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Impact of Isotope Fidelity on Fuel Cycle Calculations

The purpose of this study is to examine the importance of the isotopic composition of plutonium on PWR MOX fuel fabrication as part of a multi-tiered fuel cycle, and the effect of its evolution during a transition. Two main effects can modify the isotopic composition of the plutonium used to build the PWR-MOX fuel: decay and depletion. This analysis is based on a transition of the nuclear fuel cycle to a configuration identified as 'Evaluation Group 29' or 'EG29', in the recently-published Evaluation and Screening (E and S) report. The EG29 fuel cycle corresponds to a double strata fleet. The first stratum is composed of sodium-cooled fast reactors (SFRs) multi-recycling plutonium. Surplus plutonium is sent to the second stratum composed of pressurized water reactors with full mixed oxide (U/Pu)O{sub 2} cores (MOX-PWRs). The PWR stratum is also multi-recycling its plutonium. The target energy generation ratio for the final EG29 system is 70:30 (SFR:PWR), with a 1% annual growth in nuclear energy demand. All the calculation of this study have been performed using the Cyclus fuel cycle simulator framework. The facility models are from the Cycamore package, developed by the Cyclus team, and containing a Pu-equivalent fuel fabrication model as well as a simple fixed mixing ratio fuel fabrication model. A new neural network model has also been contributed to the Cyclus environment using the cyCLASS tool, allowing the use of the fuel fabrication and depletion models from the CLASS tool in Cyclus. (authors)

07 ISOTOPE AND RADIATION SOURCES↗

Repackaging of High Fissile TRU Waste at the Transuranic Waste Processing Center - 13240

Twenty-six drums of high fissile transuranic (TRU) waste from Oak Ridge National Laboratory (ORNL) operations were declared waste in the mid-1980's and placed in storage with the legacy TRU waste inventory for future treatment and disposal at the Waste Isolation Pilot Plant (WIPP). Repackaging and treatment of the waste at the TRU Waste Packaging Center (TWPC) will require the installation of additional equipment and capabilities to address the hazards for handling and repackaging the waste compared to typical Contact Handled (CH) TRU waste that is processed at the TWPC, including potential hydrogen accumulation in legacy 6M/2R packaging configurations, potential presence of reactive plutonium hydrides, and significant low energy gamma radiation dose rates. All of the waste is anticipated to be repackaged at the TWPC and certified for disposal at WIPP. The waste is currently packaged in multiple layers of containers which presents additional challenges for repackaging activities due to the potential for the accumulation of hydrogen gas in the container headspace in quantities than could exceed the Lower Flammability Limit (LFL). The outer container for each waste package is a stainless steel 0.21 m{sup 3} (55-gal) drum which contains either a 0.04 m{sup 3} or 0.06 m{sup 3} (10-gal or 15-gal) 6M drum. The inner 2R container in each 6M drum is ∼12 cm (5 in) outside diameter x 30-36 cm (12-14 in) long and is considered to be a > 4 liter sealed container relative to TRU waste packaging criteria. Inside the 2R containers are multiple configurations of food pack cans, pipe nipples, and welded capsules. The waste contains significant quantities of high burn-up plutonium oxides and metals with a heavy weight percentage of higher atomic mass isotopes and the subsequent in-growth of significant quantities of americium. Significant low energy gamma radiation is expected to be present due to the americium in-growth. Radiation dose rates on inner containers are estimated to be 1-3 mSv/hr (100-300 mrem/hr) with an unshielded dose rate on the waste itself of over 10 mSv/hr (1 rem/hr). Additional equipment to be installed at the TWPC will include a new perma-con enclosure and a shielded/inert glovebox in the process building to repackage and stabilize the waste. All of the waste will be repackaged into Standard Pipe Overpacks. Most of the waste (21 of the 26 drums) is expected to be repackaged at the food-pack can level (i.e. the food-pack cans will not be opened). Five of the incoming waste containers are expected to be repackaged at the primary waste level. Three of the containers exceed the 200 gram Pu-239 Fissile Gram Equivalent (FGE) limit for the Standard Pipe Overpack. These three containers will be repackaged down to the primary waste level and divided into eight Standard Pipe Overpacks for shipment to WIPP. Two containers must be stabilized to eliminate any reactive plutonium hydrides that may be present. These containers will be opened in the inert, shielded glovebox, and the remaining corroded plutonium metal converted to a stable oxide form by using a 600 deg. C tube furnace with controlled oxygen feed in a helium carrier gas. The stabilized waste will then be packaged into two Standard Pipe Overpacks. Design and build out activities for the additional repackaging capabilities at the TWPC are scheduled to begin in Fiscal Year 2013 with repackaging, stabilization, and certification activities scheduled to begin in Fiscal Year 2014. Following repackaging and stabilization activities, the Standard Pipe Overpacks will be certified for disposal at WIPP utilizing Non-Destructive Examination (NDE) to verify the absence of prohibited items and Non-Destructive Assay (NDA) to verify the isotopic content under the TWPC WIPP certification program implemented by the Central Characterization Project (CCP). (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Microprobe Analysis of Pu-Ga Standards

In order to obtain quantitative analysis using an Electron Scanning Microprobe it is essential to have a standard of known composition. Most elemental and multi-elemental standards can be easily obtained from places like Elemental Scientific or other standards organizations that are NIST (National Institute of Standards and Technology) traceable. It is, however, more challenging to find standards for plutonium. Past work performed in our group has typically involved using the plutonium sample to be analysed as its own standard as long as all other known components of the sample have standards to be compared to [1,2,3]. Finally, this method works well enough, but this experiment was performed in order to develop a more reliable standard for plutonium using five samples of known chemistry of a plutonium gallium mix that could then be used as the main plutonium and gallium standards for future experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Towards an Agent-Based Blackboard System for Reactor Design Optimization

The field of reactor design is rich with opportunities for applications of computational optimization algorithms; these applications can range from preliminary core design to reactor shuffling patterns. Many of these schemes rely on sets of previously generated solutions (sometimes referred to as “generations”) to inform future decisions. While it is important to build upon prior knowledge, this process requires a full generation of solutions to be formed before future solutions can be examined. Rather than relying on a generational scheme to perform an optimization, we propose using an agent-based approach in conjunction with a blackboard framework for performing reactor design optimizations. Utilizing an agent-based approach allows agents to perform tasks independently, while retaining the ability to build off of previous solutions. We develop an agent-based blackboard system (ABBS) for determining the Pareto front (PF) in sodium fast reactor design optimization problems and compared this with the Non-Dominated Sorting Genetic Algorithm II (NSGA-II). Our goal is to evaluate the viability of the ABBS in producing a PF that is comparable with the NSGA-II algorithm. The design space consists of the fuel height, fuel smear, and plutonium fraction in the core, and we seek to minimize the reactivity swing and plutonium mass, while maximizing the burnup. The diversity, coverage, and spread of the PFs generated by the two methods are examined, and the ABBS is able to converge to the same PF as the NSGA-II algorithm. These results show that the ABBS is able to find optimal designs that are similar to those found by the NSGA-II algorithm. We conclude our study by applying the ABBS to the design of a sodium-cooled fast reactor to dispose of weapons-grade plutonium. The ABBS finds a core design that can burn upwards of 17.5 kg of weapons-grade plutonium per year and degrade an additional 195 kg of weapons-grade plutonium per year into non-weapons-grade material.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Development of Metallic Magnetic Calorimeters for Nuclear Safeguards Applications

Many nuclear safeguards applications could benefit from high-resolution gamma-ray spectroscopy achievable with metallic magnetic calorimeters. This dissertation covers the development of a system for these applications based on gamma-ray detectors developed at the University of Heidelberg. It demonstrates new calorimeters of this type, which achieved an energy resolution of 45.5 eV full-width at half-maximum at 59.54 keV, roughly ten times better than current state of the art high purity germanium detectors. This is the best energy resolution achieved with a gamma-ray metallic magnetic calorimeter at this energy to date. In addition to demonstrating a new benchmark in energy resolution, an experimental system for measuring samples with metallic magnetic calorimeters was constructed at Lawrence Livermore National Laboratory. This system achieved an energy resolution of 91.3 eV full-width at half-maximum at 59.54 keV under optimal conditions. Using this system it was possible to characterize the linearity of the response, the count-rate limitations, and the energy resolution as a function of temperature of the new calorimeter. With this characterization it was determined that it would be feasible to measure 242Pu in a mixed isotope plutonium sample. A measurement of a mixed isotope plutonium sample was performed over the course of 12 days with a single two-pixel metallic magnetic calorimeter. The relative concentration of 242Pu in comparison to other plutonium isotopes was determined by direct measurement to less than half a percent accuracy. This is comparable with the accuracy of the best-case scenario using traditional indirect methods. The ability to directly measure the relative concentration of 242Pu in a sample could enable more accurate accounting and detection of indications of undeclared activities in nuclear safeguards, a better constraint on source material in forensic samples containing plutonium, and improvements in verification in a future plutonium disposition treaty.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Project 57 Air Monitoring Report: October 1, 2013, through December 31, 2014

On April 24, 1957, the Atomic Energy Commission (AEC, now the Department of Energy [DOE]) conducted the Project 57 safety experiment in western Emigrant Valley north east of the Nevada National Security Site (NNSS, formerly the Nevada Test Site) on lands withdrawn by the Department of Defense (DoD) for the Nevada Test and Training Range (NTTR). The test was undertaken to develop (1) a means of estimating plutonium distribution resulting from a nonnuclear detonation; (2) biomedical evaluation techniques for use in plutonium-laden environments; (3) methods of surface decontamination; and (4) instruments and field procedures for prompt estimation of alpha contamination (Shreve, 1958). Although the test did not result in the fission of nuclear materials, it did disseminate plutonium across the land surface. Following the experiment, the AEC fenced the contaminated area and returned control of the surrounding land to the DoD. Various radiological surveys have been performed in the area and in 2007, the DOE expanded the demarked contamination area by posting signs 200 to 400 feet (60 to 120 meters) outside of the original fence. Plutonium in soil is thought to attach preferentially to smaller particles. Therefore, redistribution of soil particulates by wind (dust) is the mechanism most likely to transport plutonium beyond the boundary of the Project 57 contamination area. In 2011, DRI installed two instrumentation towers to measure radiological, meteorological, and dust conditions. The monitoring activity was implemented to determine if radionuclide contamination was detectable in samples of airborne dust and characterize meteorological and environmental parameters that influence dust transport. Collected data also permits comparison of radiological conditions at the Project 57 monitoring stations to conditions observed at Community Environmental Monitoring Program (CEMP) stations around the NTTR. Biweekly samples of airborne particulates are submitted for laboratory assessment of gross alpha and gross beta radioactivity and for determination of gamma-emitting radionuclides. Annual average gross alpha values at the Project 57 monitoring stations are in the same range as the highest two values reported for the CEMP stations surrounding the NTTR. Annual average gross beta values at the Project 57 monitoring stations are slightly higher than the lowest value reported for the CEMP stations surrounding the NTTR. Gamma spectroscopy analyses on samples collected from the Project 57 stations identified only naturally occurring radionuclides. No manmade radionuclides were detected. Thermoluminescent dosimeters (TLDs) indicated that the average annual radioactivity dose at the monitoring stations is higher than the dose determined at surrounding CEMP stations but approximately half of the estimated national average dose received by the general public as a result of exposure to natural sources. The TLDs at the Project 57 monitoring stations are exposed to both natural sources (terrestrial and cosmic) and radioactive releases from the Project 57 contamination area. These comparisons show that the gross alpha, gross beta, and gamma spectroscopy levels at the Project 57 monitoring stations are similar to levels observed at the CEMP stations but that the average annual dose rate is higher than at the CEMP stations. Winds in excess of approximately 15 mph begin to generate dust movement by saltation (migration of sand at the ground surface) or direct suspension in the air. Saltated sand, PM10 (inhalable) dust, and PM2.5 (fine particulate dust) exhibit an approximately exponential increase with increasing wind speed. The greatest concentrations of dust occur for winds exceeding 20 mph. During the reporting period, winds in excess of 20 mph occurred approximately 1.6 percent of the time. Preliminary assessment of individual wind events suggests that dust generation is highly variable likely because of the influence of other meteorological and environmental parameters. Although winds sufficient to generate significant amounts of dust occur at the Project 57 site, they are infrequent and of short duration. Additionally, the potential for wind transport of dust is dependent on other parameters whose influence have not yet been assessed.

54 ENVIRONMENTAL SCIENCES↗

Synchrotron Based Microstructural Characterization Method Development for Pu Oxides

Identification of new plutonium oxide signatures is a high priority focus area of the technical nuclear forensics and nonproliferation communities. Comprehensive materials science studies of plutonium oxide are needed to advance the understanding of the microcrystalline properties and their relationship to macro-scale morphologies and signatures. Plutonium oxide particle growth is depenedent on the microcrystalline strucutures, grain size, and orientation. Microcrystalline structures have been found to vary for plutonium oxide based on the oxidation state of plutonium, concentration of reactants, and the physiochemical conditions of precipitation. Empirical observation confirms the relationship between processing conditions and particle morphology. High sensitivity, non destructive analysis of individual microcrystalline grains requires the use of bright sources of X-rays produced by synchrotron radiation, such as those at the Advanced Photon Source. The light source can reveal higher resolution crystallographic mapping, more sensitive chemical analysis, and higher fidelity morphological information than any current methods at SRNL.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Tonopah Test Range Air Monitoring: CY2018 Meteorological, Radiological, and Wind Transported Particulate Observations

In 1963, the U.S. Department of Energy (DOE) (formerly the Atomic Energy Commission [AEC]), implemented Operation Roller Coaster on the Tonopah Test Range (TTR) and an adjacent area of the Nevada Test and Training Range (NTTR) (formerly the Nellis Air Force Range). This operation resulted in radionuclide-contaminated soils at the Double Tracks site and Clean Slate I, II, and III sites. This report documents observations made during ongoing monitoring of radiological, meteorological, and dust conditions at stations installed adjacent to the Clean Slate sites and at the TTR Sandia National Laboratories (SNL) Range Operations Center (ROC). The primary objective of the monitoring effort is to support the DOE Environmental Management Nevada Program (EM NV) in the safe remediation of the environmental legacy of nuclear device development and testing by determining if wind blowing across the Clean Slate sites is transporting particles of radionuclide-contaminated soil beyond the physical and administrative boundaries of the sites, and to provide information for designing long-term monitoring of the sites. The monitoring program in 2018 included five stations. Station 400, located within TTR Area 3 and near the ROC, monitors conditions near the local workforce center. Stations 401 and 403 are located on the northern and southeastern perimeter fence lines, respectively, of the Clean Slate III site. Stations 404 and 405 are along the northern and eastern boundary fence, respectively, at Clean Slate II. The stations are generally downwind of the contaminated areas during either northwesterly or southerly winds, which are the predominant wind directions. The stations—which are similar in design to the Community Environmental Monitoring Program (CEMP) stations operating at locations surrounding the Nevada National Security Site and TTR—include meteorological instruments and continuous-flow, low-volume air samplers. Three pressurized ionization chambers for measuring gamma energy are in use at Stations 400, 401, and 403. Saltation sensors and saltation traps are deployed at the stations adjacent to the Clean Slate sites. Detailed meteorological data are recorded on data loggers, with periodic uploads via a satellite system to the Western Regional Climate Center (WRCC) at Desert Research Institute (DRI), to monitor instrument and site conditions. Air filter samples are collected every two weeks and the deposits in the saltation traps are collected when a sufficient sample mass for analysis has accumulated (generally a six- to eight-month interval). Monitoring at TTR in calendar year (CY) 2018 provided surveillance of both ambient conditions, and ground disturbance associated with remediation activities at Clean Slate II and III. The first half of CY2018 data from Stations 404 and 405 at Clean Slate II were collected during remediation activities at that site, and data collected during the final third of the year at Stations 401 and 403 at Clean Slate III coincided with remediation work at the site. Ambient conditions prevailed at Station 400 throughout the year. Dust transport by suspension and saltation is strongly dependent on wind speed. Concentrations of PM 10 (particulate matter of aerodynamic diameter ≤10 micrometers [μm], a size fraction of small particles that are suspended in the air and can be easily inhaled) remain low until winds exceed approximately 32 kilometers per hour (km/hr) (20 miles per hour [mph]). Saltation particle counts also increase above the same general threshold wind speed. Wind speeds in excess of 32 km/hr (20 mph) occur less than three percent of the time at the sites. Ground disturbing remediation activities were carried out at Clean Slate II from October 31, 2017, until July 26, 2018. Station 404 is located closest to the remediation area and is downwind of the area when winds are from the south. By late November, analysis of dust from the air sampler at Station 404 registered increases in plutonium-239+240 ( 239+240 Pu) concentrations. Peak plutonium concentrations, accompanied by elevated gross alpha concentrations and the detection of americium-241 ( 241 Am) by gamma spectroscopy, occurred between March and May 2018. During spring and early summer of 2018, elevated radionuclide concentrations were also measured in dust collected from the air sampler at Station 405, which is more than twice the distance from the remediation activity as Station 404. A minor but sustained increase in gross alpha concentration of suspended dust collected at Stations 400, 401, and 403 was also observed starting in May 2018 and continuing into August. Stations 401 and 403 are approximately 4.8 to 6.4 km (three to four miles) from Clean Slate II and Station 400 is approximately 13 km (eight miles) from that site. The radionuclide content of material that saltated into the passive Big Spring Number Eight (BSNE) traps during the Clean Slate II remediation period increased in both the traps facing toward and away from the fenced contamination area at Station 404, with the largest increases in concentration (almost five times the previous 239+240 Pu concentration) observed in the traps facing the fenced area. The radionuclide concentration in material in the trap facing away from the fence more than doubled from that measured in 2017. A similar increase was observed for the saltation trap facing away from the fenced area at Station 405, although no increase was observed for material captured in the trap facing the fenced area. Particles ranging in size from 50 to 500 µm generally move by saltation processes and are not expected to significantly contribute to dose for someone breathing in the standard respiratory zone for adult humans (1.5 to 1.7 m [4.9 to 5.6 ft] above ground level) because they are too large to be entrained in the air as suspended dust. Remediation activities at Clean Slate III began on September 5, 2018, and continued until a brief hiatus started on December 20, 2018. Although Station 401 is much closer to the remediation area than Station 403, the first increase in gross alpha and 239+240 Pu concentrations was noted in dust from filters collected at Station 403 in early November 2018. The highest radionuclide concentrations of 2018 at the Clean Slate III stations were recorded in air samples taken from Stations 401 and 403 in late December 2018 and these concentrations were comparable between the two station locations. Gamma rate data measured by the PICs was slightly higher than the annual average at Stations 401 and 403 after remediation activities began, but no single measurement was outside of the range observed in 2018 prior to remediation activities. No increase in radionuclide concentration was observed for the Clean Slate III remediation time period on air filters collected from the other stations. Radiological monitoring at Station 400—which is located at the ROC, and therefore the closest regularly staffed work location to the Clean Slate sites—recorded a higher mean gross alpha activity from dust collected on air sampler filters than in previous years. The individual biweekly air filters yielded measurements of gross alpha that were at or below the mean plus one standard deviation measured in CY2017, except for the period from April 25, 2018, through September 12, 2018. Nonetheless, gamma spectroscopy of all air filters from Station 400 identified only naturally occurring radionuclides, with no detection of americium-241 ( 241 Am) (which is used as an indicator of plutonium-241[ 241 Pu]). Alpha spectroscopy of selected air filters collected at Station 400 did not detect plutonium-238 ( 238 Pu) or 239+240 Pu above the analytical detection limit. Gross beta and gamma exposure rate data were comparable to data from regional CEMP stations. No saltation traps are deployed at Station 400. Considering the ambient monitoring periods during CY2018, the monitoring stations adjacent to the Clean Slate sites recorded above-background 238 Pu and 239+240 Pu concentrations (SNL, 1998; Turner et al., 2003) in samples collected by passive saltation traps and on selected air filters. These observations were consistent with previous years and indicated that radionuclide movement occurred under ambient conditions by processes of both saltation and suspension. The presence of radionuclides in all saltation traps, both upwind and downwind of the fenced contamination areas, was consistent with previous radiological survey results (EG&G, 1979) that show lower concentration radiologically contaminated material dispersed outside the fenced area. Although 239+240 Pu concentrations in the air filter samples were sometimes orders of magnitude higher than background, the concentrations were below risk-based action levels defined for an industrial area worker scenario (U.S. DOE, 2014). The interception of airborne dust with above-background radionuclide concentrations demonstrates that dispersal processes are continuing. Strong winds are the driver for both suspension and saltation of dust and soil. The recorded wind speed and PM10 during remediation activities at Clean Slate II and III identified discrete wind events lasting approximately five to eight hours each, which accounted for the greatest PM 10 concentrations at the monitoring stations. These events captured the effect of winds from the northwest and from the south. The observed differences in dust loading and radionuclide concentrations for the monitoring stations when they were either upwind or downwind of the contamination area identify the remediation area as a source of plutonium contaminated dust. The increase in concentration of radionuclides in airborne dust during the remediation activities, compared with measurements under previous ambient conditions (mean 239+240 Pu concentrations during remediation activities are approximately nine to 40 times higher compared to pre-remediation concentrations, depending on monitoring station), highlights the impact of land disturbance on wind-borne contaminant transport from the Clean Slate test areas. The meteorological and particulate matter monitoring indicated that conditions for wind-borne contaminant movement exist at the Clean Slate sites, and that transport of radionuclide-contaminated soil by both suspension and saltation occurred under ambient conditions and accelerated when the sites were disturbed. The 239+240 Pu alpha spectroscopy results indicated that airborne concentrations during remediation activities ranged from 2 × 10-16 to 380 × 10-16 µCi/ml. These results can be compared to the derived air concentration limit for 239 Pu of 6 × 10-11 µCi/ml for occupational workers contained in Code of Federal Regulations 10 CFR 835, Occupational Radiation Protection. Even though the air sampling results document an increase in concentration during remediation activities, the observed concentrations are less than 0.06 percent of the occupational limit. The Corrective Action Unit (CAU) closure strategy uses a risk-based approach, whereby acceptable contaminant concentrations are determined as a function of anticipated human exposure.

54 ENVIRONMENTAL SCIENCES↗

Investigating the Role of Defects in α-Pu Phase Transitions using Density Functional Theory

Before reaching its relatively low melting point of 913 K, plutonium undergoes six solid state phases: simple monoclinic alpha, body-centered monoclinic beta, face-centered orthorhombic gamma, face centered cubic delta, body-centered tetragonal delta-prime, and body-centered cubic epsilon phases. Due to their low symmetry, the monoclinic alpha and beta phases have not been studied extensively, however it has been previously hypothesized that the transition between alpha and beta is caused by defects in the lattices due to the incommensurate number of atoms. Additionally, the martensitic delta to alpha phase transformation in plutonium-gallium alloys induces an expanded alpha lattice known as alpha prime, most likely due to the insoluble gallium impurity atom. This work explores how defects such as plutonium interstitials and gallium interstitials and substitutionals may affect the alpha plutonium lattice, providing a better understanding of the mechanisms for the alpha-beta and martensitic phase transformations through density functional theory (DFT). Results indicate that plutonium interstitials within the alpha lattice induce beta features structurally and electronically, such as volume expansion and bonding changes, and gallium interstitials and substitutionals within the alpha lattice induce volume changes as observed experimentally in alpha prime.

36 MATERIALS SCIENCE↗

Polymer Compositions in Critical Experiments: Possibly Not What You Think

The Chlorine Worth Study (CWS) Experiment was performed at the National Criticality Experiments Research Center (NCERC) in December 2021. Its goal was to provide a validation benchmark experiment with chlorine and plutonium in the thermal neutron spectrum. This purpose is necessary to reduce the margin of subcriticality in aqueous chloride operations at the Los Alamos National Laboratory Plutonium Facility (PF-4). Reducing the margin of subcriticality will enable higher throughput, required to meet NNSA mission needs. The experiment used layers of plutonium plates, polyethylene (HDPE), aluminum, and polyvinyl chloride (PVC) or chlorinated polyvinyl chloride (CPVC). They were optimized to match plutonium-chloride solutions of 30 g/L, 300 g/L, and 600 g/L. Upon completion of the experiment, a International Criticality Safety Benchmark Evaluation Program (ICSBEP) report was immediately started. The compositions of all materials were assumed pure unless additional information was known (such as for the plutonium plates). During the benchmark analysis, the assumed CPVC composition was questioned. The follow-on work led to lessons learned on compositions in benchmarks. Materials, and specifically polymers, are often much more complex than a basic chemical formula. The CWS experiment is used as an example in this paper to document the lessons learned.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Non-invasive material discrimination using spectral x-ray radiography

Current radiographic methods are limited in their ability to determine the presence of nuclear materials in containers or composite objects. A central problem is the inability to distinguish the attenuation pattern of high-density metals from those with a greater thickness of a less dense material. Here, we show that spectrally sensitive detectors can be used to discriminate plutonium from multiple layers of other materials using a single-view radiograph. An inverse algorithm with adaptive regularization is used. The algorithm can determine the presence of plutonium in simulated radiographs with a mass resolution per unit area of at least 0.07 g cm{sup −2}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-situ Synthesis of PuCl 3 and Corresponding Raman and Density Functional Theory Vibrational Modes

The experimental and calculated Raman spectrum of PuCl 3 has been reported for the first time. PuCl 3 is a primary species found in plutonium metal refinement, specifically in pyrochemical salt processes including multicycle direct oxide reduction, metal chlorination, and electrorefining. As such, Raman signatures of PuCl 3 could serve as potential forensic indicators of material process history. A novel technique for synthesizing PuCl 3 from the in situ chlorination of plutonium metal with HCl was developed to establish these signatures. Cerium metal surrogates were utilized to ensure optimization of the plutonium experiments and to minimize personnel exposure, and all experiments were carried out in a Raman reaction chamber designed for air-tight, high vacuum environments. In situ Raman spectroscopy was employed in conjunction with density functional theory (DFT) to investigate the vibrational modes of PuCl 3 . Associated mixed oxy and hydroxyl phases are also reported. The combined Raman and DFT results have eliminated inconsistencies in Raman mode assignments for the MX 3 family of metal chlorides having P6 3 /m symmetry, and IR modes derived from the DFT calculations are additionally presented. The data observed in this study are of potential interest to nuclear forensic analyses, nuclear sample aging, nuclear energy, plutonium processing, and stockpile stewardship.

36 MATERIALS SCIENCE↗

A highly-enriched 244 Pu reference material for nuclear safeguards and nuclear forensics measurements

A highly-enriched 244 Pu isotope dilution reference material has been prepared and characterized for metrologically traceable measurements of very small quantities of plutonium. The amount of plutonium in samples associated with nuclear safeguards and nuclear forensic measurements can be significantly less than 1 ng. Accordingly, the ability to quantify the amount and isotopic composition of plutonium from a single mass-spectrometric analysis is particularly desirable. The highly-enriched 244 Pu reference material, described here, will minimize the magnitude of spike corrections necessary to obtain accurate information on plutonium isotopic composition from isotope dilution measurements.

07 ISOTOPE AND RADIATION SOURCES↗

Verification study of an emerging fire suppression system

Self-contained fire extinguishers are a robust, reliable and minimally invasive means of fire suppression for gloveboxes. Moreover, plutonium gloveboxes present harsh environmental conditions for polymer materials; these include radiation damage and chemical exposure, both of which tend to degrade the lifetime of engineered polymer components. Several studies have been conducted to determine the robustness of selfcontained fire extinguishers in plutonium gloveboxes in a nuclear facility, verification tests must be performed. These tests include activation and mass loss calorimeter tests. In addition, compatibility issues with chemical components of the self-contained fire extinguishers need to be addressed. Our study presents activation and mass loss calorimeter test results. After extensive studies, no critical areas of concern have been identified for the plutonium glovebox application of Fire Foe™, except for glovebox operations that use large quantities of bulk plutonium or uranium metal such as metal casting and pyro-chemistry operations.

42 ENGINEERING↗

Fission Yields and Other Diagnostics for Nuclear Performance

I summarize advances in our understanding of basic nuclear physics cross sections and decay properties that are needed to characterize the magnitude and energy-dependence of a neutron flux, and to determine the amount of fission burnup in plutonium fuel. The number of fissions that have occurred in a neutron environment can be deduced from measurements of the fission products created, providing that the fission product yields are known accurately. I describe how our understanding of plutonium fission product yields has improved in recent years through a meta-analysis of various measured data, and through identification of fission product yield incident-energy dependencies over the 0.2-2 MeV fast energy region. This led to the resolution of a previous discrepancy between the Los Alamos and Lawrence Livermore National Laboratories in their plutonium yield assessments in the fast energy region, although more experimental work is still needed to resolve discrepancies at 14 MeV. Work is also described that has improved our understanding of (n,2n) cross sections that are used as diagnostics of the high-energy neutron spectrum – both on plutonium and americium, and on the radiochemical detectors yttrium, iridium, and thulium. Finally, some observations are made on the importance of continuing to develop our Evaluated Nuclear Data Files (ENDF) database using physics insights from differential cross section and integral laboratory experiments and from nuclear theory advances.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Density functional theory study of defects in unalloyed δ-Pu

Using density functional theory, we explore in this paper various classical point and complex defects within the face-centered cubic unalloyed δ-plutonium matrix that are potentially induced from self-irradiation. For plutonium only defects, the most energetically stable defect is a distorted split-interstitial. Gallium, the δ-phase stabilizer, is thermodynamically stable as a substitutional defect, but becomes unstable when participating in a complex defect configuration. Finally, complex uranium defects may thermodynamically exist as uranium substitutional with neighboring plutonium interstitial and stabilization of uranium within the lattice is shown via partial density of states and charge density difference plots to be 5f hybridization between uranium and plutonium.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Impact of Reprocessed Uranium Management on the Homogeneous Recycling of Transuranics in PWRs

This article presents the results of a neutronics analysis related to the homogeneous recycling of transuranics (TRU) in PWRs with a MOX fuel using enriched uranium instead of depleted uranium. It also addresses an often, if not always, overlooked aspect related to the recycling of TRU in PWRs, namely the use of reprocessed uranium. From a neutronics point of view, it is possible to multi-recycle the entirety of the plutonium with or without neptunium and americium in a PWR fleet using MOX-EU fuel in between one third and two thirds of the fleet. Recycling neptunium and americium with plutonium significantly decreases the decay heat of the waste stream between 100 to 1,000 years compared to those of an open fuel cycle or when only plutonium is recycled. The uranium present in MOX-EU used fuel still contains a significant amount of 235 uranium and recycling it makes a major difference on the natural uranium needs. For example, a PWR fleet recycling its plutonium, neptunium and americium in MOXEU needs 28 percent more natural uranium than a reference UO 2 open cycle fleet generating the same energy if the reprocessed uranium is not recycled and 19 percent less if the reprocessed uranium is recycled back in the reactors, i.e. a 47 percent difference.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Selective Extraction of Uranium from Liquid or Supercritical Carbon Dioxide

Current liquid-liquid extraction processes used in recycling irradiated nuclear fuel rely on (1) strong nitric acid to dissolve uranium oxide fuel, and (2) the use of aliphatic hydrocarbons as a diluent in formulating the solvent used to extract uranium. The nitric acid dissolution process is not selective. It dissolves virtually the entire fuel meat which complicates the uranium extraction process. In addition, a solvent washing process is used to remove TBP degradation products, which adds complexity to the recycling plant and increases the overall plant footprint and cost. A liquid or supercritical carbon dioxide (l/sc-CO 2 ) system was designed to mitigate these problems. Indeed, TBP nitric acid complexes are highly soluble in l/sc-CO 2 and are capable of extracting uranium directly from UO 2 , UO 3 and U 3 O 8 powders. This eliminates the need for total acid dissolution of the irradiated fuel. Furthermore, since CO 2 is easily recycled by evaporation at room temperature and pressure, it eliminates the complex solvent washing process. In this report, we demonstrate: (1) A reprocessing scheme starting with the selective extraction of uranium from solid uranium oxides into a TBP-HNO 3 loaded Sc-CO 2 phase, (2) Back extraction of uranium into an aqueous phase, and (3) Conversion of recovered purified uranium into uranium oxide. The purified uranium product from step 3 can be disposed of as low level waste, or mixed with enriched uranium for use in a reactor for another fuel cycle. After an introduction on the concept and properties of supercritical fluids, we first report the characterization of the different oxides used for this project. Our extraction system and our online monitoring capability using UV-Vis absorbance spectroscopy directly in sc-CO 2 is then presented. Next, the uranium extraction efficiencies and kinetics is demonstrated for different oxides and under different physical and chemical conditions: l/sc-CO 2 pressure and temperature, TBP/HNO 3 complex used, reductant or complexant used for selectivity, and ionic liquids used as supportive media. To complete the extraction and recovery cycle, we then demonstrate uranium back extraction from the TBP loaded sc-CO 2 phase into an aqueous phase and the characterization of the uranium complex formed at the end of this process. Another aspect of this project was to limit proliferation risks by either co-extracting uranium and plutonium, or by leaving plutonium behind by selectively extracting uranium. We report that the former is easily achieved, since plutonium is in the tetravalent or hexavalent oxidation state in the oxidizing environment created by the TBP-nitric acid complex, and is therefore co-extracted. The latter is more challenging, as a reductant or complexant to plutonium has to be used to selectively extract uranium. After undertaking experiments on different reducing or complexing systems (e.g., AcetoHydroxamic Acid (AHA), Fe(II), ascorbic acid), oxalic acid was chosen as it can complex tetravalent actinides (Pu, Np, Th) in the aqueous phase while allowing the extraction of hexavalent uranium in the sc-CO 2 phase. Finally, we show results using an alternative media to commonly used aqueous phases: ionic liquids. We show the dissolution of uranium in ionic liquids and its extraction using sc-CO 2 with and without the presence of AHA. The possible separation of trivalent actinides from uranium is also demonstrated in ionic liquids using neodymium as a surrogate and diglycolamides as the extractant.

carbone dioxide↗