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Rapid fusion method for determination of plutonium isotopes in large rice samples

A new rapid fusion method for the determination of plutonium in large rice samples has been developed at the Savannah River National Laboratory (Aiken, SC, USA) that can be used to determine very low levels of plutonium isotopes in rice. The recent accident at Fukushima Nuclear Power Plant in March, 2011 reinforces the need to have rapid, reliable radiochemical analyses for radionuclides in environmental and food samples. Public concern regarding foods, particularly foods such as rice in Japan, highlights the need for analytical techniques that will allow very large sample aliquots of rice to be used for analysis so that very low levels of plutonium isotopes may be detected. The new method to determine plutonium isotopes in large rice samples utilizes a furnace ashing step, a rapid sodium hydroxide fusion method, a lanthanum fluoride matrix removal step, and a column separation process with TEVA Resin cartridges. The method can be applied to rice sample aliquots as large as 5 kg. Plutonium isotopes can be determined using alpha spectrometry or inductively-coupled plasma mass spectrometry (ICP-MS). The method showed high chemical recoveries and effective removal of interferences. The rapid fusion technique is a rugged sample digestion method that ensures that any refractory plutonium particles are effectively digested. The MDA for a 5 kg rice sample using alpha spectrometry is 7E-5 mBq g{sup -1}. The method can easily be adapted for use by ICP-MS to allow detection of plutonium isotopic ratios.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Impact of natural organic matter on plutonium vadose zone migration from an NH4Pu(V)O2CO3(s) source

Large amounts of plutonium produced at the Savannah River Site (SRS) in the latter half of the last century led to the release of plutonium to the subsurface. Low-level waste containing plutonium has also been disposed of in the SRS vadose zone. The mobility and risk posed by these plutonium sources is not well understood, in part, because of unknown interactions of the various mobile plutonium species with natural organic matter (NOM). This study investigated the influence of NOM on the behavior of plutonium(V) in the vadose zone through a combination of field lysimeter and laboratory studies. Well-defined solid sources of NH4PuVO2CO3(s) placed in 5-L lysimeters containing vadose zone soils NOM-amended or unamended were exposed to natural SRS meteorological conditions for three years. These lysimeters were removed from the field and analyzed using wet chemistry methods and X-ray absorption spectroscopy (XAS). Plutonium desorption from soils recovered from the lysimeters and laboratory batch sorption experiments using Pu-free soils both indicated that surface mediated reduction of Pu(V) to Pu(IV) was influencing Pu sorption behavior. For both lysimeters (amended and unamended with NOM), Pu migrated slowly through the lysimeter core, with > 95% of the Pu remaining within 2 cm of the source. However, without the NOM amendments, Pu was transported significantly farther than in the presence of NOM. Thus, the presence of NOM appeared to decrease the mobility. Working hypotheses to explain this behavior are that 1) formation of ternary surface-NOM-Pu complexes enhanced Pu sorption affinity causing less mobility and/or 2) formation of these ternary surface-NOM-Pu complexes prevented reoxidaiton of Pu(IV) to more mobile Pu(V) in the pore water.

plutonium, organic matter↗

Effect of chemical environment on the radiation chemistry of N , N -di-(2-ethylhexyl)butyramide (DEHBA) and plutonium retention

N,N-di-(2-ethylhexyl)butyramide (DEHBA) has been proposed as part of a hydro-reprocessing solvent extraction system for the co-extraction of uranium and plutonium from spent nuclear fuel, owing to its selectivity for hexavalent uranium and tetravalent plutonium. However, there is a critical lack of quantitative understanding regarding the impact of chemical environment on the radiation chemistry of DEHBA, and how this would affect process performance. Here we present a systematic investigation into the radiolytic degradation of DEHBA in a range of n-dodecane solvent system formulations, where we subject DEHBA to gamma irradiation, measure reaction kinetics, ligand integrity, degradation product formation, and investigate solvent system performance through uranium and plutonium extraction and strip distribution ratios. The rate of DEHBA degradation in n-dodecane was found to be slow (G = -0.31 ± 0.02 μmol J -1 ) but enhanced upon contact with the oxidizing conditions of the investigated solvent systems (organic-only, or in contact with either 0.1 or 3.0 M aqueous nitric acid). Two major degradation products were identified in the organic phase, bis-2-ethylhexylamine (b2EHA) and N-(2-ethylhexyl)butyramide (MEHBA), resulting from the cleavage of C–N bonds, and could account for the total loss of DEHBA up to ~300 kGy for organic-only conditions. Both b2EHA and MEHBA were also found to be susceptible to radiolytic degradation, having G-values of -0.12 ± 0.01 and -0.08 ± 0.01 μmol J -1 , respectively. Solvent extraction studies showed: (i) negligible change in uranium extraction and stripping with increasing absorbed dose; and (ii) plutonium extraction and retention exhibits complex dependencies on absorbed dose and chemical environment. Organic-only conditions afforded enhanced plutonium extraction and retention attributed to b2EHA, while acid contacts inhibited this effect and promoted significant plutonium retention for the highest acidity. Overall it has been demonstrated that chemical environment during irradiation has a significant influence on the extent of DEHBA degradation and plutonium retention.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

A Python Tool for Aqueous Plutonium Nitrate Density Law Input Preprocessing in MCNP6

Here, this work develops a predictive density tool in Python, named Plutonium Nitrate Solutions (PuNS), to reduce bias and uncertainty in nuclear criticality safety calculations for plutonium nitrate systems. The Pitzer method and an empirical method were implemented into the PuNS tool to generate atom densities for use in MCNP6 material cards. These material cards are directly prepared into an MCNP6 input text file and are calculated based on customizable user inputs of plutonium content, nitric acid content, temperature, and plutonium isotope weight percentages. The PuNS tool is validated and verified against the International Criticality Safety Benchmark Evaluation Project Handbook experiments and is observed to predict densities within a root mean square error of 0.89% for the Pitzer method and 1.82% for the empirical method. These errors in density lead to up to 1569 pcm difference in MCNP6 calculated k eff for the Pitzer method and up to a 1751 pcm difference for the empirical method when compared to experimental benchmarks. Simultaneous work is also being performed at Los Alamos National Laboratory and the University of New Mexico to create a similar tool for plutonium chloride solutions, named Plutonium Chloride Solution, which aims to provide the accreditation of the chlorine absorption. These capabilities will not only provide more accurate models but also facilitate an improved understanding of solution systems and a potential relaxation in the conservatism of current aqueous plutonium processing criticality safety limits.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Compatibility of molten plutonium with wrought and additively manufactured metal crucibles

Understanding plutonium’s interaction with metals is crucial for optimizing pyrochemical operations, nuclear fuel containment, and various actinide processing techniques. Traditionally, tantalum crucibles are employed for plutonium processing due to their high durability, excellent temperature stability, and low solubility in plutonium. However, tantalum faces challenges such as plutonium wetting and diffusion, making surface coatings particularly important for crucibles in pyrochemical applications to enhance corrosion resistance against plutonium. Tantalum is also expensive and difficult to machine, prompting the need for advanced manufacturing techniques to address these challenges. Here, in this work, we investigate the interaction of Pu with tantalum and titanium crucibles fabricated using both traditional machining methods and laser powder bed fusion (LPBF) additive manufacturing (AM). LPBF-AM is an advanced technique that allows for the creation of complex geometries from traditionally difficult-to-machine metals by using a high-powered laser to build parts. Previous studies of conventional manufactured tantalum have utilized oxidation and carburization of the surface to mitigate plutonium wetting; however, no studies of surface modified LPBF-AM material have been undertaken. These studies are crucial, given the typical differences in the grain structure between conventional and LPBF-AM materials. All crucibles underwent differential scanning calorimetry to confirm the melting of plutonium. Subsequently, the crucibles were sectioned and mounted in epoxy for microstructural analysis using optical microscopy and scanning electron microscopy. This investigation, comparing the performance of wrought vs AM metal crucibles, provides a basis for future tooling applications in actinide processing techniques and can address the challenges associated with traditional machining, particularly in pyrochemical applications.

Actinides↗

Literature Review Investigating Historical Plutonium Solubility in SRS Tank Waste

The Savannah River Site (SRS) has designed the Accelerated Basin De-inventory (ABD) program to accelerate the de-inventory of L-Basin and accelerate the Spent Nuclear Fuel (SNF) disposition mission. Similarly, the H-Canyon facility at SRS is reestablishing the 6.3D electrolytic dissolver for dissolving unirradiated stainless-steel (SS) clad Fast Critical Assembly (FCA) fuel. In both discard types (ABD and FCA), plutonium is present and its complex solubility when composited to Concentration, Storage, and Transfer Facility (CSTF) sludge is being investigated as it may have downstream impacts to the liquid waste (LW) organization. This literature review aims to highlight and compile the existing literature on plutonium solubility in waste streams relevant to ABD and FCA discards, as well as discuss some considerations in analyzing solubility data of plutonium. This review serves to help define the analysis methods for future experiments involving plutonium (and other actinides) and in designing appropriate testing conditions surrounding these studies. This review is broken up into five parts and will discuss: (i) The possible effects of testing hold time and temperature on plutonium solubility, (ii) the influence of neutralization rate and particle size of freshly precipitated discards, (iii) the coprecipitation of plutonium with iron and uranium, (iv) predictive solubility modeling and the influence of supernate anions on solubility, and (v) the speciation of plutonium in solutionas a result of supernate anions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Application of an Empirical Density Law via Python for Aqueous Plutonium Chloride Systems in MCNP6

Current aqueous plutonium processing models for criticality safety often contain significant bias due to material modeling assumptions. These solutions include plutonium chloride solutions, which are modeled as fictitious plutonium metal-water mixtures because little is known about the actual density of the solution. Furthermore, there is no current predictive capability for modeling plutonium metal-water mixtures that is approved for use at Los Alamos National Laboratory (LANL). Recent density measurements for aqueous plutonium chloride systems (PuCl 3 -HCl-H 2 O) now allow for the development and application of a more realistic density law. This work develops a Python-based density law for this ternary solution using an empirical method. This code can be used in conjunction with an MCNP6 input to determine the density and composition of a solution based upon user inputs of plutonium concentration, hydrochloric acid concentration, and temperature. The tool allows users to input plutonium and acid content of a solution in terms of molality, molarity, or concentration, and predicts density within the current data range within 1.4% of experimental data. Current preliminary MCNP6 calculations utilizing this tool have demonstrated a minimum decrease in system reactivity of 5% in comparison to the current modeling conventions. Thus, this tool enables more accurate criticality safety operational limits by better crediting chorine content while still maintaining necessary conservatism.

Density Law↗

Elucidating the Radiation-Induced Redox Chemistry of Plutonium Under Used Nuclear Fuel Reprocessing Conditions

Plutonium plays a critical role in the development of sustainable nuclear fuel cycles, and yet, our fundamental understanding of this element’s inherent radiation-induced redox chemistry and associated impacts on nuclear fuel cycle technologies is limited. Unanticipated changes in oxidation state distribution can influence the speciation and transport of plutonium in a given process. Control of these parameters is especially important for used nuclear fuel reprocessing technologies, wherein the separation and recovery of plutonium is typically achieved by the selective formation, maintenance, and complexation of specific oxidation states. Furthermore, plutonium’s inherent radiation-induced redox chemistry has the capacity to influence the radiolytic behavior of its complexes, the longevity of which are critical in the design of efficient and cost-effective advanced reprocessing technologies. These radiation-induced processes are unavoidable under fuel cycle conditions owing to the inherency of ionizing radiation fields to the decay of plutonium’s isotopes and to the various other radioisotopes generated by nuclear fission and neutron-capture process and the subsequent radioactive decay of their products. As such, mechanistically understanding the response of plutonium’s multiple oxidation states to multi-component ionizing radiation fields is essential for predicting the behavior of this critical element under used nuclear fuel reprocessing conditions. Here, through a combination of time-resolved (electron pulse) and steady-state (alpha and gamma) irradiation experiments complemented by quantitative, multiscale modeling calculations, we present advances in our understanding of radiation-induced plutonium redox chemistry!

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigations into validation of plutonium solutions for criticality safety analysis

Plutonium solution chemistry is among the most complex of all the elements in the periodic table. Under acidic conditions up to four different oxidation states can be present in significant amounts in a single solution. From the perspective of nuclear criticality safety, accurate information regarding the concentration of plutonium and other constituents in solution must be well-known in order to correctly model plutonium solution systems for analysis. This requires knowledge of the solution system along with the ability to make accurate assumptions and predictions of the chemical and physical properties of the solution system. If neutron transport methods are used to assess subcriticality in a nuclear criticality safety analysis, the models must be compared with benchmark experiments which are similar and the suitability of the computer code system must be quantified. This paper describes some investigations undertaken to support the validation of plutonium solution systems for nuclear criticality safety analysis and how the Whisper sensitivity/uncertainty (S/U) tool can provide information to support validation of such systems. Case study results for various solution systems such as aqueous plutonium nitrate, aqueous plutonium chloride and hypothetical metal-water mixture are presented. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electrolytic Oxide Reduction of Plutonium Oxide Surrogates

Our research team has investigated electrolytic oxide reduction (EOR) as an improved metal production process versus the currently employed multiple cycle direct oxide reduction (MCDOR) process for the conversion of plutonium oxide to plutonium metal. Inherent advantages in safety, waste generation, efficiency, and operational ease make EOR an attractive alternative to traditional metal production practices. Phase I of the project consisted of the construction of a prototype electrochemical cell, and proof of concept experiments towards the reduction of SnO 2 and CeO 2 compounds. Phase II of the project was focused on the optimization of the cerium system in preparation for future plutonium EOR experiments. We observed the electrolytic reduction of cerium oxide resulting in mixed degrees of success, and discovered this was a result of parasitic side reactions and partial reduction. We employed cyclic voltammetry (CV) to identify the products of these side reactions and characterize partially reduced species. We also observed that, when metal was successfully produced by EOR, a large amount of passed charge was required. We concluded that this observation was due to several inefficiencies of the process relating to the reduction mechanism (e.g. inefficient use of cathodically produced calcium). We used our CV results to guide our optimization of the EOR of CeO 2 by refining our electrochemical method, cell geometry, and materials of construction. Finally, we developed a next generation cell, worked to establish a new molten salt electrochemical capability in the Plutonium Facility, and completed a strategy for plutonium experiments. Our electrochemical method to produce plutonium metal clearly supports the core mission of the laboratory. Furthermore, this project has allowed for the development of capabilities that will provide valuable data to programs interested in characterization and detection, as well as science of signatures. Additionally, establishing this capability in the plutonium facility will facilitate future safeguard studies that can assist with safeguard development in molten salt reprocessing flowsheets, and molten salt reactor designs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NNSS Soils Monitoring: Plutonium Valley (CAU 366) FY2019

Desert Research Institute (DRI) conducted a field assessment of the potential for radionuclide-contaminated soil to be transported from the Plutonium Valley Dispersion Sites Contamination Area (CA) because of both wind and storm water runoff. This activity supported U.S. Department of Energy (DOE) Environmental Management Nevada Program (EM NV) efforts to establish post-closure monitoring plans for the Plutonium Valley Dispersion Sites Corrective Action Unit (CAU) 366. The DRI task was intended to identify the likely mechanism(s) of transport and determine the meteorological conditions that might cause the movement of radionuclide-contaminated soils. The emphasis of the work was on collecting sediment transported by channelized storm runoff and measuring airborne dust concentrations and associated wind conditions. These data will facilitate an appropriate post-closure monitoring program. In 2011, DRI installed meteorological monitoring stations north and south of the Plutonium Valley CA—known as Pu Valley North and Pu Valley South, respectively—as well as a fluvial sediment sampling station within the CA. Since installation, temperature, wind speed, wind direction, relative humidity, precipitation, solar radiation, barometric pressure, soil temperature, volumetric soil moisture content, and airborne particulate concentrations have been collected at both meteorological stations. The maximum, minimum, and average or total (as appropriate) for each of these parameters were recorded for each 10-minute interval. The sediment sampling station included an automatically activated sampling pump with collection bottles for suspended sediment, which was activated when sufficient flow was present in the channel, and passive traps for bedload material that was transported down the channel during runoff events. This report presents data collected from these stations during fiscal year (FY) 2019. During the FY2019 (October 1, 2018, through September 30, 2019) reporting period, the warmest month was July and the coldest month was February. Monthly total solar radiation was highest in June or July (depending on the station) and lowest in December. Monthly mean wind speeds were highest during February. At the Pu Valley North station, winds were commonly northerly, northwesterly, and southerly. At the Pu Valley South station, the wind direction was more variable and winds frequently came from most directions, excluding westerly and northwesterly winds. Winds above 15.0 miles per hour (mph) (24.1 kilometers per hour [km/hr]) were frequently southerly at both stations, and less-frequent strong winds were northerly (at the Pu Valley South station) or northwesterly (at the Pu Valley North station). Monthly average relative humidity ranged from 18 percent in August to 62 percent in January and February. Monthly total precipitation ranged from zero at both stations in September to 2.23 inches (in) (56.6 millimeters [mm]) during February at the Pu Valley South station and 2.09 in (53.1 mm) during March at the Pu Valley North station. From October 1, 2018, through September 30, 2019, the total precipitation was 8.23 in (209 mm) and 8.15 in (207 mm) at the Pu Valley South and Pu Valley North stations, respectively. The largest daily precipitation totals of 1.46 in (37.1 mm) and 1.14 in (29.0 mm) occurred at the Pu Valley South and Pu Valley North stations, respectively, on March 6, 2019. However, the ISCO autosampler was not activated during any storm event in FY2019 because the channel water depth measurements were insufficient for suspended sediment sample collection. Additionally, because no significant flow through the channel was indicated, no bedload samples were collected. Light breezes of 0.0 mph to 5.0 mph (0.0 km/hr to 8.0 km/hr) occurred most frequently (approximately 55 percent to 57 percent of the time). The frequency of occurrence diminished exponentially as the wind speed increased such that winds in excess of 25.0 mph (40.2 km/hr) occurred less than 0.01 percent of the time. Winds in excess of 15.0 mph (24.1 km/hr) were most commonly southerly, which is likely controlled by the topography of the valley because topographic highs define the east and west sides of the valley and converge toward the north.The concentrations of PM2.5 (particulate matter with an aerodynamic diameter ≤2.5 micrometers [μm]) and PM10 (particulate matter with an aerodynamic diameter ≤10 μm) in the air generally increase as wind speed increases. However, the particle profiler at the Pu Valley South station regularly malfunctioned, which resulted in poor data quality and a limited period of record within FY2019. Therefore, discussion of the annual dust observations is mostly limited to the Pu Valley North station. At the Pu Valley North station, significant increases in windblown dust concentrations were observed when wind speeds exceeded 15.0 mph (24.1 km/hr), especially during southerly winds. When all wind speeds were considered, high dust concentrations at the Pu Valley North station were frequently associated with northerly, northwesterly, or southerly winds. The majority of PM10 transport at the Pu Valley North station occurred when winds were blowing northerly and northwesterly because of the high frequency of winds up to 15.0 mph (24.1 km/hr). The ratio of PM10 to PM2.5 is a qualitative indicator of the proximity of dust sources to the observation point and the values of the PM10 to PM2.5 ratio tend to be higher nearer to the source. The PM10 to PM2.5 ratio increased from 1.2 to 2.8 with higher wind speeds at the Pu Valley North station. This increase suggests that some locally sourced PM10 was present in the air when local winds exceeded 15.0 mph (24.1 km/hr). Local dust suspension is interpreted during major dust events when peaks in the PM10 to PM2.5 ratio occur simultaneously with the maximum wind speed and the peak PM10 concentration. Analysis of the five major dust events in FY2019 revealed that northerly winds were dominant in three events and southerly winds were dominant in two events. Local suspension of dust within Plutonium Valley is suspected to have occurred during two of the five major events (April 9, 2019, and September 28 to 29, 2019), and a nonlocal source of dust is presumed for the three other major dust events (October 14, 2018; May 16, 2019; and September 2, 2019). The three suspected regional dust transport events exhibited winds that typically did not exceed the 15.0 mph (24.1 km/hr) wind speed threshold for local dust transport and featured PM10 to PM2.5 ratios that indicate large-scale regional dust transport. Similar event characteristics (e.g., wind speed and PM10 concentration) were observed at air monitoring stations approximately 70 mi (113 km) to the northwest within the Tonopah Test Range (TTR). Therefore, these three regional events may not reflect transport from the Plutonium Valley CA. Routine monitoring of meteorological and hydrologic parameters at Plutonium Valley has been discontinued at the request of EM NV, effective at the conclusion of FY2019. Environmental data acquisition has been completed, and both Pu Valley North and Pu Valley South meteorological stations within Plutonium Valley as well as the ISCO autosampler station within the CA were removed on October 14, 2019.

54 ENVIRONMENTAL SCIENCES↗

Effects of Chlorine Capture and a Proposed Density Law on the Reactivity of Plutonium Solution Systems

During fissionable material processing, all normal and credible abnormal conditions must remain safely subcritical. Nuclear Criticality Safety (NCS) uses a number of methods to determine subcriticality, one of which is the use of neutron transport codes such as MCNP6. In order to create models for use with MCNP6, both the geometry and materials in fissionable material processes must be known, or assumptions must be made and quantified for the impact to bias. One of the systems with a significant amount of bias due to material modeling assumptions is in the area of aqueous plutonium processing. These solutions are typically plutonium nitrate solutions or plutonium chloride solutions, which are modeled as fictitious plutonium metal-water mixtures because little is known about the actual density of the solution and there is no current predictive capability approved for use at Los Alamos National Laboratory (LANL) for modeling them. This research is currently underway to fill the gap and develop an algorithm for use with MCNP6 to model the density of plutonium chloride solutions. The method is to be validated with experimental data for density, and also validated with critical experiments using MCNP6. Note that the Chlorine Worth Study (CWS) was performed in December 2021 to help bridge the gap in chlorine data for critical experiments, and is currently awaiting International Criticality Safety Benchmark Evaluation Project (ICSBEP) review. This study was performed by LANL at the National Criticality Experiments Research Center (NCERC) at the Nevada National Security Site (NNSS). Additional information regarding this experiment may currently be found in LA-UR- 22-29180. Additionally, the Chemistry-Actinide Analytical Chemistry (C-AAC) at LANL has performed a number of solution density measurements for PuCl 3 -HC 1 -H 2 O, allowing for such data be used to create a semi-empirical density via the Pitzer method. The published dataset for the measurements is documented in LA-UR-22-25454. This method has already been tested successfully for aqueous plutonium nitrate solutions in SCALE. Current solution density measurements exist of plutonium concentrations of 0-~142g/L, all at 2M HC1, at temperatures 20-40°C. Additional data was taken for HC1-corrected density values, which essentially mimics the data for a pure PuCl x -water solution. The calculations in this report aim to support the current research by demonstrating the difference in system reactivity for the current modeling method when compared to the new proposed modeling with a density law implementation, which is being written as a Python tool to be used with MCNP6.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Solvent extraction system for plutonium colloids and other oxide nano-particles

The invention provides a method for extracting plutonium from spent nuclear fuel, the method comprising supplying plutonium in a first aqueous phase; contacting the plutonium aqueous phase with a mixture of a dielectric and a moiety having a first acidity so as to allow the plutonium to substantially extract into the mixture; and contacting the extracted plutonium with second a aqueous phase, wherein the second aqueous phase has a second acidity higher than the first acidity, so as to allow the extracted plutonium to extract into the second aqueous phase. The invented method facilitates isolation of plutonium polymer without the formation of crud or unwanted emulsions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Thermal and Physical Properties of Plutonium Dioxide Produced from the Oxidation of Metal: a Data Summary

The ARIES Program at the Los Alamos National Laboratory removes plutonium metal from decommissioned nuclear weapons, and converts it to plutonium dioxide in a specially-designed Direct Metal Oxidation furnace. The plutonium dioxide is analyzed for specific surface area, particle size distribution, and moisture content. The purpose of these analyses is to certify that the plutonium dioxide powder meets or exceeds the specifications of the end-user, and the specifications for the packaging and transport of nuclear materials. Analytical results from plutonium dioxide from ARIES development activities, from ARIES production activities, from muffle furnace oxidation of metal, and from metal that was oxidized over a lengthy time interval in air at room temperature, are presented. The processes studied produce plutonium dioxide powder with distinct differences in measured properties, indicating the significant influence of oxidation conditions on physical properties.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Plutonium metal vs. oxide determination with the pulse-shape-discrimination-capable plastic scintillator EJ-299-33

Neutron measurements can be used to distinguish plutonium in metal or oxide form, a capability that is of great interest in nuclear nonproliferation, treaty verification, and other applications. This paper describes measurements performed on well-characterized samples of plutonium oxide and plutonium metal using the pulse-shape-discrimination-capable plastic scintillator EJ-299-33. Results are compared to those obtained with a same-sized detector cell using the liquid scintillator EJ-309. The same optimized, digital pulse shape discrimination technique is applied to both detectors and the neutron pulse height distributions are compared. Results show that the EJ-299-33 plastics can be successfully used for plutonium measurements, where the gamma ray to neutron detection ratio is much higher than for typical radioactive sources. Results also show that EJ-299-33 detectors can be used to characterize plutonium samples, specifically to discriminate between plutonium metal and oxide.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Density-functional theory for plutonium

We review here developments in the theoretical description and understanding of plutonium in terms of a metal with itinerant (band) 5f electrons. Within this picture most facets of this remarkable and anomalous material are accurately described by first-principle, parameter-free, density-functional-theory (DFT) calculations. We show that the model explains plutonium’s phase stability, elasticity, lattice vibrations, electronic structure, alloy properties, and magnetism. Fluctuations are addressed by means of constrained DFT calculations and new light is shed on the anomalous properties of δ plutonium, including explaining its negative thermal expansion. Effects of alloying and point defects in plutonium are also addressed. It is further emphasized that strong electron correlations, originating from a large intra-atomic Coulomb repulsion (~4 eV) of the 5f electrons, that has often been assumed for plutonium in the literature, is inconsistent with the experimental phase diagram of plutonium.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Small-scale production of bespoke accelerated aging plutonium alloy

Here, this study demonstrates the 100 g scale manufacture of a plutonium alloy that ages at an accelerated rate. The resulting alloy ages six times faster than typical weapons-grade plutonium due to the addition of 238 Pu. As a major innovation, the process involved using a partial direct oxide reduction technique. This method was achieved by developing a new, complex geometry stirrer using additive manufacturing to reduce the 238Pu oxide and efficiently incorporate it into weapons-grade plutonium metal. The material was then purified by molten salt extraction and electrorefining before being alloyed with gallium. The alloy was then cold-rolled and annealed in a homogenization heat treatment. The resulting disk was characterized by metallography and differential scanning calorimetry, and the impurity content was determined using analytical chemistry techniques. The results show that a homogeneous delta phase plutonium alloy was achieved with expected microstructure and minimal impurities. This study was also successful in changing the plutonium isotopic composition by incorporating additional 238 Pu to accelerate the effects of radiation damage. This enables researchers to study long-term aging phenomena in a reduced time frame, thus avoiding the need for large-scale material production and circumventing the limitations of using naturally aged, archived plutonium.

Aging theory↗

Separation of Plutonium from Irradiated Fuels and Targets

Spent nuclear fuel from power production reactors contains moderate amounts of transuranium (TRU) actinides and fission products in addition to the still slightly enriched uranium. Originally, nuclear technology was developed to chemically separate and recover fissionable plutonium from irradiated nuclear fuel for military purposes. Military plutonium separations had essentially ceased by the mid-1990s. Reprocessing, however, can serve multiple purposes, and the relative importance has changed over time. In the 1960’s the vision of the introduction of plutonium-fueled fast-neutron breeder reactors drove the civilian separation of plutonium. More recently, reprocessing has been regarded as a means to facilitate the disposal of high-level nuclear waste, and thus requires development of radically different technical approaches. In the last decade or so, the principal reason for reprocessing has shifted to spent power reactor fuel being reprocessed (1) so that unused uranium and plutonium being recycled reduce the volume, gaining some 25% to 30% more energy from the original uranium in the process and thus contributing to energy security and (2) to reduce the volume and radioactivity of the waste by recovering all long-lived actinides and fission products followed by recycling them in fast reactors where they are transmuted to short-lived fission products; this reduces the volume to about 20%, reduces the long-term radioactivity level in the high-level waste, and complicates the possibility of the plutonium being diverted from civil use – thereby increasing the proliferation resistance of the fuel cycle. In general, reprocessing schemes can be divided into two large categories: aqueous/hydrometallurgical systems, and pyrochemical/pyrometallurgical systems. Worldwide processing schemes are dominated by the aqueous (hydrometallurgical) systems. This document provides a historical review of both categories of reprocessing.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗