18 Search Results

We report that small-particle analysis is a highly promising emerging forensic tool for analysis of interdicted special nuclear materials. Integration of microstructural, morphological, compositional, and molecular impurity signatures could provide significant advancements in forensic capabilities. We have applied rapid, high-sensitivity, hard X-ray synchrotron chemical imaging to analyze impurity signatures in two differently fabricated fuel pellets from the 5th Collaborative Materials Exercise (CMX5) of the IAEA Nuclear Forensics International Working Group. The spatial distributions, chemical compositions, and morphological and molecular characteristics of impurities were evaluated using X-ray absorption near-edge structure (XANES) and X-ray fluorescence chemical imaging to discover principal impurities, theirmore » granularity, particle sizes, modes of occurrence (distinct grains vs incorporation in the UO₂ lattice), and sources and mechanisms of incorporation. Differences in UO_2+x stoichiometry were detected at the microscale in nominally identical UO₂ ceramics (CMX5-A and CMX5-B), implying the presence of multiple UO₂ host phases with characteristic microstructures and feedstock compositions. Al, Fe, Ni, W, and Zr impurities and integrated impurity signature analysis identified distinctly different pellet synthesis and processing methods. For example, two different Al, W, and Zr populations in the CMX5-B sample indicated a more complex processing history than the CMX5-A sample. K-edge XANES measurements reveal both metallic and oxide forms of Fe and Ni but with different proportions between each sample. Altogether, these observations suggest multiple sources of impurities, including fabrication (e.g., force-sieving) and feedstock (mineral oxides). This study demonstrates the potential of synchrotron techniques to integrate different signatures across length scales (angstrom to micrometer) to detect and differentiate between contrasting UO₂ fuel fabrication techniques.« less

The study of nuclear forensics harkens back to the Manhattan Project-era, when scientists first started to analyze the debris from the 1945 Trinity test. Political turmoil stemming from the Cold War and the rehabilitation of Germany following WWII has led to new challenges in international security involving nuclear proliferation. Nuclear materials have, on occasion, been lost, misplaced, or stolen from former Soviet countries, and illicit materials have been interdicted all over the world. The National Technical Nuclear Forensics Center (NTNFC) was established in 2006, and has been at the forefront of drive to advance nuclear forensic capabilities in the Unitedmore » States. The ultimate goal of nuclear forensics is to examine nuclear and other radioactive materials using analytical techniques to determine origin and history of the material, particularly in the context of law enforcement investigations. Nuclear forensics can be divided into two parts: predetonation and post-detonation. Pre-detonation forensics, as the name implies, is the investigation of a nuclear material or weapon that has not been detonated or involved in an explosion, whereas postdetonation forensics is the study of activation or fission products in debris or the environment following the use of a nuclear or radiological dispersal device (RDD). Both parts require a number of analytical chemical and radiochemical techniques to determine identification of the material. Many advancements in analytical techniques, including rapidity, sample size, and forensic signatures have been made in recent years. The analytical methods that can be used in a nuclear forensic investigation, such as mass spectrometry and gamma spectroscopy, have been described in detail in previous reviews, including Straub et.al, and will not be explained here. This review will discuss recent publications (from 2016 to present) describing advancements of techniques such as radiochronometry, morphology, development of novel reference materials, and inter-laboratory collaborations for both pre- and post-detonation nuclear forensics.« less

A major goal in pre-detonation nuclear forensics is to infer the processing conditions and/or facility type that produced radiological material. This review paper focuses on analyses of particle size, shape, texture (“morphology”) signatures that could provide information on the provenance of interdicted materials. For example, uranium ore concentrates (UOC or yellowcake) include ammonium diuranate (ADU), ammonium uranyl carbonate (AUC), sodium diuranate (SDU), magnesium diuranate (MDU), and others, each prepared using different salts to precipitate U from solution. Once precipitated, UOCs are often dried and calcined to remove adsorbed water. The products can be allowed to react further, forming uranium oxidesmore » UO3, U3O8, or UO2 powders, whose surface morphology can be indicative of precipitation and/or calcination conditions used in their production. This review paper describes statistical issues and approaches in using quantitative analyses of measurements such as particle size and shape to infer production conditions. Statistical topics include multivariate t tests (Hotelling’s T²), design of experiments, and several machine learning (ML) options including decision trees, learning vector quantization neural networks, mixture discriminant analysis, and approximate Bayesian computation (ABC). ABC is emphasized as an attractive option to include the effects of model uncertainty in the selected and fitted forward model used for inferring processing conditions.« less

The speciation of NO₂, NO, and N₂O gases formed from the dissolution of copper in nitric acid is measured and characterized using Fourier-transform infrared (FTIR) spectroscopy. This study describes analysis of the gas phase species formed and ingrowths of their concentrations as a function of time. Acid concentrations range from 14 to 4 M and the NO₂, NO, and N₂O are analyzed using FTIR between 1585 and 2209 wavenumbers. The concentrations of the gases range from 0 to 230 ppm and change over time and as a function of acid concentration.

Changes in chemical speciation of uranium oxides following storage under varied conditions of temperature and relative humidity are valuable for characterizing material provenance. In this study, subsamples of high purity α-UO₃ were stored under four sets of controlled conditions of temperature and relative humidity over several years, and then measured periodically for chemical speciation. Powder X-ray diffraction (XRD) analysis and extended X-ray absorption fine structure spectroscopy confirm hydration of α-UO₃ to a schoepite-like end product following storage under each of the varied storage conditions, but the species formed during exposure to the lower relative humidity and lower temperature condition followsmore » different trends from those formed under the other three storage conditions (high relative humidity with high or low temperatures, and low relative humidity with a high temperature). Thermogravimetry coupled with XRD analysis was carried out to distinguish desorption pathways of water from the hydrated end products. Density functional theory calculations discern changes in the structure of α-UO₃ following incorporation of 1, 2 or 3 H₂O molecules or 1, 2 or 3 OH groups into the orthorhombic lattice, revealing differences in lattice constants, U–O bond lengths, and U–U distances. The collective results from this analysis are in contrast to analogous studies that report that U₃O₈ is oxidized and hydrated in air during storage under high relative humidity conditions.« less

The speciation of gases formed in the vapor phase above HNO₃-H₂O mixtures at room temperature is measured and characterized using Fourier-transform infrared (FTIR) spectroscopy. Although studies of speciation of compounds have been performed in the solution phase, in this study we focus solely on the gas phase species formed over HNO₃-H₂O mixtures and their concentrations as a function of time. The nitric acid concentration in the experiments range from 14 to 4 M. The NO₂, NO, and N₂O (collectively known at NOx) gases are measured by FTIR at 1585, 1850, and 2208 wavenumbers, respectively. The concentrations of these NOx speciesmore » ranges from 0 to 3 ppm and change over time as a function of acid concentration. Two purities of commercially available HNO₃ are used to prepare the HNO₃-H₂O mixtures. An analysis of thermodynamic data shows that the formation of NOx gases without the presence of a catalyst are thermodynamically favorable.« less

Typical fission product formation experiments utilize metal or oxide target materials that must be dissolved prior to product separation. In this study, we report here a novel study using metal–organic frameworks for recovery of fission products into acidic media. We further show that the frameworks are largely preserved, such that this bulk target material could be retained for additional irradiations or characterizations. Through this approach, fission products can be separated from the actinide-based metal–organic framework using 0.01 M HNO₃ without the need to dissolve the framework itself, reducing the amount of acidic waste. Extraction yields of four frameworks with varyingmore » pore sizes are compared. In conclusion, the results suggest that it may be possible to use porous frameworks as target materials for the extraction of select fission products.« less

Here, we report here an initial isolation study based upon the use of small uranium oxide particles dispersed in a soluble salt matrix to evaluate the relative recovery of fission products into acidic media. We further show that the macrostructures of the uranium microparticles are largely preserved, such that the bulk target material could be retained for additional irradiations or characterizations. Through this approach, fission products can be separated from the actinide-based target using low molarities of acid without the need to dissolve the actinide itself, reducing the amount of acidic waste. Extraction yields using two molarities of HCl andmore » HNO₃ are compared.« less

The primary oxide of plutonium, PuO₂, is a complex material due to ongoing change in lattice structure resulting from radioactive alpha decay. In addition, the element plutonium is complex, existing in various allotropes, which can influence formation of oxides due to different nucleation and growth mechanisms. The juxtaposition of these unique properties, along with formation conditions of the initial oxide, makes for PuO₂ materials with a wide variety of local and bulk experimental signatures. This work measures these signatures with X-ray diffraction and Raman spectroscopy from five different oxide materials, and relates these signatures to specific PuO₂ production and agingmore » routes. Furthermore this information is of potential use in nuclear fuels processing and production, nuclear non-proliferation, forensics analyses, and interplanetary power sources.« less

We are developing an imaging capability (“Hyperspectral X-ray Imaging”) for mapping chemical information (molecular formula, phase, oxidation state, hydration) that is based on ultra-high-resolution X-ray emission spectroscopy with large transition-edge sensor microcalorimeter arrays in the scanning electron microscope. By combining microcalorimeter arrays with hundreds of pixels, high-bandwidth microwave frequency-division multiplexing, and fast digital electronics for near real-time data processing, our goal is to enable measurements using laboratory-scale instrumentation rather than synchrotron beamlines. Our application focus here is on mapping the chemical form of uranium compounds on the nanoscale. Furthermore, we will present our approach to developing the Hyperspectral X-ray Imagingmore » capability, progress toward a 128-pixel microwave multiplexed X-ray fluorescence instrument at LANL, and the path to high-throughput nanoscale chemical mapping.« less