reactions in a long-term unsaturated disposal scenario. Experiments were also conducted with samples that simulate the composition of Savannah River Plant nuclear waste glasses. Radiolytic product formation in batch tests (340 m{sup {minus}1}, 90 C) resulted in a small increase in the release rates of many glass components, such as alkali and alkaline earth elements, although silicon and uranium release rates were slightly reduced indicating an overall beneficial effect of radiation on waste form stability. The radiolytic acids increased the rate of ion exchange between the glass and the thin film of condensate, resulting in accelerated corrosion rates for the glass. The paragenetic sequence of alteration phases formed on both the irradiated and nonirradiated glass samples reacted in the vapor hydration tests matches closely with those developed during volcanic glass alteration in naturally occurring saline-alkaline lake systems. This correspondence suggests that the high temperatures used in these tests have not changed the underlying glass reaction mechanism relate to that which controls glass reactions under ambient surficial conditions.

Tests have been conducted at Argonne National Laboratory (ANL) in support of the efforts of Lockheed Idaho Technology Company (LITCO) to vitrify high-level waste calcines. Tests were conducted with three classes of LITCO glass formulations: Formula 127 (fluorine-bearing), Formula 532 (fluorine-free), and 630 series (both single- and mixed-alkali) glasses. The test matrices included, as appropriate, the Product Consistency Test Method B (PCT-B), the Materials Characterization Center Test 1 (MCC-1), and the Argonne vapor hydration test (VHT). Test durations ranged from 7 to 183 d. In 7-d PCT-Bs, normalized mass losses of major glass-forming elements for the LITCO glasses are similar to, or lower than, normalized mass losses obtained for other domestic candidate waste glasses. Formula 532 glasses form zeolite alteration phases relatively early in their reaction with water. The formation of those phases increased the dissolution rate. In contrast, the Formula 127 glass is highly durable and forms alteration phases only after prolonged exposure to water in tests with very high surface area to volume ratios; these alteration phases have a relatively small effect on the rate of glass corrosion. No alteration phases formed within the maximum test duration of 183 d in PCT-Bs with the 630 series glasses. The corrosion behavior of the mixed-alkali 630 series glasses is similar to that of 630 series glasses containing sodium alone. In VHTs, both single- and mixed-alkali glasses form zeolite phases that increase the rate of glass reaction. The original 630 series glasses and those based on a revised surrogate calcine formulation react at the same rate in PCT-Bs and form the same major alteration phases in VHTs.