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DOE OSTI2025

Utilization of traceable standards to validate plutonium isotopic purification and separation of plutonium progeny using AG MP-1M resin for nuclear forensic investigations

Radio-chronometric studies on plutonium (Pu) materials require independent measurement of the Pu (parent) content and isotopic distribution as well as concentration and isotopic distribution of the plutonium isotopic decay products. We performed a series of experiments to demonstrate the consistency of separations using the Lewatit MP 800 macroporous anion exchange resin and the AG MP-1M resin with traceable Pu isotopic certified reference material (CRM) standards 136, 137, 138, and 126-A. Two different mesh-sizes of the AG MP-1M resin were tested and the 50–100 mesh size resin was found to work more efficiently for the separation task. Both Lewatit and AG MP-1M resins were found to perform satisfactorily for quantitatively extracting the americium (Am) and uranium (U) progeny as well as gallium (Ga) present as a tracer in the Pu material. Both resins were effective in removing isobaric interferences from the Pu fraction used in isotopic measurements by thermal ionization mass spectrometry (TIMS). To address the co-elution of uranium and gallium, Alizarin red S (ARS) was used as a colorimetric dye to determine the behavior of UO 2 2+ and Ga 3+ on AG MP-1M resin with various acidic solutions as eluents using UV–vis spectra. Poor resolution of these peaks complicated quantitative analysis by UV–vis spectroscopy, but these results were informative in planning automated separation experiments by HPLC. LA-UR-24-28919.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2025

Radiolytic degradation of 240 Plutonium and 242 Plutonium oxalates

Raman, FTIR, and diffuse reflectance spectroscopy were used to study the auto-radiolytic degradation of 240 Pu and 242 Pu oxalates. The significant differences in the lifetimes of 240 Pu and 242 Pu enabled the differentiation between environmental and radiolytic mechanisms. 240 Pu oxalates were observed to decompose to PuOCO 3 at intermediate times (~ 20 weeks) followed by partial conversion to PuO 2 at times greater than one year. Atmospheric oxidation was shown to be the primary decomposition mechanism for 242 Pu(IV) oxalate, and the alpha radiolysis of aquo and oxalate ligands serves as a secondary decomposition mechanism. In conclusion, this study offers a fresh perspective on radiolytic aging, which is crucial for long-term storage applications.

Analytical Techniques in Art Conservation↗

DOE OSTI2024

Neutron spectroscopy of plutonium using a handheld detection system

The ability to distinguish multiple forms of plutonium from one another, such as oxide and metal, is paramount in areas of nuclear nonproliferation and international safeguards. In its metal form, plutonium can be readily used in a nuclear weapon, while oxide forms are associated with nuclear reactor fuel. Oxide-based plutonium forms emit neutrons with an energy spectrum that is significantly different from the fission neutrons that are emitted from plutonium metal. Organic scintillation detectors output pulses that are proportional to the neutron energy deposited, and therefore present a means of distinguishing these plutonium forms based on their energy spectra. In this work, metal and oxide forms of plutonium were measured using a handheld detection system based on an organic glass scintillator. Monte Carlo modeling of these experiments was performed to provide insight into the origin of the features in the observed light output spectra. Through analysis of multiple regions of these spectra, in a matter of minutes we were able to unambiguously discriminate oxide and metal plutonium forms from one another and from a plutonium-beryllium neutron source, which was considered for comparison because these sources are commonly used in industrial applications. The ability to discriminate weapons-usable material from nuclear reactor fuel has applications in nuclear treaty verification and safeguards.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

DOE OSTI2024

Radiation-Induced Plutonium Redox Chemistry

Plutonium plays a key role in global actinide research and nuclear fuel cycle technologies, and yet, our fundamental understanding of its inherent radiation-induced chemical behavior is limited. These radiation-induced processes cannot simply be switched off, as they are as fundamentally inherent to plutonium as the impact of relativistic effects on its f-electrons. In less chemically complex actinide systems, such as aqueous solutions of neptunium and americium, , radiolysis products play a significant role in the redox cycling of their oxidation states. However, plutonium's multiple, coexisting, and chemically active oxidation states, which comprise of bare ions and dioxo cations, provide additional redox pathways that complicate radiation-induced processes. Oxidation state control is critical for the manipulation of plutonium, especially in used nuclear fuel reprocessing technologies, where oxidation specific states are successfully extracted, and others rejected. Consequently, mechanistically understanding the behavior of plutonium’s multiple oxidation states in the presence of intense ionizing radiation fields is essential for predicting the behavior of this element under multiple conditions that support the development and innovation of nuclear fuel cycle technologies. Here, we present recent advances in our understanding of plutonium radiation chemistry, including the first-ever multiscale model for predicting gamma radiation-induced plutonium redox chemistry, and new chemical kinetics for the reaction of plutonium and its complexes of tributyl phosphate (TBP), N,N-di-(2-ethylhexyl)butyramide (DEHBA), and N,N-di-(2-ethylhexyl)isobutyramide (DEHiBA) with transients radiolysis products, a measured using electron pulse radiolysis.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2025

Unravelling the radiation-induced redox chemistry of plutonium ions in aqueous solution

Plutonium plays a critical role in nuclear fuel cycle technologies, but our understanding of its fundamental radiation-induced redox chemistry is limited. Changes in oxidation states affect the speciation and transport of plutonium ions in solution. For example, solvent extraction techniques used to separate and recover plutonium from used nuclear fuel rely on the selective formation, maintenance, and complexation of specific plutonium oxidation states. However, radiolytically generated radicals, ions, and molecules can drive the oxidation state distribution of plutonium ions far from equilibrium, ultimately changing the physical and chemical properties of the bulk system. These radiation-induced processes are inevitable due to the ionizing radiation fields generated by the radioactive decay of plutonium and its daughter nuclides. Therefore, mechanistically understanding how plutonium's various oxidation states respond to ionizing radiation is essential for predicting its behavior in solution. Here, we present significant advances in our understanding of radiation-induced plutonium redox chemistry by using time-resolved (electron pulse) and dose accumulation (alpha and gamma) irradiation techniques, along with quantitative multiscale modeling methods.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2026

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↗

DOE OSTI2025

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↗

DOE OSTI2025

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↗

DOE OSTI2024

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↗

DOE OSTI2025

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↗

DOE OSTI2025

Plutonium Solubility and Supernate Concentration for Neutralized Fast Critical Assembly Discards to Savannah River Site Tank Waste

The Savannah River Site (SRS) plans to dissolve non-irradiated stainless steel (SS)-clad bundles of Fast Critical Assembly (FCA) materials in eighteen batches.1 FCA dissolution is currently underway in the 6.3D dissolver by simultaneous chemical and electrolytic dissolution, which is required to generate the harsh conditions necessary for dissolution of metal-oxide (MOX) and non-aluminum spent nuclear fuels (NASNFs).2 Nitric acid and potassium fluoride are used to promote chemical dissolution.2 Gadolinium will be added during processing as a thermal neutron poison for criticality control. There are no plans for recovering plutonium from this waste stream. After FCA dissolution, the acidic (HNO3/KF) “discards” containing the dissolved metals will be neutralized by addition of 50 wt% sodium hydroxide to a final free hydroxide concentration of 1.2 M.1 Neutralization will precipitate a slurry of insoluble solids, predominantly metal oxides/hydroxides of plutonium, uranium, and SS components. Small fractions of the SS components, Pu, U, and Gd will remain dissolved in the supernate. The neutralized slurry will be composited to existing radioactive waste storage tanks within the SRS Concentration, Storage, and Transfer Facilities (CSTF) containing other similar sludge batch (SB) materials.1 The fate of soluble plutonium and freshly-precipitated, colloidal plutonium from this process are of concern since the total Pu can challenge the waste acceptance criteria (WAC) at the downstream SRS Liquid Waste (LW) facility. Supernate decants including the neutralized FCA discards (nFCAd) within the CSTF will be composited with salt batch (StB) materials and transferred to the SRS Salt Waste Processing Facility (SWPF), where total plutonium is also of concern.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2024

Predicting Radiation-Induced Plutonium Redox Chemistry using Multi-scale Modeling Methods

Over the the last 70 years plutonium (Pu) has been integral in the development of several technologies that have changed the world, yet our fundamental understanding of its chemistry is still far from complete. This is a testament to this element’s unique and complex properties, such as its ability to coexist as multiple oxidation states in aqueous solution. Careful manipulation of plutonium oxidation states is essential in the study and utilization of its rich chemistry. To achieve this level of control, a comprehensive mechanistic understanding of radiation-induced plutonium redox chemistry is critical due to the unavoidable exposure of plutonium to ionizing radiation fields, both inherent and from in-process applications. For this reason, we have developed an experimentally evaluated multi-scale computer model for the prediction of gamma radiation-induced Pu(IV) redox chemistry in concentrated nitric acid solutions (1.0, 3.0, and 6.0 M). Under these acidic, aqueous solution conditions, cobalt-60 gamma irradiation afforded negligible net change in the steady-state oxidation state distribution of Pu(IV). Multi-scale calculations, which are in excellent agreement with experimental data, indicate that this observation is due to radiation-induced redox cycling between Pu(IV) and Pu(III), as achieved by the reduction of Pu(IV) by radiolytic nitrous acid and hydrogen peroxide, and the oxidation of Pu(III) by nitrate and hydroxyl radicals. These radiation-induced redox processes are augmented by plutonium’s inherent disproportionation reactions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2024

Modeling Plutonium Decorporation in a Female Nuclear Worker Treated with Ca-DTPA after Inhalation Intake

The present work models plutonium (Pu) biokinetics in a female former nuclear worker. Her bioassay measurements are available at the US Transuranium and Uranium Registries. The worker was internally exposed to a plutonium-americium mixture via acute inhalation at a nuclear weapons facility. She was medically treated with injections of 1 g Ca-DTPA on days 0, 5, and 14 after the intake. Between days 0 and 20, fecal and urine samples were collected and analyzed for 239 Pu and 241 Am. Subsequently, she was followed up for bioassay monitoring over 14 y, with additional post-treatment urine samples collected and analyzed for 239 Pu. The uniqueness of this dataset is due to the availability of: (1) both early and long-term bioassay data from a female with plutonium intake; (2) data on chelation therapy for a female; and (3) fecal measurement results. Chelation therapy with Ca- and/or Zn-salts of DTPA is known to aid in reducing the internal radiation dose by enhancing the excretion of plutonium and americium from the body. Such enhancement affects plutonium biokinetics in the human body, posing a challenge to the internal dose assessment. The current radiation dose assessment practice is to exclude the data affected by Ca-DTPA from the analysis. The present analysis is the first to explicitly model the chelation-affected bioassay data in a female by using a newly developed chelation model. Thus, the bioassay data collected during and after the Ca-DTPA administrations were used for biokinetic modeling and dose assessment. The Markov Chain Monte Carlo method was used to investigate model parameter uncertainty, based on the bioassay data and assumed prior probability distributions. A χ 2 /nData (number of data points) ≈ 1 was observed in this study, which indicates self-consistency of the data with the model. Results of this study show that the worker’s 239 Pu intake was 12 Bq, with a committed effective dose to the whole-body of 1.2 mSv and a committed equivalent dose to the bone surfaces, liver, and lungs of 37.8, 9.1, and 0.8 mSv, respectively. This study also discusses the worker’s dose reduction due to chelation treatment.

61 RADIATION PROTECTION AND DOSIMETRY↗

DOE OSTI2026

Development of PNNL’s Plutonium Metallography Capability

The goal of this project was to develop plutonium metallography capabilities and establish workflows for characterization at PNNL’s Radiological Processing Facility (RPL). Developing and expanding on this capability opens more opportunities for PNNL to better support science through collaborations with other labs, plants, and sites withing the Department of Energy Complex and through programs within the National Nuclear Security Administration. This project established metallography equipment in an air glovebox, polishing protocols, as well as radiological and facility controls and procedures so that gram quantities of plutonium metal could be analyzed on multiple characterization tools. Data was collected and analyzed on two different delta phase plutonium - Gallium samples and a calciothermically reduced alpha plutonium metal using a combination of optical and electron microscopy, powder X-ray diffraction, and atom probe tomography. This report highlights the metallography capabilities, some preliminary data collections, and plans at PNNL to support plutonium material science.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Characterization Techniques Investigated for Characterization of Anomalous Materials in Plutonium Oxide – 25666

The DOE has adopted a Dilute and Dispose approach for processing surplus plutonium which consists of blending plutonium oxide with adulterants and packaging it in a form which is acceptable for disposal at the Waste Isolation Pilot Plant. The feed material for the downblend process is intended to be pure plutonium oxide powder, however other objects are occasionally encountered within the oxide, particularly with legacy material. Potential technologies which could assist in the resolution of incidents where such anomalies are encountered have been investigated. Resolution of these incidents requires characterization of the anomalous object so that plutonium oxide processing can resume and so that a disposition pathway can be determined for the anomalous material. Technologies including gamma ray spectroscopy, alpha-gamma coincidence, LiDAR volumetric measurements, and surface conductivity measurements were investigated for this purpose, with a focus on systems which can be easily introduced into the processing environment when an anomaly is encountered, then removed from the environment after resolution to avoid impeding normal processing activities. This places an emphasis on small and portable measurement systems and systems that can operate in a high-background, oxide-processing environment. Gamma ray systems investigated include the GR1™a CZT detector and the MicroGe™a germanium detector, with a focus on detecting characteristic gamma rays from Pu-239 and other actinides. A gamma ray and alpha particle coincidence method was investigated with the goal of identifying actinides in the presence of a gamma ray background produced by adjacent plutonium oxide material. Leica™b BLK360 G1 and Keyence™c LJ-X8300 LiDAR systems were investigated for use in conjunction with mass measurements to gain accurate material density values, and a Foerster Sigmatest™d 2.070 was tested to determine surface conductivity. The combination of these properties would allow improved identification and characterization of a wide variety of potential anomalous material.

Munson, Justin M.↗

DOE OSTI2026

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

Criticality safety models for aqueous plutonium chloride systems often contain a significant bias due to assumptions in material compositions. These systems are currently modeled as a fictitious metal-water mixture because little is known about the true solution density. Furthermore, no predictive density tools or capabilities for modeling aqueous plutonium chloride systems are approved for use at Los Alamos National Laboratory. Recent density measurements of this ternary system (PuCl 3 -HCl-H 2 O) have allowed for the development of a more realistic density law, which is applied in this work via an empirical method based in Python. This tool, entitled PuCS (Plutonium Chloride Solution tool) may be used to determine solution density and composition based on the plutonium content, acid content, and temperature for MCNP6 inputs. PuCS has been found to predict density within 2% of experimental data. In conclusion, MCNP6 calculations have found that crediting minimal amounts of free acid (0.5 M) may correspond to a ~12% decrease in peak reactivity in comparison to current modeling methods.

42 ENGINEERING↗

DOE OSTI2025

First principles free energy model with dynamic magnetism for δ -plutonium

We present an ab initio free energy model derived from a fully relativistic density functional theory (DFT) electronic structure with dynamic magnetism for δ -plutonium (face-centered cubic, fcc). The DFT model is extended with orbital-orbital interaction in a parameter free orbital polarization (OP) mechanism consistent with previous modeling of plutonium. Gibbs free energy is built from components associated with the temperature dependence of the electronic structure and the corresponding electronic entropy, lattice vibrations within an anharmonic lattice dynamics model, and dynamical fluctuations of the magnetization density, i.e. magnetic fluctuations. The fluctuation model consists of transverse and longitudinal modes driven by temperature induced excitations of the DFT + OP electronic structure. The ab initio model thus incorporates fluctuating states beyond the electronic ground state. Thanks to the dynamic magnetism, the theory predicts excellent thermodynamic properties and a Gibbs free energy in accord with CALPHAD and semi-empirical modeling developed from the thermodynamic observables. The magnetic fluctuations further explain anomalous behaviors of the thermal expansion in plutonium. Specifically, a thermal expansion for the δ -plutonium system turning from positive to negative at temperatures above room temperature, a tendency for gallium to reduce and remove the negative thermal expansion depending on composition, and a positive thermal expansion for the high temperature ϵ phase.

dynamic↗

DOE OSTI2024

Predicting Radiation-Induced Plutonium Redox Chemistry using Multiscale Modeling Methods

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗