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At least 1,045 records · Page 58

Separation of tritiated water using graphene oxide membrane

In future nuclear fuel reprocessing plants and possibly for nuclear power plants, the cleanup of tritiated water will be needed for hundreds of thousands of gallons of water with low activities of tritium. This cleanup concept utilizes graphene oxide laminar membranes (GOx) for the separation of low-concentration (10 -3 -10 µCi/g) tritiated water to create water that can be released to the environment and a much smaller waste stream with higher tritium concentrations. Graphene oxide membranes consist of hierarchically stacked, overlapping molecular layers and represent a new class of materials. A permeation rate test was performed with a 2-µm-thick cast Asbury membrane using mixed gas permeability testing with zero air (highly purified atmosphere) and with air humidified with either H 2 O or D 2 O to a nominal 50% relative humidity. The membrane permeability for both H 2 O and D 2 O was high with N 2 and O 2 at the system measurement limit. The membrane water permeation rate was compared to a Nafion® membrane and the GOx permeation was approximately twice as high at room temperature. The H 2 O vapor permeation rate was 5.9 × 10 2 cc/m 2 /min (1.2 × 10 -6 g/min-cm 2 ), which is typical for graphene oxide membranes. To demonstrate the feasibility of such isotopic water separation through GOX laminar membranes, an experimental setup was constructed to use pressure-driven separation by heating the isotopic water mixture at one side of the membrane to create steam while cooling the other side. Several membranes were tested and were prepared using different starting materials and by different pretreatment methods. The average separation result was 0.8 for deuterium and 0.6 for tritium. Higher or lower temperatures may also improve separation efficiency but neither has been tested yet. A rough estimate of cost compared to current technology was also included as an indication of potential viability of the process. The relative process costs were based on the rough size of facility to accommodate the large surface area of the membranes and the energy needed to evaporate the water and pass through the membranes as compared to the currently used combined electrolysis and catalytic exchange process.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Milestone Report - M4FT-15OR03120218 - A Literature Search on the Effects of the Decay of 85 Kr to 85 Rb on Long-term Storage Options

Reprocessing of UNF that has been out of the reactor for less than about 50 y requires the removal of 85 Kr from the process off-gas streams. This is needed despite the relatively small amount of that isotope in the combined Xe and Kr inventory (Table 1). The decay of 85 Kr to 85 Rb presents challenges to the materials that will potentially be used to remove and store the Kr recovered from the off-gas. To address some of these problems, a thorough literature survey was completed, and the results of that analysis are summarized in this document.

Bruffey, Stephanie H.↗

Determination of Desorbed Species During Heating of AgI-Mordenite Provided by ORNL

This study is focused on describing the desorbed off gases due to heating of the AgIMordenite (MOR) produced at ORNL for iodine (I 2 ) gas capture from nuclear fuel aqueous reprocessing. In particular, the interest is for the incorporation of the AgI-MOR into a waste form, which might be the Sandia developed, low temperature sintering, Bi-Si oxide based, Glass Composite Material (GCM). The GCM has been developed as a waste form for the incorporation any oxide based getter material. In the case where iodine may be released during the sintering process of the GCM, additional Ag flake is added as further insurance in total iodine capture and retention. This has been the case for the incorporated ORNL developed AgIMOR. Thermal analysis studies were carried out to determine off gasing processes of ORNL AgIMOR. Independent of sample size, ~7wt% of total water is desorbed by 225°C. This includes both bulk surface and occluded water, and are monitored as H2O and OH. Of that total, ~5.5wt% is surface water which is removed by 125°C, and 1.5wt% is occluded (in zeolite pore) water. Less than ~1 wt% total water continues to desorb, but is completely removed by 500°C. Above 300°C, the detectable remaining desorbing species observed are iodine containing compounds, including I and I 2 .

09 BIOMASS FUELS↗

Multi-pack Disposal Concepts for Spent Fuel (Rev. 0)

At the initiation of the Used Fuel Disposition (UFD) R&D campaign, international geologic disposal programs and past work in the U.S. were surveyed to identify viable disposal concepts for crystalline, clay/shale, and salt host media (Hardin et al., 2012). Concepts for disposal of commercial spent nuclear fuel (SNF) and high-level waste (HLW) from reprocessing are relatively advanced in countries such as Finland, France, and Sweden. The UFD work quickly showed that these international concepts are all “enclosed,” whereby waste packages are emplaced in direct or close contact with natural or engineered materials . Alternative “open” modes (emplacement tunnels are kept open after emplacement for extended ventilation) have been limited to the Yucca Mountain License Application Design (CRWMS M&O, 1999). Thermal analysis showed that, if “enclosed” concepts are constrained by peak package/buffer temperature, waste package capacity is limited to 4 PWR assemblies (or 9-BWR) in all media except salt. This information motivated separate studies: 1) extend the peak temperature tolerance of backfill materials, which is ongoing; and 2) develop small canisters (up to 4-PWR size) that can be grouped in larger multi-pack units for convenience of storage, transportation, and possibly disposal (should the disposal concept permit larger packages). A recent result from the second line of investigation is the Task Order 18 report: Generic Design for Small Standardized Transportation, Aging and Disposal Canister Systems (EnergySolution, 2015). This report identifies disposal concepts for the small canisters (4-PWR size) drawing heavily on previous work, and for the multi-pack (16-PWR or 36-BWR).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Multi-Pack Disposal Concepts for Spent Fuel (Revision 1)

At the initiation of the Used Fuel Disposition (UFD) R&D campaign, international geologic disposal programs and past work in the U.S. were surveyed to identify viable disposal concepts for crystalline, clay/shale, and salt host media. Concepts for disposal of commercial spent nuclear fuel (SNF) and high-level waste (HLW) from reprocessing are relatively advanced in countries such as Finland, France, and Sweden. The UFD work quickly showed that these international concepts are all “enclosed,” whereby waste packages are emplaced in direct or close contact with natural or engineered materials . Alternative “open” modes (emplacement tunnels are kept open after emplacement for extended ventilation) have been limited to the Yucca Mountain License Application Design. Thermal analysis showed that if “enclosed” concepts are constrained by peak package/buffer temperature, that waste package capacity is limited to 4 PWR assemblies (or 9 BWR) in all media except salt. This information motivated separate studies: 1) extend the peak temperature tolerance of backfill materials, which is ongoing; and 2) develop small canisters (up to 4-PWR size) that can be grouped in larger multi-pack units for convenience of storage, transportation, and possibly disposal (should the disposal concept permit larger packages). A recent result from the second line of investigation is the Task Order 18 report: Generic Design for Small Standardized Transportation, Aging and Disposal Canister Systems. This report identifies disposal concepts for the small canisters (4-PWR size) drawing heavily on previous work, and for the multi-pack (16-PWR or 36-BWR).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Pebble-Bed Breed-and-Burn Reactor

The primary objective of this project is to use three-dimensional fuel shuffling in order to reduce the minimum peak radiation damage of ~550 dpa present Breed-and-Burn (B&B) fast nuclear reactor cores designs (they feature 2-D fuel shuffling) call for to as close as possible to the presently accepted value of 200 dpa thereby enabling earlier commercialization of B&B reactors which could make substantial contribution to energy sustainability and economic stability without need for fuel recycling. Another objective is increasing the average discharge burnup for the same peak discharge burnup thereby (1) increasing the fuel utilization of 2-D shuffled B&B reactors and (2) reducing the reprocessing capacity required to support a given capacity of FRs that are to recycle fuel.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Modeling CO 2 Sequestration in Saline Aquifer and Depleted Oil Reservoir To Evaluate Regional CO 2 Sequestration Potential of Ozark Plateau Aquifer System, South-Central Kansas

1. Drilled, cored, and logged three wells to the basement and collecting more than 2,700 ft of conventional core; obtained 20 m i2 of multicomponent 3D seismic imaging and merged and reprocessed more than 125 mi 2 of existing 3D seismic data for use in modeling CO 2 - EOR oil recovery and CO 2 storage in five oil fields in southern Kansas. 2. Determined the technical feasibility of injecting and sequestering CO 2 in a set of four depleted oil reservoirs in the Cutter, Pleasant Prairie South, Eubank, and Shuck fields in southwest Kansas; of concurrently recovering oil from those fields; and of quantifying the volumes of CO2 sequestered and oil recovered during the process. 3. Formed a consortium of six oil operating companies, five of which own and operate the four fields. The consortium became part of the Southwest Kansas CO 2 -EOR Initiative for the purpose of sharing data, knowledge, and interest in understanding the potential for CO 2 -EOR in Kansas. 4. Built a regional well database covering 30,000 mi 2 and containing stratigraphic tops from ~90,000 wells; correlated 30 major stratigraphic horizons; digitized key wells, including wireline logs and sample logs; and analyzed more than 3,000 drill stem tests to establish that fluid levels in deep aquifers below the Permian evaporites are not connected to the surface and therefore pressures are not hydrostatic. Connectivity with the surface aquifers is lacking because shale aquitards and impermeable evaporite layers consist of both halite and anhydrite. 5. Developed extensive web applications and an interactive mapping system that do the following: a. Facilitate access to a wide array of data obtained in the study, including core descriptions and analyses, sample logs, digital (LAS) well logs, seismic data, gravity and magnetics maps, structural and stratigraphic maps, inferred fault traces, earthquakes, Class I and II disposal wells, and surface lineaments. b. Provide real-time analysis of the project dataset, including automated integration and viewing of well logs, core, core analyses, brine chemistry, and stratigraphy using the Java Profile app. A cross-section app allows for the display of log data for up to four wells at a time. 6. Integrated interpretations from the project’s interactive web-based mapping system to gain insights to aid in assessing the efficacy of geologic CO 2 storage in Kansas and insights toward understanding recent seismicity to aid in evaluating induced vs. naturally occurring earthquakes. 7. Developed a digital type-log system, including web-based software to modify and refine stratigraphic nomenclature to provide stakeholders a common means for communication about the subsurface. 8. Contracted use of a nuclear magnetic resonance (NMR) log and ran it slowly to capture response and characterize larger pores common for carbonate reservoirs. Used NMR to extend core analyses to apply permeability, relative permeability to CO 2 , and capillary pressure to the major rock types, each uniquely expressed as a reservoir quality index (RQI), present in the Mississippian and Arbuckle rocks. 9. Characterized and evaluated the possible role of microbes in dense brines. Used microbes to compliment H/O stable isotopes to fingerprint brine systems. Used perforation/swabbing to obtain samples from multiple hydrostratigraphic units and confirmed equivalent results using less expensive drill stem tests (DST). 10. Used an integrated approach from whole core, logs, tests, and seismic to verify and quantify properties of vuggy, brecciated, and fractured carbonate intervals. 11. Used complex geocellular static and dynamic models to evaluate regional storage capacity using large parallel processing. 12. Carbonates are complex reservoirs and CO 2 -EOR needs to move to the next generation to increase effectiveness of CO 2 and efficiency and safety of the injection.

54 ENVIRONMENTAL SCIENCES↗

Modeling CO 2 Sequestration in Saline Aquifer and Depleted Oil Reservoir To Evaluate Regional CO 2 Sequestration Potential of Ozark Plateau Aquifer System, South-Central Kansas

1. Drilled, cored, and logged three wells to the basement and collecting more than 2,700 ft of conventional core; obtained 20 m i2 of multicomponent 3D seismic imaging and merged and reprocessed more than 125 mi 2 of existing 3D seismic data for use in modeling CO 2 - EOR oil recovery and CO 2 storage in five oil fields in southern Kansas. 2. Determined the technical feasibility of injecting and sequestering CO 2 in a set of four depleted oil reservoirs in the Cutter, Pleasant Prairie South, Eubank, and Shuck fields in southwest Kansas; of concurrently recovering oil from those fields; and of quantifying the volumes of CO2 sequestered and oil recovered during the process. 3. Formed a consortium of six oil operating companies, five of which own and operate the four fields. The consortium became part of the Southwest Kansas CO 2 -EOR Initiative for the purpose of sharing data, knowledge, and interest in understanding the potential for CO 2 -EOR in Kansas. 4. Built a regional well database covering 30,000 mi 2 and containing stratigraphic tops from ~90,000 wells; correlated 30 major stratigraphic horizons; digitized key wells, including wireline logs and sample logs; and analyzed more than 3,000 drill stem tests to establish that fluid levels in deep aquifers below the Permian evaporites are not connected to the surface and therefore pressures are not hydrostatic. Connectivity with the surface aquifers is lacking because shale aquitards and impermeable evaporite layers consist of both halite and anhydrite. 5. Developed extensive web applications and an interactive mapping system that do the following: a. Facilitate access to a wide array of data obtained in the study, including core descriptions and analyses, sample logs, digital (LAS) well logs, seismic data, gravity and magnetics maps, structural and stratigraphic maps, inferred fault traces, earthquakes, Class I and II disposal wells, and surface lineaments. b. Provide real-time analysis of the project dataset, including automated integration and viewing of well logs, core, core analyses, brine chemistry, and stratigraphy using the Java Profile app. A cross-section app allows for the display of log data for up to four wells at a time. 6. Integrated interpretations from the project’s interactive web-based mapping system to gain insights to aid in assessing the efficacy of geologic CO 2 storage in Kansas and insights toward understanding recent seismicity to aid in evaluating induced vs. naturally occurring earthquakes. 7. Developed a digital type-log system, including web-based software to modify and refine stratigraphic nomenclature to provide stakeholders a common means for communication about the subsurface. 8. Contracted use of a nuclear magnetic resonance (NMR) log and ran it slowly to capture response and characterize larger pores common for carbonate reservoirs. Used NMR to extend core analyses to apply permeability, relative permeability to CO 2 , and capillary pressure to the major rock types, each uniquely expressed as a reservoir quality index (RQI), present in the Mississippian and Arbuckle rocks. 9. Characterized and evaluated the possible role of microbes in dense brines. Used microbes to compliment H/O stable isotopes to fingerprint brine systems. Used perforation/swabbing to obtain samples from multiple hydrostratigraphic units and confirmed equivalent results using less expensive drill stem tests (DST). 10. Used an integrated approach from whole core, logs, tests, and seismic to verify and quantify properties of vuggy, brecciated, and fractured carbonate intervals. 11. Used complex geocellular static and dynamic models to evaluate regional storage capacity using large parallel processing. 12. Carbonates are complex reservoirs and CO 2 -EOR needs to move to the next generation to increase effectiveness of CO 2 and efficiency and safety of the injection.

54 ENVIRONMENTAL SCIENCES↗

Modeling CO 2 Sequestration in Saline Aquifer and Depleted Oil Reservoir To Evaluate Regional CO 2 Sequestration Potential of Ozark Plateau Aquifer System, South-Central Kansas

1. Drilled, cored, and logged three wells to the basement and collecting more than 2,700 ft of conventional core; obtained 20 m i2 of multicomponent 3D seismic imaging and merged and reprocessed more than 125 mi 2 of existing 3D seismic data for use in modeling CO 2 - EOR oil recovery and CO 2 storage in five oil fields in southern Kansas. 2. Determined the technical feasibility of injecting and sequestering CO 2 in a set of four depleted oil reservoirs in the Cutter, Pleasant Prairie South, Eubank, and Shuck fields in southwest Kansas; of concurrently recovering oil from those fields; and of quantifying the volumes of CO2 sequestered and oil recovered during the process. 3. Formed a consortium of six oil operating companies, five of which own and operate the four fields. The consortium became part of the Southwest Kansas CO 2 -EOR Initiative for the purpose of sharing data, knowledge, and interest in understanding the potential for CO 2 -EOR in Kansas. 4. Built a regional well database covering 30,000 mi 2 and containing stratigraphic tops from ~90,000 wells; correlated 30 major stratigraphic horizons; digitized key wells, including wireline logs and sample logs; and analyzed more than 3,000 drill stem tests to establish that fluid levels in deep aquifers below the Permian evaporites are not connected to the surface and therefore pressures are not hydrostatic. Connectivity with the surface aquifers is lacking because shale aquitards and impermeable evaporite layers consist of both halite and anhydrite. 5. Developed extensive web applications and an interactive mapping system that do the following: a. Facilitate access to a wide array of data obtained in the study, including core descriptions and analyses, sample logs, digital (LAS) well logs, seismic data, gravity and magnetics maps, structural and stratigraphic maps, inferred fault traces, earthquakes, Class I and II disposal wells, and surface lineaments. b. Provide real-time analysis of the project dataset, including automated integration and viewing of well logs, core, core analyses, brine chemistry, and stratigraphy using the Java Profile app. A cross-section app allows for the display of log data for up to four wells at a time. 6. Integrated interpretations from the project’s interactive web-based mapping system to gain insights to aid in assessing the efficacy of geologic CO 2 storage in Kansas and insights toward understanding recent seismicity to aid in evaluating induced vs. naturally occurring earthquakes. 7. Developed a digital type-log system, including web-based software to modify and refine stratigraphic nomenclature to provide stakeholders a common means for communication about the subsurface. 8. Contracted use of a nuclear magnetic resonance (NMR) log and ran it slowly to capture response and characterize larger pores common for carbonate reservoirs. Used NMR to extend core analyses to apply permeability, relative permeability to CO 2 , and capillary pressure to the major rock types, each uniquely expressed as a reservoir quality index (RQI), present in the Mississippian and Arbuckle rocks. 9. Characterized and evaluated the possible role of microbes in dense brines. Used microbes to compliment H/O stable isotopes to fingerprint brine systems. Used perforation/swabbing to obtain samples from multiple hydrostratigraphic units and confirmed equivalent results using less expensive drill stem tests (DST). 10. Used an integrated approach from whole core, logs, tests, and seismic to verify and quantify properties of vuggy, brecciated, and fractured carbonate intervals. 11. Used complex geocellular static and dynamic models to evaluate regional storage capacity using large parallel processing. 12. Carbonates are complex reservoirs and CO 2 -EOR needs to move to the next generation to increase effectiveness of CO 2 and efficiency and safety of the injection.

54 ENVIRONMENTAL SCIENCES↗

Modeling CO 2 Sequestration in Saline Aquifer and Depleted Oil Reservoir To Evaluate Regional CO 2 Sequestration Potential of Ozark Plateau Aquifer System, South-Central Kansas

1. Drilled, cored, and logged three wells to the basement and collecting more than 2,700 ft of conventional core; obtained 20 m i2 of multicomponent 3D seismic imaging and merged and reprocessed more than 125 mi 2 of existing 3D seismic data for use in modeling CO 2 - EOR oil recovery and CO 2 storage in five oil fields in southern Kansas. 2. Determined the technical feasibility of injecting and sequestering CO 2 in a set of four depleted oil reservoirs in the Cutter, Pleasant Prairie South, Eubank, and Shuck fields in southwest Kansas; of concurrently recovering oil from those fields; and of quantifying the volumes of CO2 sequestered and oil recovered during the process. 3. Formed a consortium of six oil operating companies, five of which own and operate the four fields. The consortium became part of the Southwest Kansas CO 2 -EOR Initiative for the purpose of sharing data, knowledge, and interest in understanding the potential for CO 2 -EOR in Kansas. 4. Built a regional well database covering 30,000 mi 2 and containing stratigraphic tops from ~90,000 wells; correlated 30 major stratigraphic horizons; digitized key wells, including wireline logs and sample logs; and analyzed more than 3,000 drill stem tests to establish that fluid levels in deep aquifers below the Permian evaporites are not connected to the surface and therefore pressures are not hydrostatic. Connectivity with the surface aquifers is lacking because shale aquitards and impermeable evaporite layers consist of both halite and anhydrite. 5. Developed extensive web applications and an interactive mapping system that do the following: a. Facilitate access to a wide array of data obtained in the study, including core descriptions and analyses, sample logs, digital (LAS) well logs, seismic data, gravity and magnetics maps, structural and stratigraphic maps, inferred fault traces, earthquakes, Class I and II disposal wells, and surface lineaments. b. Provide real-time analysis of the project dataset, including automated integration and viewing of well logs, core, core analyses, brine chemistry, and stratigraphy using the Java Profile app. A cross-section app allows for the display of log data for up to four wells at a time. 6. Integrated interpretations from the project’s interactive web-based mapping system to gain insights to aid in assessing the efficacy of geologic CO 2 storage in Kansas and insights toward understanding recent seismicity to aid in evaluating induced vs. naturally occurring earthquakes. 7. Developed a digital type-log system, including web-based software to modify and refine stratigraphic nomenclature to provide stakeholders a common means for communication about the subsurface. 8. Contracted use of a nuclear magnetic resonance (NMR) log and ran it slowly to capture response and characterize larger pores common for carbonate reservoirs. Used NMR to extend core analyses to apply permeability, relative permeability to CO 2 , and capillary pressure to the major rock types, each uniquely expressed as a reservoir quality index (RQI), present in the Mississippian and Arbuckle rocks. 9. Characterized and evaluated the possible role of microbes in dense brines. Used microbes to compliment H/O stable isotopes to fingerprint brine systems. Used perforation/swabbing to obtain samples from multiple hydrostratigraphic units and confirmed equivalent results using less expensive drill stem tests (DST). 10. Used an integrated approach from whole core, logs, tests, and seismic to verify and quantify properties of vuggy, brecciated, and fractured carbonate intervals. 11. Used complex geocellular static and dynamic models to evaluate regional storage capacity using large parallel processing. 12. Carbonates are complex reservoirs and CO 2 -EOR needs to move to the next generation to increase effectiveness of CO 2 and efficiency and safety of the injection.

54 ENVIRONMENTAL SCIENCES↗

Direct Measurement of U235 and Pu239 in Spent Fuel Rods with Gamma-Ray Mirrors

The amounts of fissile Pu and U in spent nuclear fuel are of primary concern to the safeguards community. In particular, there are issues when safeguards transitions from an item accountancy basis (such as fuel bundles) to a fissile material mass basis as occurs when spent fuel enters a reprocessing plant. Discrepancies occur because item accountancy requires estimating the content of fissile material using indirect techniques such as the fuel burn-up and item-level measurements of radiation emissions from fission by-products. Direct measurement of the fissile content by monitoring line emissions from fissile species themselves is impossible because the lines are much weaker than those emitted by shorter-lived isotopes in the fuel. The goal of this project is to develop a technique to directly measure these weaker lines despite the presence of overwhelming radiation from other isotopes. This is achieved by using gamma-ray mirrors as a narrow band-pass filter. The mirrors reflect only energies of interest toward a HPGe detector that is shielded from direct view of the spent fuel and its fierce emissions. This can significantly improve the reliability with which the mass of fissile material is tracked.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Seismic Performance of Dry Casks Storage for Long- Term Exposure

The main goal of this study is to evaluate the long-term seismic performance of freestanding and anchored Dry Storage Casks (DSCs) using experimental tests on a shaking table, as well as comprehensive numerical evaluations that include the cask-pad-soil system. The study focuses on the dynamic performance of vertical DSCs, which can be designed as free-standing structures resting on a reinforced concrete foundation pad, or casks anchored to a foundation pad. The spent nuclear fuel (SNF) at nuclear power plants (NPPs) is initially stored in fuel-storage pools to control the fuel temperature. After several years, the fuel assemblies are transferred to DSCs at sites contiguous to the plant, known as Interim Spent Fuel Storage Installations (ISFSIs). The regulations for these storage systems (10 CFR 72) ensure adequate passive heat removal and radiation shielding during normal operations, off-normal events, and accident scenarios. The integrity of the DSCs is important, even if the overpack does not breach, because eventually the spent fuel-rods need to be shipped either to a reprocessing plant or a repository. DSCs have been considered as a temporary storage solution, and usually are licensed for 20 years, although they can be relicensed for operating periods of up to 60 years. In recent years, DSCs have been reevaluated as a potential mid-term solution, in which the operating period may be extended for up to 300 years. At the same time, recent seismic events have underlined the significant risks DSCs are exposed. The consideration of DCSs for storing spent fuel for hundreds of years has created new challenges. In the case of seismic hazard, longer-term operating periods not only lead to larger horizontal accelerations, but also increase the relative effect of vertical accelerations that usually are disregarded for smaller seismic events. These larger seismic demands could lead to casks sliding and tipping over, impacting the concrete pad or adjacent casks. The casks may also slide and collide with other casks or structural components. Also, the different DSC components may impact each other during these events. This study provides a comprehensive evaluation of DSCs subjected to these extreme demands, including the effect of vertical accelerations, and soilstructure interaction.

36 MATERIALS SCIENCE↗

Improvement of INVS Measurement Uncertainty for Pu and U-Pu Nitrate Solution

In the Tokai Reprocessing Plant (TRP) and the Plutonium Conversion Development Facility (PCDF), a large amount of plutonium nitrate solution which is recovered from light water reactor (LWR) and advanced thermal reactor (ATR), FUGEN are being stored. Since the solution is designated as a direct use material, the periodical inventory verification and flow verification are being conducted by Japan Safeguard Government Office (JSGO) and International Atomic Agency (IAEA).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Performance of a Steel/Oxide Composite Waste Form for Combined Waste Steams from Advanced Electrochemical Processes

The results of electrochemical corrosion tests and modeling activities performed collaboratively by researchers at the University of Illinois at Chicago and Argonne National Laboratory as part of workpackage NU-13-IL-UIC-0203-02 are summarized herein. The overall objective of the project was to develop and demonstrate testing and modeling approaches that could be used to evaluate the use of composite alloy/ceramic materials as high-level durable waste forms. Several prototypical composite waste form materials were made from stainless steels representing fuel cladding, reagent metals representing metallic fuel waste streams, and reagent oxides representing oxide fuel waste streams to study the microstructures and corrosion behaviors of the oxide and alloy phases. Microelectrodes fabricated from small specimens of the composite materials were used in a series of electrochemical tests to assess the corrosion behaviors of the constituent phases and phase boundaries in an aggressive acid brine solution at various imposed surface potentials. The microstructures were characterized in detail before and after the electrochemical tests to relate the electrochemical responses to changes in both the electrode surface and the solution composition. The results of microscopic, electrochemical, and solution analyses were used to develop equivalent circuit and physical models representing the measured corrosion behaviors of the different materials pertinent to long-term corrosion behavior. This report provides details regarding (1) the production of the composite materials, (2) the protocol for the electrochemical measurements and interpretations of the responses of multi-phase alloy and oxide composites, (3) relating corrosion behaviors to microstructures of multi-phase alloys based on 316L stainless steel and HT9 (410 stainless steel was used as a substitute) with added Mo, Ni, and/or Mn, and (4) modeling the corrosion behaviors and rates of several alloy/oxide composite materials made with added lanthanide and uranium oxides. These analyses show the corrosion behaviors of the alloy/ceramic composite materials are very similar to the corrosion behaviors of multi-phase alloy waste forms, and that the presence of oxide inclusions does not impact the corrosion behaviors of the alloy phases. Mixing with metallic waste streams is beneficial to lanthanide and uranium oxides in that they react with Zr in the fuel waste to form highly durable zirconates. The measured corrosion behaviors suggest properly formulated composite materials would be suitable waste forms for combined metallic and oxide waste streams generated during electrometallurgical reprocessing of spent nuclear fuel. Electrochemical methods are suitable for evaluating the durability and modeling long-term behavior of composite waste forms: the degradation model developed for metallic waste forms can be applied to the alloy phases formed in the composite and an affinity-based mineral dissolution model can be applied to the ceramic phases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

FY-2016 Methyl Iodide Higher NOx Adsorption Test Report

Deep-bed methyl iodide adsorption testing has continued in Fiscal Year 2016 under the Department of Energy (DOE) Fuel Cycle Technology (FCT) Program Offgas Sigma Team to further research and advance the technical maturity of solid sorbents for capturing iodine-129 in off-gas streams during used nuclear fuel reprocessing. Adsorption testing with higher levels of NO (approximately 3,300 ppm) and NO2 (up to about 10,000 ppm) indicate that high efficiency iodine capture by silver aerogel remains possible. Maximum iodine decontamination factors (DFs, or the ratio of iodine flowrate in the sorbent bed inlet gas compared to the iodine flowrate in the outlet gas) exceeded 3,000 until bed breakthrough rapidly decreased the DF levels to as low as about 2, when the adsorption capability was near depletion. After breakthrough, nearly all of the uncaptured iodine that remains in the bed outlet gas stream is no longer in the form of the original methyl iodide. The methyl iodide molecules are cleaved in the sorbent bed, even after iodine adsorption is no longer efficient, so that uncaptured iodine is in the form of iodine species soluble in caustic scrubber solutions, and detected and reported here as diatomic I2. The mass transfer zone depths were estimated at 8 inches, somewhat deeper than the 2-5 inch range estimated for both silver aerogels and silver zeolites in prior deep-bed tests, which had lower NOx levels. The maximum iodine adsorption capacity and silver utilization for these higher NOx tests, at about 5-15% of the original sorbent mass, and about 12-35% of the total silver, respectively, were lower than for trends from prior silver aerogel and silver zeolite tests with lower NOx levels. Additional deep-bed testing and analyses are recommended to expand the database for organic iodide adsorption and increase the technical maturity if iodine adsorption processes.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Stability of Tritium and Iodine Sorbents in TPOG Conditions

US regulations could require the removal of both iodine and tritium from the off-gas stream of a used nuclear fuel (UNF) reprocessing facility. Advanced tritium pretreatment is a pretreatment step that uses high concentrations of NOR2R in a gas stream to volatilize tritium and iodine from UNF prior to traditional dissolution. The gaseous effluent from this process would then require abatement to remove tritium and iodine, but high levels of NOR2R could have a detrimental effect on the ability of various solid sorbents to remove the volatile radionuclides. For tritium and iodine, the sorbents of interest are 3Å molecular sieve (3AMS) for tritium and reduced silver mordenite (AgP 0 PZ), silver-functionalized silica-aerogel (AgAerogel), and silver-nitrate-impregnated alumina (AgA) for iodine. Prior research has demonstrated that exposure to high concentrations of NOR2R can reduce the iodine loading capacity of AgP 0 PZ by > 90% when exposed for 1 week. Research in Japan has demonstrated that AgA is more robust to NOR2R exposure than AgZ. The testing described here was intended to assess the effects of high concentrations of NOR2R on the iodine capture capacity of AgA and the water adsorption capacity of 3AMS. To determine the effect of extended exposure of the sorbents to NOR2R, both 3AMS and AgA were aged in a 75% NOR2R environment prior to loading. The 3AMS samples were aged for 1, 4, and 5.5 weeks at 40°C. They were then loaded with water in a 10°C dew point stream (corresponding to a water concentration of ~12,000 ppmv) at 40°C. There was no significant change in the water adsorption capacity of the 3AMS upon exposure to 75% NOR2R. The AgA samples were aged for 1, 2, and 4 weeks at 150°C and were loaded with 50 ppmv IR2R at 150°C. The results show that the iodine capture capacity of AgA is reduced by exposure to high concentrations of NOR2R. The iodine capacity reductions were 16%, 36%, and 76% for 1, 2, and 4 week exposures, respectively. This is less of a capacity loss than that seen in similar testing with the AgP 0 PZ sorbent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

FCRD Advanced Reactor (Transmutation) Fuels Handbook

Transmutation of minor actinides such as Np, Am, and Cm in spent nuclear fuel is of international interest because of its potential for reducing the long-term health and safety hazards caused by the radioactivity of the spent fuel. One important approach to transmutation (currently being pursued by the DOE Fuel Cycle Research & Development Advanced Fuels Campaign) involves incorporating the minor actinides into U-Pu-Zr alloys, which can be used as fuel in fast reactors. U-Pu-Zr alloys are well suited for electrolytic refining, which leads to incorporation rare-earth fission products such as La, Ce, Pr, and Nd. It is, therefore, important to understand not only the properties of U-Pu-Zr alloys but also those of U-Pu-Zr alloys with concentrations of minor actinides (Np, Am) and rare-earth elements (La, Ce, Pr, and Nd) similar to those in reprocessed fuel. In addition to requiring extensive safety precautions, alloys containing U, Pu, and minor actinides (Np and Am) are difficult to study for numerous reasons, including their complex phase transformations, characteristically sluggish phasetransformation kinetics, tendency to produce experimental results that vary depending on the histories of individual samples, rapid oxidation, and sensitivity to contaminants such as oxygen in concentrations below a hundred parts per million. Although less toxic, rare-earth elements such as La, Ce, Pr, and Nd are also difficult to study for similar reasons. Many of the experimental measurements were made before 1980, and the level of documentation for experimental methods and results varies widely. It is, therefore, not surprising that little is known with certainty about U-Pu-Zr alloys, particularly those that also contain minor actinides and rare-earth elements. General acceptance of results commonly indicates that there is only a single measurement for a particular property. This handbook summarizes currently available information about U, Pu, Zr, Np, Am, La, Ce, Pr, and Nd and alloys of two or three of these elements. It contains information about phase diagrams and related information (including phases and phase transformations); heat capacity, entropy, and enthalpy; thermal expansion; and thermal conductivity and diffusivity. In addition to presenting information about materials properties, the handbook attempts to provide information about how well the property is known and how much variation exists between measurements. Although it includes some results from models, its primary focus is experimental data. The Handbook is organized in two sections: one with information about the U-Pu-Zr ternary and one with information about other elements and binary and vi ternary alloys in the U-Np-Pu-Am-La-Ce-Pr-Nd-Zr system. Within each section, information about elements is presented first, followed by information about binary alloys, then information about ternary alloys. The order in which the elements in each alloy are mentioned follows the order in the first sentence of this paragraph. Much of the information on the U-Pu-Zr system repeats information from the FCRD Transmutation Fuels Handbook 2015. Most of the other data has been published elsewhere (although scattered throughout numerous references, some quite obscure); however, some data from Idaho National Laboratory is presented here for the first time. As the FCRD programmatic mission evolves, future editions of this handbook will begin to include other advanced reactor fuel designs and compositions. Hence, the title of the handbook will transition to the Advanced Reactor Fuels Handbook.

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Non-Ideality in Solvent Extraction Systems: PNNL FY 2014 Status Report

The overall objective of this project is to develop predictive modeling capabilities for advanced fuel cycle separation processes by gaining a fundamental quantitative understanding of non-ideality effects and speciation in relevant aqueous and organic solutions. Aqueous solutions containing actinides and lanthanides encountered during nuclear fuel reprocessing have high ionic strength and do not behave as ideal solutions. Activity coefficients must be calculated to take into account the deviation from ideality and predict their behavior. In FY 2012-2013, a convenient method for determining activity effects in aqueous electrolyte solutions was developed. Our initial experiments demonstrated that water activity and osmotic coefficients of the electrolyte solutions can be accurately measured by the combination of two techniques, a Water Activity Meter and Vapor Pressure Osmometry (VPO). The water activity measurements have been conducted for binary lanthanide solutions in wide concentration range for all lanthanides (La-Lu with the exception of Pm). The osmotic coefficients and Pitzer parameters for each binary system were obtained by the least squares fitting of the water activity data. However, application of Pitzer model for the quantitative evaluation of the activity effects in the multicomponent mixtures is difficult due to the large number of the required interaction parameters. In FY 2014, the applicability of the Bromley model for the determination of the Ln(NO 3 ) 3 activity coefficients was evaluated. The new Bromley parameters for the binary Ln(NO 3 ) 3 electrolytes were obtained based on the available literature and our experimental data. This allowed for the accurate prediction of the Ln(NO 3 ) 3 activity coefficients for the binary Ln(NO 3 ) 3 electrolytes. This model was then successfully implemented for the determination of the Ln(NO 3 ) 3 activity coefficients in the ternary Nd(NO 3 ) 3 /HNO 3 /H2O, Eu(NO 3 ) 3 /HNO 3 /H 2 O, and Eu(NO 3 ) 3 /NaNO 3 /H 2 O systems. The main achievement of this work is the verified pathway for the estimation of the activity coefficients in the multicomponent aqueous electrolyte systems. The accurate Bromley electrolytes contributions obtained in this work for the entire series of lanthanide(III) nitrates (except Pm) can be applied for predicting activity coefficients and non-ideality effects for multi-component systems containing these species. This work also provides the proof-of-principle of extending the model to more complex multicomponent systems. Moreover, this approach can also be applied to actinide-containing electrolyte systems, for determination of the activity coefficients in concentrated radioactive solutions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗